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The basis of adsorption of water pollutants by coal 1977

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THE BASIS OF ADSORPTION OF WATER POLLUTANTS BY COAL BY SAMIA MASSOUD MOHAMED^(FADL) B.Sc. Chem. Eng., Univ. of Alexandria, Egypt, 1965 M.Sc. Chem. Eng.., Univ. of Alexandria, Egypt, 1969 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY i n THE FACULTY OF GRADUATE STUDIES I n t e r d i s c i p l i n a r y Studies: Department of Bio-Resource Engineering Department of Chemical Engineering Department of Mineral Engineering WE ACCEPT THIS THESIS AS CONFORMING TO THE REQUIRED STANDARD THE UNIVERSITY OF BRITISH COLUMBIA OCTOBER, 1977. Samia Maasoud Mohamed (Fadl), 1977 In presenting th i s thes is in pa r t i a l fu l f i lment of the requirements for an advanced degree at the Univers i ty of B r i t i s h Columbia, I agree that the L ibrary sha l l make it f ree ly ava i l ab le for reference and study. I fur ther agree that permission for extensive copying of th is thesis for scho lar ly purposes may be granted by the Head of my Department or by his representat ives. It is understood that copying or pub l i ca t ion o f th is thes is fo r f i nanc ia l gain sha l l not be allowed without my wr i t ten permission. Department of The Univers i ty of B r i t i s h Columbia 2075 Wesbrook Place Vancouver, Canada V6T 1W5 Date i ABSTRACT An approach for studying the basis of adsorption of water pollutants, by coal, i s presented. Oxidized and non-oxidized coal samples, mined from the Hat Creek deposits of B r i t i s h Columbia, were evaluated. During the f i r s t phase of the research,electron microanalysis, and macrochemical techniques were used to investigate the surface properties and the pore structure of the Hat Creek coal in comparison with activated carbon. The second phase of the study was focussed on the extensive evaluation of the adsorption capacity and e f f i c i e n c y of the coal to remove some dissolved components from synthetic wastewaters using both batch and continuous leaching tests.. Heavy metals, dissolved organics, n i t r a t e s , phosphates, ammonia, phenol and cyanide were tested either i n d i v i d u a l l y or mixed in some combinations. The s e l e c t i v i t y exhibited by coal towards mixed metals i s also discussed. Adsorption isotherms and break through curves were plotted and i n t e r - preted for each material. A comparative study using other adsorbents such as activated carbon, s o i l and construction sand was also conducted. The effect of some factors i n influencing the adsorption process were s t a t i s t i c a l l y analyzed. i i During the t h i r d phase of the study two mechanisms for the adsorption of heavy metal ions and dissolved organics were investigated. Spectroscopic, electron microscopic, and chemical methods were used to confirm that metal ions are adsorbed by coal through a chemisorption type of mechanism where the adsorbed metal ions interact with the available acid groups (mostly carb.oxylic COOH and phenolic -OH) to form metal complexes. In the case of removal of dissolved organics by coal, there was a combining e f f e c t of physical adsorption and b i o l o g i c a l oxidation. A material balance on the coal bed systems was u t i l i z e d to estimate the bio-oxidizable f r a c t i o n of the organic substrate. The l a s t phase of th i s work i s concerned with some design applications using the actual flow from municipal and i n d u s t r i a l sewage. Data from long term experiments on larger columns were u t i l i z e d to predict the size and performance of a coal bed to treat large quantities of flow. It appears from the research conducted that low rank coals w i l l be a s a t i s f a c t o r y material for the removal of pollutants from wastewaters. i i i TABLE OF CONTENTS PAGE ABSTRACT . i TABLE OF CONTENTS i i i LIST OF TABLES . . v i LIST OF FIGURES . v i i i ACKNOWLEDGEMENTS , x i i NOMENCLATURE x i v I. INTRODUCTION 1 1 . 1 J u s t i f i c a t i o n 1 1 . 2 Objectives • -3 I I . LITERATURE REVIEW. A A. General on Coal 4 1 . B a s i c concepts and d e f i n i t i o n s . . . . 4 2 . I m p u r i t i e s i n c o a l 5 3 . D e t e r i o r a t i o n and weathering during storage . . . . J6 4 . Surface area 7 5 . Porosity" of coals • • • H 6 . C o l l o i d a l s t r u c t u r e 1 3 7 . Pe rme ab i 1 i ty • • • • • .. • J- 4 8 . I n f r a - r e d s p e c t r a 1 5 9 . Chemical s t r u c t u r e -'\ • . .- 1 7 1 0 . Adsorption on c o a l surface 2 1 1 1 . Suggested adsorption mechanisms 2 6 1 2 . Adsorption of metals on a c t i v a t e d carbon . . . . . 2 8 B. Hat Creek Coals . . . • • • • • • • • • • • • • • - 3 0 I I I . EXPERIMENTAL MATERIALS 36 IV. PROPERTIES OF HAT CREEK COALS . 4 3 1 . M a t e r i a l s . 4 3 2 . Methods 4 3 3 . Results and d i s c u s s i o n . . .. . . . 4 8 i v PAGE TV. PROPERTIES OF HAT CREEK COALS (Continued) 3.1 Chemical properties 48 3.2 Contaminants in the coal 50 3.3 Surface properties 52 3.3.1 General features of the surface . . . 52 3.3.2 Infra-red spectra .54 3.3.3 Surface area .62 3.3.4 Pore size d i s t r i b u t i o n . 66 3.3.5 Permeability 68 3.3.6 Iodine number 69 V. SORPTIVE CHARACTERISTICS 71 1. Design of experiments 73 2. Description of the sorptive tests 75 3. A n a l y t i c a l methods 80 4. Results and discussion. 83 4.1 Adsorption of heavy metals . . . . . . . . . 84 4.1.1 Batch tests . . . . . . . . . . . . . 84 4.1.2 Comparison with activated carbon . . . 86 4.1.3 Variables influencing adsorption . . . 89 4.1.4 S t a t i s t i c a l analyses 99 4.1.5 Column adsorption tests 100 4.1.6 Long term column adsorption. . . . . 103 4.1.7 S e l e c t i v i t y i n adsorption of mixed metals 105 4.2 Adsorption of dissolved organics. . . . . . 108 4.2.1 Contact process . . .108 4.2.2 Column process I l l 4.2.3 Mixed organics and heavy metals . . .118 4.2.4 Comparison of coal with sand . . . . 118 4.3 Adsorption of phosphates 120 4.4 Adsorption of n i t r a t e s 127 4.5 Adsorption of ammonia 131 4.6 Adsorption of phenol 137 4.7 Adsorption of cyanide . 139 VI. MECHANISM STUDIES . . . . . . . . . .143 A. Mechanism of adsorption of heavy metals by coal. 143 1. Materials 145 2. Methods 145 3. Results and discussion 152 3.1 Electron Microscopic. Studies 152 3.2 Infra-red spectra 162 V PAGE VI. MECHANISM STUDIES (Continued) 3.2.1 Study the proximity of carboxyl groups 170 3.3 Cation exchange capacity . 172 3.4 Molar r a t i o of reacted lead and released hydrogen 175 3.5 Acid groups 177 3.5.1 Carboxyl groups 178 3.5.2 Phenolic hydroxyls . 180 3.6 Lead exchanged with barium or calcium during acid group tests 183 4. Suggested mechanism for adsorption of lead by coal 184 B. Mechanism of adsorption of dissolved organics by coal . . 1§1 1. Materials 191 2. Design of experiments . • . -192 3. Results and discussion- . 194 3.1 Regeneration of coal by backwashing . . . . 196 3.2 Suggested mechanism 201 VII- APPLICATIONS IN SEWAGE TREATMENT . 20 5 1. Materials .206 2. Methods . 206 3. Results and discussion 209 3.1 Municipal sewage . . . . . . .209 3.1.1 Batch tests 209 3.1.2 Column tests . . . . . . ." . . . . .210 3.1.3 Design applications 212 3.1.3.1 To remove lead ions from Iona sewage 212 3.1.3.2 To remove dissolved organics from Iona sewage 216 3.2 Industrial sewage (refinery waste effluent). 219 3.2.1 Batch tests -220 3.2.2 Column tests 222 3.2.3 Design application to remove phenol, ammonia and cyanide. . . . 22 3 VIII. SUMMARY AND CONCLUSIONS • • • • • 226 IX. RECOMMENDATIONS FOR FUTURE RESEARCH • • 229 REFERENCES 232 APPENDICES . . . . . .. 242 LIST OF TABLES PAGE Nitrogen and carbon dioxide surface areas 10 Band positions i n the in f r a - r e d spectra of coals and the i r assignments 16a Comparison of adsorbents for n i c k e l . .26 Mean values of Hat Creek coal 33 ASTM c l a s s i f i c a t i o n of coals by rank 33a Levels of metals in the coal ash . .41 Chemical analysis of the Hat Creek coal 49 Leaching of ammonia and n i t r a t e from the co a l . . .51 Leaching of heavy metals from the coal 53 Sp e c i f i c extinction c o e f f i c i e n t s "K" of main in f r a - r e d bands of the coal- 60 BET surface area, micropore volumes and pore diameters . .• 64 Degree of permeability of oxidized surface coal 68 Comparison of iodine number of the coal with other adsorbents. . . 69 Synthetic wastewaters used in the standard adsorption tests . . . .72 Public Health Drinking Water Quality Standards. . 75 Comparison of the adsorptive capacities of the coal for six heavy metals . 37 E f f e c t of the metal ion concentration on the adsorption .94 Comparison between adsorption e f f i c i e n c i e s of di f f e r e n t metals Long term adsorption of mixed metals m c v i i . TABLE PAGE 19. Comparison between coal and activated carbon in removal of dissolved organics I l l 20. Removal of dissolved organics mixed with lead ions through coal . . . 119 21. Comparison between coal and construction sand for removal of dissolved organics- . 121 22. Eff e c t of percentage coal on the adsorption of phosphates 125 23. Comparison between coal and Abbotsford s o i l for removal of phosphates 128 24a. Contact process for n i t r a t e removal . 130 24b. Column test for removal of n i t r a t e 132 25a. Comparison between coal and activated carbon for ammonia removal 133 25b. Comparison between oxidized surface coal and non-oxidized core coal for ammonia removal . . . .134 25c. Adsorption of ammonia on water washed coal- • . . 136 25d. Column test for removal of ammonia 137 26a. Batch test for removal of phenol . . . . . . . . .138 26b. Column test for removal of phenol. 140 27a. Batch test for removal of cyanide 141 27b. Column test for removal of cyanide. 142 28. Exchangeable cations and t o t a l exchange capacity of coal and activated carbon . .173 29. Molar ration of adsorbed lead ions and exchangeable hydrogen ions 176 30a. Mean values of carboxyl groups in coal and activated carbon - e f f e c t of lead adsorption- . . 179 30b. Mean values of phenolic hydroxyl groups in coal and activated carbon - eff e c t of lead adsorption .181 30c. Released lead ions during the t o t a l a c i d i t y and carboxyl group measurements 183a 31. Material balance on the coal bed system for removal of dissolved organics -195 v i i i LIST OF FIGURES FIGURE PAGE 1. Ash c a l o r i f i c value regression of Hat Creek Coal 32 2. Hat Creek location plan .37 3. Cross section view showing the coal seams 37 4. Index plan for the Hat Creek deposits . . . . . . .38 5. Sampling location plan 39 6. Low power l i g h t microscope images >of Hat Creek, coal .55 7a. Scanned electron micrographs of polished coal surface 56 . 7b. ] X-ray energy spectrum of Hat Creek coals 57 8. Infra-red spectra of Hat Creek coals . . . . . . .58 9. Infra-red spectra of activated carbon. . . . . . .63 10. Pore size d i s t r i b u t i o n curves for the coal and activated carbon. . .67 11. Schematic diagram of the continuous leaching process 76 12. A§B Adsorption isotherm lines of removal of heavy metals by coal 85a^b 13. Comparison between the coal and the activated carbon for adsorption of lead. 88 14. E f f e c t of contact time on adsorption of lead. . .90 15a. Ef f e c t of coal dosage on adsorption of copper. . .92 15b. E f f e c t of coal dosage on removal e f f i c i e n c y of copper 93 16a. E f f e c t of solution concentration on adsorption of mercury. 96 16b. E f f e c t of solution concentration on adsorption of copper 96 i x . FIGURE PAGE 17a. E f f e c t of coal p a r t i c l e size on adsorption of lead . . . . . . . . . . . 98 17b. E f f e c t of coal p a r t i c l e size on adsorption of mercury .98 18. Column test for adsorption of mercury. . . . . . . .101 19. Long term column adsorption of lead 104 20. S e l e c t i v i t y in adsorption of mixed metals by coal .107 21a. Adsorption isotherms for removal of BOD^ with coal and activated carbon. 109 21b. Adsorption isotherms for removal of COD with coal and activated carbon. . . 110 22a. Aerobic removal of dissolved organics . . . . . . . 112 22b. E f f i c i e n c y of removal of B0D5 and COD by adsorption through coal 113 2 3a. Cumulative removal of BOD^ by coal. 115 2 3b. Cumulative removal of COD by coal 116 23c. Relationship between BOD5 and COD . . . . . . . . . 117 24. Comparison of e f f i c i e n c y of removal of dissolved organics by coal and sand. 122 25. Adsorption isotherm for phosphate removal 124 26. Cumulative removal of phosphate by coal 126 27. Break through curves for coal and s o i l for adsorption of phosphates 129 2 8a. X-ray images showing the d i s t r i b u t i o n of adsorbed lead on the coal surface 153 28b. X-ray images for tracing the pattern of lead and carbon d i s t r i b u t i o n 154 X FIGURE PAGE 29. Elemental mapping across fractured p a r t i c l e of oxidized coal a f t e r lead adsorption. . . . . .156 30a. Elemental mapping of layered p a r t i c l e of non-oxidized coal after lead adsorption 157 30b. Elemental mapping of fractured p a r t i c l e of non-oxidized coal a f t e r lead adsorption. - . . . 158 • 31. Comparison between the elemental mapping across p a r t i c l e s of oxidized and non-oxidized. • 159 coal 32a. Elemental mapping for areas of two p a r t i c l e s of activated carbon- ' - 160 32b. Adsorption of lead on the activated carbon. . • -161 33(a-d) Infra-red spectra of coal samples showing the ;changes occurring upon adsorption of metal ions 33a. Water washed oxidized surface coal 163 33b. Acid washed oxidized surface coal • . . 164 33c. Water washed non-oxidized core c o a l . . . . . . . 165 33d. Acid washed non-oxidized core coal . . . . . . . 166 34a. Cumulative removal of TOC by spent coal a f t e r backwashing 19 7 34b. Cumulative removal of COD by spent c o a l . . . . . 198: 34c. Cumulative removal of.BODj. by spent coal 199 34d. E f f e c t of inoculation on the removal e f f i c i e n c y of organic carbon by c o a l . - . 2 0 2 35. Schematic inte r p r e t a t i o n of the mode of the mechanism of removal of dissolved organics by. • 20 3 coal , 36. E f f i c i e n c y of removal of pollutants from Iona sewage by coal using contact process- 213 3.7. E f f i c i e n c y of removal of pollutants from Iona sewage by coal using column adsorption process- ...213 x i . FIGURE PAGE 38. Break through curve at 30 cm l e v e l for removal of lead ions by coal 2 1 4 39. Column tests for removal of BOD,, by coal. . . ... . 2 2 4 x i i . ACKNOWLEDGEMENTS During the course of t h i s extensive i n t e r d i s c i p l i n a r y study, I wish to g r a t e f u l l y thank Professor T.L. Coulthard, Department of Bio-Resource Engineering for serving as Supervisor for th i s work and for obtaining the f i n a n c i a l assistance throughout the period of the research program. Also, I am deeply indebted to a l l members of my committee: Dr. J . Leja, Department of Mineral Engineering, who acted as research advisor for the surface chemistry study; Dr. G.W. Poling, Department of Mineral Engineering; Dr. J.W. Zahradnik, Chairman of the Department of Bio-Resource Engineering; and Dr. K.L. Pinder, Department of Chemical Engineering. The he l p f u l advice and constructive c r i t i c i s m offered by these s c i e n t i s t s , during a number of stimulating discussions of the project, as well as t h e i r encouragement, was invaluable. Of the many people who also helped i n various ways, I am also grateful to those who conducted the electron microanalysis and Miss L. Robinson for computer programming. Sincere thanks are due to Dr. L.T. Jory of Dolmage Campbell Associates and to C. Jones of Interprovincial Patents Ltd. for the supply of Hat Creek coal samples u t i l i z e d i n the experiments. The assistance of Mrs. E.M. Stewart i n typing the thesis i s sincerely acknowledged. Sincere thanks are due to Mr. A.F. Fadl, the author's husband, for standing by her with encouragement and understanding throughout the e f f o r t . My sincere thanks also to Dr. and Mrs. Micko for conducting the chemical analyses. Financial support from the University of B r i t i s h Columbia, the B.C. Department of Lands, Forests and Water Resources and the B.C. Petroleum Corporation are very sincerely acknowledged. xiv NOMENCLATURE AC Activated carbon AEI Absorption Electron Image A.W.A. Acid washed activated carbon A.W.C. Acid washed core coal A.W.S. Acid washed surface coal BOD Biochemical oxygen demand, mg/1 C.C. Core coal (non-oxidized) CEC Cation exchange capacity COD Chemical oxygen demand, mg/1 gpm/ft Gallons per minute per square foot of surface area- 6.79 X 10" 5 L/sec/cm 2 m.eq/gm M i l l i e q u i v a l e n t per gram mg/1 Milligrams per l i t e r MGD M i l l i o n gallons per day ppm Parts per m i l l i o n = mg/1 NĤ -N Ammonia nitrogen NÔ -N Nitrate nitrogen 0-PO^-P Ortho phosphate phosphorus S.C. Surface coal TIC Total inorganic carbon . T-N Total nitrogen T.K.N. Total Kjeldahl nitrogen TOC Total organic carbon T-P Total phosphorus •% w/w Percentage weight by weight W.W.A. Water washed activated carbon W.W.C. Water washed core coal W.W.S. Water washed surface coal I. INTRODUCTION 1.1 J u s t i f i c a t i o n The increasing population, i n d u s t r i a l growth and increasing water use has already created p o l l u t i o n problems in many locations in the world. During the past decade an increasing i n t e r e s t and concern has developed with regard to our environment. The detrimental ef f e c t of releasing wastes to s o i l or water "sinks" i s only beginning to be understood, although that practice has been used for centuries. Recently, the d i r e c t i o n of concern i s changing from the general p o l l u t i o n aspects to more s p e c i f i c problems such as the removal of organics, phosphates and n i t r a t e s from wastewaters. In p a r t i c u l a r , the problem of e f f i c i e n t heavy metal removal becomes important, since heavy metals have a high pote n t i a l t o x i c i t y to various b i o l o g i c a l organisms at extremely low concentrations. Lead, zinc and copper represent the greatest "heavy" metal loading in surface waters (Hendren, 1973; Evans, 1973 and Sarter, 1972). Therefore, advanced wastewater treatment i s necessary to remove pollutants which are not adequately removed by conventional, secondary treatment processes. Activated carbon is now extensively used in t e r t i a r y treatment processes and i t s use has become firmly established as a p r a c t i c a l , r e l i a b l e new tool which has many uses in preserving water q u a l i t y , and meeting discharge requirements (Linstedt and O'Connor, 1971). Because of the expensive cost of this process, a keen interest in the creation of a new, less expensive method for t e r t i a r y treatment has developed rapidly during the past few years. For many years, crushed anthracite coal has been used as a mechanical f i l t e r i n g medium for water supplies (Turner, 1943). Recently, a renewed interest has developed for the use of low fuel value coal as a material for water p u r i f i c a t i o n (Office of coal research, Report No. 55, 1971). However, the subsequent use of t h i s material as an energy source may require appropriate pretreatment to remove toxic matters. Locally, the i n t e r e s t has been directed towards the use of low grade coals from B r i t i s h Columbia i n wastewater p u r i f i c a t i o n . Some laboratory experiments indicated that some of the B.C. coals do possess adsorptive c h a r a c t e r i s t i c s (Coulthard, 1974; Riaz, 1974 and Hendren, 1974). Considerable interest has been generated i n the use of Hat Creek coal for water p u r i f i c a t i o n since i t i s available in a large and economical reserve i n B r i t i s h Columbia. Because very l i t t l e i s known about the surface chemistry and porous structure of t h i s coal and the cause of i t s effectiveness in the adsorption of metal ions and dissolved organic constituents, the a b i l i t y of this coal as an adsorbent material for use in water p u r i f i c a t i o n i s s t i l l the subject of much discussion and many claims. Accordingly, there i s a need for more investigation with emphasis on surface structure of the Hat Creek coal, also, on the study of the mechanism involved i n the adsorption of heavy metals and dissolved organics. Then, there is a d e f i n i t e need to conduct larger p i l o t experiments to treat actual sewage effluents in order to reinforce the encouraging results obtained from the laboratory experimentation. 1.2 Obj ectives 1) To evaluate the surface properties and porous structure of Hat Creek coal in comparison to activated carbon. 2) To determine the sorptive properties of the coal, through batch and continuous adsorption t e s t s , to remove dissolved constituents from water including metal ions, dissolved organics, phosphates, n i t r a t e s , ammonia, phenol and cyanide. 3) To evaluate the effect of factors influencing the adsorption process. - 4) To investigate the mechanisms involved i n the adsorption of metal ions. 5) To investigate the mechanism involved in the adsorption of dissolved organics. 6) To predict the size and performance of the larger coal beds required to treat actual wastewater sewage discharges. 4. II. LITERATURE REVIEW A. General on Coal 1. Basic concept and d e f i n i t i o n s Coal i s not a uniform substance but rather a heterogeneous mixture of organic substances and mineral matter (Leonard and Mitchel, 1968). As coal i s derived by meta- morphism of plant debris, the terms "mineralized plants" and "mineral f u e l " have been widely used to define coal (Spackman, 1966). However, coal i s not a mineral of constant composition, but a mixture of organic and inorganic materials representing matter of d i f f e r e n t origins (Van Krevelen, 1961). Therefore, the composition and physical properties of coals vary among d i f f e r e n t deposits and even within single seams in some mines. Coal i s a compact s t r a t i f i e d mass of combustible metamorphosed plant remains (Spackman, 1966). The d i v e r s i t y of the o r i g i n a l plant materials and the degree of metamorphism or c o a l i f i c a t i o n that has affected these materials are the two major reasons for the variety of the physical components in coal. Most coals are unstable, or more c o r r e c t l y , meta- stable s o l i d s , the most mature coals such as anthracite are the most stable. Coal i s used commonly as a f u e l , a source of carbon for the metallurgical industry and, to a lesser extent, as a source of organic chemicals (Lowry, 1963). 5. Methods have therefore been devised to c l a s s i f y coals accor- ding to properties of greatest importance to these industries and to the coal producers. The most important are rank (Table 4b) , type and analysis for certain chemical components. These properties are described in d e t a i l s i n Chapter IV. For coal to be used in sewage treatment the f i r s t requirement i s that i t retains i t s physical i n t e g r i t y when wet. Most coals do so with the exception of l i g n i t e and subbituminous which have been found to disintegrate. The next variable of importance i s the a b i l i t y of a given coal to adsorb dissolved species from solutions. Therefore, this l i t e r a t u r e review is focussed on discussing the research work conducted on the adsorptive properties of coal and other related c h a r a c t e r i s t i c s such as surface properties, pore structure, chemical structure and s i m i l a r factors. 2. Impurities in Coal (Leonard, 1968) These are c l a s s i f i e d into: a) Those components that form ash-. b) Those that contribute sulphur to a i r p o l l u t i o n . Both of these impurities may be subdivided into two types. i ) Impurities that are s t r u c t u r a l l y a part of coal, intimately mixed with i t , and are named "True" or "Inherent" impurities. i i ) Impurities that can be eliminated by appropriate cleaning methods. 2.1 Minerals in coal (Leonard, 1968) The p r i n c i p a l mineral groups in coal are: shale, kaolin, s u l f i d e s , carbonates, chlorides and numerous forms of s i l i c a t e s . 2.2 Elements in coal (Leonard, 1968) The following table gives the approximate ranges of the major oxides present in the ash of bituminous coals of the United States. Constituent Percentage S i l i c a (Si0 2) 20-60 A1 20 3 10-35 ' F e 2 0 3 - 5-35 CaO 1-20 MgO 0.3-4 T i 0 2 0.5-2.5 A l k a l i s (Na 20 + K 20) 1-4 S0 3 0.1-12 In addition, minor elements can also be present such as L i , Rb, Sr, Ba, Ag, As, B, Be, B i , Sb, Co, Cr, Cu, Ga, rig, Ge, Zn, P, N, Mn, Mo, U, V, W, Zr. 3. Deterioration or Weathering During Storage 3.1 Dehydration and "slacking". Berkowitz (1971) reported that dehydration of low rank coal with 20-30% moisture i s accompanied by extensive and p a r t i a l l y i r r e v e r s i b l e volume shrinkage, after that the coal loses i t s cohesion and disintegrates into small pieces. This behavior i s c a l l e d "slacking". Sub-bituminous and l i g n i t e coals undergo "slacking" during storage while higher rank coals do not. 3.2 Oxidative deterioration Oxidation takes place through chemisorption of oxygen at the exposed surface followed by the formation of ether (-0-), phenolic hydroxyl (-0H) and carboxyl (-COOH) groups on the surface layers. Phenolic hydroxyl and carboxyl groups render the coal more a c i d i c and increase the contents of a l k a l i - s o l u b l e "humic acids" (Berkowitz, 1971). 4. Surface Area . Many years of research have been spent in the testing of numerous adsorbates at various temperatures. The experimental res u l t s have then been interpreted i n terms of t h e o r e t i c a l l y derived isotherms. These studies have revealed an extreme complexity of the structure of coal from both chemical and physical viewpoints. The t h e o r e t i c a l BET adsorption equation, as developed by Brunauer, Emmett and T e l l e r (1938), i s extensively used for the measurement of s p e c i f i c surface areas by the adsorption of nitrogen gas at a temperature of 77°K. Dubinin (1966) and Spencer (1966) questioned the use of the BET equation for microporous materials, 8. whenever micropore f i l l i n g by an adsorbate occurs before the monolayer formation. Consequently, Dubinin (1966) modified the adsorption p o t e n t i a l theory, proposed by Polanyi in 1932, and developed the Dubinin-Polanyi (DP) equation, from which the micropore volume and a function of micropore size can be estimated. Marsh et a l . (1965) tested extensively the application of the DP equation in adsorption of carbon dioxide at room temperature on coals and proved that i t i s s a t i s f a c t o r y . Walker (1970) compared the surface areas of coal calculated from the carbon dioxide adsorption isotherms at 298°K using BET and DP equations. He found no appreciable differences between the two values and concluded that the use of the DP equation i s more advantageous and simpler. In excellent reviews, Marsh (1965) and Spencer (1967) discussed the problem of determining the surface areas of coals which has been, up u n t i l now, the subject of considerable controversy. Both pointed out that the area calculated from nitrogen at 77°K using the BET equation i s associated with the external area of the p a r t i c l e plus the area contained i n pores of diameter greater than o 5.0 A, while the area calculated from carbon dioxide at a higher temperature of 298°K, also using the BET equation, 9. is considered to be a closer approximation to the t o t a l surface area of coals. The l a t t e r was also confirmed by Walker (1965). Any method applicable at ordinary temperatures indicates larger s p e c i f i c i n t e r n a l areas. In bituminous coals, these areas are found to be i n the 2 range of 30 to 100 m /gm situated almost e n t i r e l y i n the o u l t r a f i n e c a p i l l a r i e s with widths below 40 A (Lowry, 1963). These surface areas can be measured only by methods using temperatures not too far below room temperature; the exact temperature depends on the nature of the gas used. Measurements at l i q u i d a i r temperatures, as used for nitrogen adsorption, relate only to external surfaces of p a r t i c l e s and those of macro c a p i l l a r i e s and therefore y i e l d values too low by a factor of up to 100; this i s explained e a r l i e r by Maggs (1952) as an activated d i f f u s i o n into the micro c a p i l l a r y system becoming exceedingly slow at low temperatures. Most recently, Gan and Nandi e_t al_. (1972) showed that the surface area calculated from carbon dioxide adsorption at 298°K are consistently higher than those calculated from nitrogen at 77°K. The comparison i s shown i n Table 1. TABLE 1. NITROGEN AND CARBON DIOXIDE AREAS OF AMERICAN COALS Coal Sampling Carbon Surface Area (m2/g, mm Cb)** Location (% daf)* Nitrogen Carbon Dioxide Pa 91. 7 Pa 90. ,8 W. Va. 90 . ,5 Pa 89 . , 5 Alabama 89. , 3 Alabama 88. ,3 Kentucky 83. .8 Pa 83. .4 Indiana 82. .7 Washington 81. .6 Indiana 81. . 3 Kentucky 81. .3 I l l i n o i s 80 . 0 Indiana 79. .9 Kentucky 78. .8 I l l i n o i s 78. . 7 I l l i n o i s 77. . 2 Pa . 76. .5 I l l i n o i s 75 . 9 I l l i n o i s * 75. .5 Wyoming 75. .0 Texas 74. . 3 Wyoming 72, .0 Texas 71, .7 Montana 71. .5 N. Dakota 71. .2 N. Dakota 63, . 3 6.1 426 7.0 408 < 1.0 231 < 1.0 253 < 1.0 197 < 1.0 214 < 1.0 213 < 1.0 141 32 .0 148 < 1.0 168 43.0 114 1.6 179 2.2 228 17.0 147 27.3 160 88.4 169 35.0 133 46.6 127 83.0 96 < 1.0 359 2.2 225 2.6 308 2.3 250 2.0 264 < 1.0 268 < 1.0 238 Dry, ash-free basis. Mineral matter containing basis. Spencer and Bond (1966) f e e l that the "sorption uptake" (moles per unit weight or volume of a given adsorbent) under defined conditions i s the correct parameter that should be used to describe the sorptive properties of porous materials, and that the concept of " s p e c i f i c surface" should not be applied since adequate reference materials are not available. They also advise to use of adsorption/desorption isotherms for revealing information on the pore structure of microporous s o l i d s and on the changes these undergo upon various treatment. 5. Porosity of Coals Hirsch (1954) used the scattering obtained i n his X-ray d i f f r a c t i o n studies of v i t r i n i t e to demonstrate the existence of two types of porosity present i n coals: a) The "open structure" c h a r a c t e r i s t i c of low rank coals with high porosity. b) The " l i q u i d structure" c h a r a c t e r i s t i c of coking coals with very l i t t l e porosity. The work by Bond in 1956 and 1957 has also indicated that "the holes in coal tend to be f l a t rather than c y l i n d r i c a l or spherical. recently, Toda et aJ. (1971) concluded that: The micropore volume decreases with an increase in the rank of coal and shows a minimum at 85% carbon. The micropore volume decreases with an increase in the a l i p h a t i c , c y c l i c or aromatic C-H hydrogen, i d e n t i f i e d by infra-red spectroscopy. The nature of porosity of a number of American coals has been studied by Gan ejt al_. (1972) who concluded that coals vary widely i n t h e i r t o t a l pore volumes (porosites range between 4.1 and 23.2%). Most of the in t e r n a l surface area i n a coal p a r t i c l e i s contained within the u l t r a f i n e region of the t o t a l porous structure, which may represent only 50 to 80% of the inte r n a l free volume. In the lower rank coals (carbon content less than 75%), macropores predominate while i n coals with 76-84% carbon content, about 80% of the t o t a l open pore volume i s due to micro and t r a n s i t i o n a l pores. Their f i n a l conclusion i s that coals having about 35-55% of th e i r t o t a l open pore volume i n the t r a n s i t i o n a l range are expected to be most suitable for use i n the adsorption of dissolved molecules from solutions and thus they are of interest as possible materials for use in water p u r i f i c a t i o n . The i n i t i a l oxygen content of the coal i s found to have an e f f e c t on the formation of t r a n s i t i o n a l pores (Bonnet, 1970). The s p e c i f i c surface and the c a p i l l a r y values increases with the degree of oxidation of the coal and gives lower values for non-oxidized coal (Rusin, 1973). Toda (1972) calculated the pore volume of coals by the measurement of the coal densities i n various l i q u i d He then u t i l i z e d t h i s technique i n the study of the changes i n the pore structure of Japanese coals with heat treatment (Toda, 1973). 6. C o l l o i d a l Structure Colloids are defined as materials with at least one dimension less than 0.5 urn. According to McBain (1950), a single material cannot be defined as c o l l o i d a l , rather a combination of materials must be s p e c i f i e d to designate a c o l l o i d system. Accordingly, charcoal i s not a true c o l l o i d , even though i t has " c o l l o i d a l " dimensions, while brown coals and l i g n i t e s are considered as true c o l l o i d s in t h e i r n a t u r a l l y occurring state (Evans, 1973a). The f i n e l y divided coal substance i s dispersed i n a continuous water medium to form a gel 14. s t a b i l i z e d by the carboxyl and hydroxyl groups i n the coal. As these groups are removed, the coal loses i t s c o l l o i d a l nature. Evans (1973b) reported that any attempt to measure surface area or porosity after removing the dispersing medium (water), for example by drying, w i l l at least measure the values of the resultant xerogel, which may be d i f f e r e n t from the o r i g i n a l coal. 7. Permeability The permeability was found to be d i r e c t l y proportional to the square of the size of p a r t i c l e s of 2 coal at constant porosity (Kuprin, 1973), i.e. K = C d where K i s the permeability, d i s the average diameter of the p a r t i c l e s (nm) and C i s a constant (4 X 10 ^ ) . He also derived the formulae for c a l c u l a t i n g the permeability of coal and sand at d i f f e r e n t p o r o s i t i e s c i t e d as follows: 2 1 2 K = C c /R " for coal (c = p a r t i c l e diameter of coal) 2 0 8 K = C d /R " for sand (d = p a r t i c l e diameter of sand) R i s a p a r t i c l e size parameter determined by data from a 15 . sieve analysis. These equations can be used to control the f i l t r a t i o n through coal media on the basis of p a r t i c l e size d i s t r i b u t i o n . 8. Infra-red Spectra The infra-red methods can in s i t u detect the presence of chemical groups, preclude or l i m i t the existence of proposed structures, and demonstrate s i m i l a r i t i e s and differences in the chemical structure of coal. Work on the infra-red spectroscopy of coal and coal products was originated in Great B r i t a i n by Sutherland (1944). Early investigators (Cannon and Sutherland, 1945) were successful i n assigning some of the absorption bands to s p e c i f i c chemical bonds. Cannon (1953) l a t e r made further assignments such as oxygen-containing functional groups, Cr^ and Crl^ groups and both single r i n g and condensed aromatic structures. He discussed the decrease in bands of oxygen- containing groups with increase i n rank. Many studies have been carried out by Brown (1955) on the v a r i a t i o n of infr a - r e d spectra with the rank of coal. F r i e d e l et al_. (1956) compiled i n a report most of the spectral studies on the chemical composition of coal, including a comparison between various experimental techniques of which the potassium bromide p e l l e t technique i s the easiest and most successful one. Several new str u c t u r a l assignments being made during t h i s work for the absorption bands obtained. Interference due to minerals i n the coal has been recognized, Kaolinite has been i d e n t i f i e d as the p r i n c i p a l cause of a band hitherto assigned to aromatic ethers. A complete survey of the positions of c h a r a c t e r i s t i c infra-red bands and their assignments by various authors i s presented by Tschamler§ De Riuter i n Loury (1963), a modified l i s t , including the recently assigned bands i s shown in Table 2 . F u j i i et a l . (1970) concluded that the aromatic C-H hydrogen band at 3030 cm 1 appears i n coal with 81.1% carbon and becomes stronger as the coal rank increases. However, the a l i p h a t i c C-H hydrogen band at 2920 cm * increases gradually with the rank u n t i l 86% carbon, but decreases sharply beyond that point. He also confirmed that the band at 1600 cm ^ increases i n i n t e n s i t y with increase of the oxygen content. For the -OH absorption band at 3450 cm only semi-quantitative information can be obtained (Osawa et a l . 1971) because t h i s band i s affected greatly by the moisture content of the KBr disc. Recently, the infra-red spectra of t e r t i a r y l i g n i t e s were measured and related to t h e i r chemical structure (Siskov, 1974). 16a. TABLE 2. BAND > POSITIONS IN THE INFRA-RED SPECTRA OF COALS AND THEIR ASSIGNMENTS Band Position. -1 cm u Assignment 3300 3 OH Str ^ Phenolic'OH 0 * ) -OH (hydroperoxide) -NH Str. ) > NH. N 30 30 3.3 ar. CH Str. 29 78 Sh. 3. 36 CH 3 Str. 2925 2860 3.42 3.5 j CH 3 Str., CH2 S t r . , a l . CH Str. 1700 5.9 C = 0 Str. of COOH or ketonic carboxyl 1600 v.intense 6.25 ar. C = C Str. C = 0. . H0- Double band conjugated with carboxyl more recently g r a p h i t i c structure. C O O " , 1450 6.9 CH sym. def., ar. C = C Str., a l . C - ^ 0 also C ^ _ Q -H 1300 to 1000 7.7 to 10.0 C - 0 Str. (phenols) OH def. Car,-0-Car. s t r . C - 0 Str. (alcohol) Car.-0-Car. a l . S t r . Cal,-0-Cal. Str. 1050 to 900 9.6 to 11.0 S. - O of s i l i c a t e impurity and other mineral matters 900 to 700 11.0 to 14.3 Aromatic bands 860 to 750 11.5 to 13.3 Substituted benzene ring s , Carbonates C0 3~" u (microns) = a measure for the wavelength (A) i n microns. - l cm = a measure for the wave number V". The two units are connected by the re l a t i o n 10,000 _ -1 In comparison, the f i r s t scan of the spectrum of activated carbon i n the infra-red shows complete or nearly complete ele c t r o n i c absorption. However, on expanded scale and using wider s l i t and slower scanning speeds, a spectrum has been observed by Friedel (1970 and 1972). This spectrum shows d e f i n i t e bands at 1735 cm *, 1590 cm"1 and 1215 cm-*. These are interpreted, respectively, in terms of carboxyl, aromatic structures or unconjugated chelated carbonyl and C-0 groups. However, due to the great magnification, i t i s possible to reach a point where the apparent transmittance may consist of an appreciable amount of instrumental scattered energy. 9. Chemical Structure In the l a s t several years, excellent work has been done which contributes to a better understanding of the basic s t r u c t u r a l models of the coal molecule (Given, 1960; H i l l , 1962; Smirnov, 1973; Loewenber, 1973; Chakrabartty and Berkowitz, 1974). Although Given's model i s widely recognized by many coal chemists, i t appears to be the least promising i n r e l a t i o n to the research ca r r i e d out for t h i s report for the following reasons: a) The model i s proposed for high rank coals with 82% carbon while a l l experiments in t h i s research were performed on low rank l i g n i t e coals, b) The absence of methylene bridges,side chains and functional groups i n Given's 18. model i s contrary to our findings where there i s an appreciable amount of a c i d i c groups present i n Hat Creek coal samples. In comparison, the model proposed by H i l l (1962) for the high v o l a t i l e bituminous coal i s more consistent with our objectives. It incorporates a large number of functional groups and other bonds. Recently, Chakrabartty and Berkowitz (1974) developed a s t r u c t u r a l model for coal which shows that the s k e l e t a l carbon arrangements of coal are l a r g e l y made up of non- aromatic structures and i t i s not therefore an aromatic s o l i d as believed previously. 9.1 Oxygen-functional groups A c h a r a c t e r i s t i c of low rank coals, peats and related humic materials i s that much of the oxygen associated with t h e i r structure i s present as carboxyl and phenolic hydroxyl groups (Brooks, 1957). The d i s t r i b u t i o n of oxygen- containing functional groups i n humic acids of the coal was measured by Moschopedis (1962) for some l i g n i t e samples, and found to have a t o t a l a c i d i t y of 7.3 m. eq/gm, carboxyl COOH of 4.4 m.eq/gm and phenolic OH of 2.9 m.eq/gm. Meanwhile, s o i l humic acids are found to have very s i m i l a r values. The a c i d i t y or exchange capacity of humic substances i s due mainly to the presence of dissociable hydrogen in aromatic and a l i p h a t i c COOH and phenolic -OH groups. The active hydrogen in coal i s determined using Grignard Reagent (methyl magnesium iodide). However, the reaction i s not always stoichiometric and lower values are often obtained. (Jones et al_. 1962) . Kasotochin et a l . (1964) showed the fundamental structure of humic acids to consist of f l a t aromatic condensed rings with functional groups as well as other simple aromatic hydrocarbon chains. He pointed out that nitrogen occurred in c y c l i c and in a l i p h a t i c forms. The structure of brown coal i s related to that of oxidized hard coal by Kukharenko et a l . (1969). He oxidized humic acids extracted from brown coals and weathered coals, and then isol a t e d carboxylic acids from the reaction mixture, using gas-liquid chromatography. It was shown that t r i - and tetra-basic aromatic carboxylic acids predominated. The proportions of oxygen i n the major functional groups were calculated for coal humic acids (Moschopedis,1962) who found that only 74% of the oxygen present can be accounted for i n functional-oxygen groups mainly the carboxyl COOH of > 49%, phenolic OH of >16% and methoxyl groups of - 9%. At the present time, the characterization of this unaccountable oxygen has yet to be c l e a r l y achieved. A number of theories exist which confirm the presence of quinones and ether-like linkage units i n the humic substances. Davies et a l . 20. (1969) showed that blocking of the quinone groups produced a s i g n i f i c a n t decrease in the copper retention capacity of the humLc acid. Rachid (1972a) has measured the quinone content of humic substances i s o l a t e d from a marine environment. More recently, Goodman and Cheshire (1973) have suggested an e n t i r e l y d i f f e r e n t type of group containing nitrogen - "porphyrin group". Because nitrogen i s such a well-known electron donor in coordination compounds, therefore, i t i s l i k e l y that the "porphyrin group" also plays a role i n binding the heavy metal ions. Schafer (1970a) studied the ion-exchange properties of low rank coal with a view to obtaining optimum conditions for the determination of carboxyl groups i n the presence of phenolic groups. He assessed the alt e r n a t i v e procedures known for estimating the carboxyl groups and he concluded that exchange with barium acetate at pH 8.25 under re f l u x (single for 4 hours) followed by potentiometric t i t r a t i o n to pH 8.25 i n the presence of the coal provided the most r e l i a b l e approach. In another work by Schafer (1970b) the procedure for the determination of t o t a l a c i d i t y of low rank coal, using barium hydroxide, was re-examined and i t was concluded that barium hydroxide reacts with a c i d i c hydrogens i n both a l i p h a t i c and aromatic compounds. Therefore, i t i s a successful reagent for measuring both phenolic OH and carboxyl COOH groups defined as " t o t a l a c i d i t y " . 21. A l i p h a t i c hydroxyls are not thought to contribute s i g n i f i c a n t l y to the t o t a l a c i d i t y , so the difference between " t o t a l a c i d i t y " and carboxyl COOH groups gives a measure of phenolic OH (Brooks, 1957). A recent study by Schafer (1972) suggested that the moisture content of low rank coals i s d i r e c t l y related to the carboxyl content and to a lesser extent to phenolic hydroxyl content. The hydrophilic character of these groups leads to the in t e r a c t i o n through hydrogen bonding between water and the functional groups. 10. Adsorption on Coal Surface 10.1 Adsorption of dissolved organics 10.1.1 Biodegradable organics For many years crushed anthracite coals have been used for f i l t r a t i o n in both water p u r i f i c a t i o n and sewage treatment (Turner, 1943). Only during the past decade has the use of coal as an adsorbent for p u r i f y i n g wastewaters been examined. Jhanson and Kunka (1962) reported that c e r t a i n coals have the capacity to remove up to 41 of t h e i r weight of oxygen-demanding materials, measured in terms of COD, from se t t l e d raw sewage. 22. The Rand Corporation (U.S. Dept. of Interior Report, 1971) operated a 10,000 U.S. gal/day p i l o t plant coal f i l t e r recommending the use of coal for post or t e r t i a r y treatment of secondary sewage effluent, since i t i s far less expensive than activated carbon which i s now extensively used in t e r t i a r y treatment processes (Hassler, 1974; P e r r o t t i , 1973; Kalinske, 1972; and Culp, 1971). Shannon (1970) examined the adsorptive capacity of some Canadian coals to remove some components from sewage. He found a pronounced s e l e c t i v i t y between d i f f e r e n t components which were mixed in a form of synthetic waste. The b i o l o g i c a l oxidation a c t i v i t y during sewage treatment with carbon or coal has been confirmed. A study of Biospherics Research Inc. (1969) showed that the surface of the coal p a r t i c l e s provided an enriched micro-environment for microbial growth, therefore, enhancing the b i o l o g i c a l oxidation of the organic matter. The large surface area and the chemical f u n c t i o n a l i t y of the available surface are found to be the major factors responsible for the enhancement of the b i o l o g i c a l oxidation a c t i v i t y ( P e r r o t t i , 1973). A study on powdered coal (Kehoe, 1967) showed that i t i s e f f e c t i v e in agglomeration of the organic p a r t i c u l a t e s from the primary sewage. 10.1.2 Dyes Some American coals were found to adsorb dyes from an aqueous solution (Nandi et a l . , 1971). The removal of dye by coal was shown to be p a r t l y due to the interaction with some mineral constituents, mostly p y r i t e and soluble a l k a l i s a l t s , and due to adsorption on the porous surface of the coal. This study also proved that adsorption of dyes on l i g n i t e s was not influenced by the oxygen groups on the surfac 10.1.3 O i l s The use of coal i n the removal of o i l and other organic contaminants from r e f i n e r y wastes was studied recently by Bunn (1974). 24. Other research on the removal of o i l by powdered coal containing 10 mg/1 of a coagulant (e.g. A^CSO^)^)) was conducted by Merkel (1972), who used the spent coal af t e r treatment for combustion. 10.1.4 Alcohols and phenols Oxidized coal was found to adsorb n - a l i p h a t i c alcohols (Vlasova, 1973). The oxygen-containing groups, e s p e c i a l l y phenolic -OH and carboxyl COOH form active centers for adsorption. The adsorption of butanol, hexanol and phenol was proven to be greater on waste rock of 97% ash content than on high grade coal with 2% ash content. 10.1.5 Colors The study of color removal by coal was car r i e d out i n Japan by Motohisa et a l . (1973) who found that a mixture of coal with a small amount of activated charcoal showed considerable a c t i v i t y . An e a r l i e r study on coal ash proved that the l a t t e r removed the color completely from effluents and residual liquors from yeast production (Drub, 1967). Other sorbents including activated carbon have been found to be less e f f e c t i v e than coal. 10.2 Adsorption of heavy metals In 1971, the L i n f i e l d Research Inst i t u t e in McMinnville, Oregon completed a preliminary study on the removal of heavy metal ions from solutions by coal (Hinrichs, 19 71) . 1 During the l a s t few years, research studies proved that some l o c a l B.C. coals possess a good adsorptive qua l i t y for the removal of heavy metals (Coulthard, 1976) , (Hendren, 1974) , (Riaz, 1974). Other research studies i n Japan by Kawazoe (19 71) found that chromium was removed completely from e l e c t r o - p l a t i n g waste effluents when i t was in contact with low grade coal for 24 hours. Powdered l i g n i t e has been found f i r s t to reduce hexavalent chromium (Cr VI) to t r i v a l e n t chromium (Cr III) in an a c i d i c s olution, then the l a t t e r . i s r e a d i l y adsorbed by coal (Motoshi, 1974). Other extensive studies have been c a r r i e d out on the adsorption and desorption behavior of some heavy metals such as beryllium, titanium and gallium on coal and peat. The e f f e c t of pH and presence of other ion electrolytes was also studied (Eskenazy, 1972, 1970 and 1967). Recently, process f e a s i b i l i t y studies have been i n i t i a t e d in India to determine the p o s s i b i l i t y of extracting m e t a l l i c n i c k e l by a lignite-adsorption route (Altekar et a l . , 1974) . Lignite coal proved to be more e f f e c t i v e for adsorption of n i c k e l than other adsorbents such as coke, charcoal, activated carbon, sawdust, etc. as shown in Table 3. TABLE 3. COMPARISON OF ADSORBENTS FOR NICKEL* Adsorbent Adsoprtion ' (% of Ni in solution) M e t a l l u r g i c a l coke Trace Charcoal 1.6 Hardwood sawdust 2 7.2 Petroleum coke 39.6 Activated carbon 55.1 Lignite 98.4 , 11. Suggested Mechanisms for Adsorption of Metal Ions No d e f i n i t e mechanism for the adsorption of the metal ions by coal has, as yet, been proven because of the complexity of the chemical composition of coal. Eskenazy (1970, 1972) supposed that the binding of beryllium to coal leads to the formation of chemical com- pounds of various s t a b i l i t i e s and the presence of functional groups c h i e f l y hydroxyl and carboxyl groups, making i t possible for ion exchange reactions. He also noticed that a decrease of the functional groups brings about a reduction of beryllium adsorption per unit surface area; he assumed Sorbent/Sorbate r a t i o for the above solut i o n i s 26.7g adsorbent per g. Ni. that adsorption has a chemical nature due to i t s i r r e v e r s i - b i l i t y , and that the metals slowly form more stable chemical bonds with coal. From the results of h i s experiments he con- cluded that a chemisorption process proceeds through an ion exchange. Eskenazy's explanations for the mechanism involved in the adsorption of metals are not adequately confirmed and require further research work to support h i s hypothesis. In Japan, Terajima (19 73) studied the adsorption mechanism of removing heavy metal ions from wastewater using nitro-humic acid. He concluded that the adsorption of heavy metal ions by the humic acid i s mainly due to the chelate formation at low concentration of metal ions and mainly due to ion exchange at high concentrations. He used infra-red spectroscopy to confirm his theory. 11.1 Complexing of metals with humic substances Coal i s considered as one of the n a t u r a l l y occurring humic substances and i t contains humic acid i n i t s structure Therefore, theories related to the i n t e r a c t i o n of metal ions with the humic acids extracted from coal, peat, s o i l etc. can be assumed to be p a r t i a l l y applicable to the adsorption of metal ions on coal. As early as 1952, Broadbent and Bradford showed the importance of carboxyl COOH and phenolic hydroxyl -OH groups in cation exchange reactions of s o i l organic matter. 28. Davies et a l . (1969) concluded that the retaining s i t e s probably involved carboxyl and hydroxyl groups acting together. Although these workers suggested that alternate groups such as hydroxy quinones might also be implicated in the reaction. Schnitzer and Skinner (1965) suggested a simul- taneous involvement of a c i d i c carboxyls and phenolic 3 + 3 + 2+ hydroxyls with Fe , A l , and Cu , while alcohol hydroxyls are not involved in the in t e r a c t i o n . They concluded that s a l i c y l i c acid type structure was present i n the humic organic matter. Most recently, Cross (1975) provided additional evidence for the hypothesis that s a l i c y l i c and phthalic acid- l i k e functional groups play a s i g n i f i c a n t role i n the formation of metal-organic complexes in s o i l . It can be seen that the metal reaction with a c i d i c groups must involve a proton release; Van Dijk (1971) conducted t i t r a t i o n curve experiments comparing the magnitude of the pH drop upon the addition of several inorganic s a l t s to the solution. The pH reductions were related to the bond strengths of the complexes formed. 12. Adsorption of Metals on Activated Carbon Although the merits of activated carbon for the removal of organic compounds from water have been well 29. documented in the l i t e r a t u r e (Hassler, 1974), (Culp, 1971), l i t t l e , i f any, work has been performed within the water treatment f i e l d relevant to the use of activated carbon for removing trace metals and compounds. Sigworth et a l . (19 72) were able to extrapolate the results of a test performed, and came to the conclusion that activated carbon needs appropriate conditions of pH to carry out an e f f i c i e n t p u r i f i c a t i o n of water from trace metals. They predicted that several mechanisms are probably involved as follows / 1) Carbon w i l l p h y s i c a l l y adsorb on i t s tremendous i n t e r n a l surface molecular compounds such as acids, complexes and high molecular weight polymers. 2) Because of the very small number of oxygen complexes and functional groups fixed on the carbon surface, a limited ion exchange action i s expected to take place. 3) Carbon can induce p r e c i p i t a t i o n of a super saturated solution by nucleation and can reduce the s o l u b i l i t y of a m e t a l l i c s a l t . 4) Commercial activated carbons contain traces of reduced forms of iron and other metals, which can enter into reactions with metallic ions lower i n the electromotive series causing the heavy metal to be deposited on the surface. 30 B. Hat Creek Coals 1. History: (Campbell and Jory, 1977). "The Hat Creek coal deposits were f i r s t reported by Dr. n.M. Dawson of the Geological Survey of Canada i n 1877. The coal exposures were li m i t e d to a small area along the bank of Hat Creek, xvhere erosion had stripped the cover of g l a c i a l t i l l . By 1925, three shallow shafts and two short adits had been driven into the coal and seven holes had been bored into i t . No further work was done u n t i l 1933. From 1933 u n t i l 1942 a few hundred tons of coal were mined from the workings each year and sold l o c a l l y for thermal use; this a c t i v i t y ceased during World War II and was not renewed. In 19 57, Western Development and Power Ltd., a subsidiary of B.C. E l e c t r i c Co. Ltd., optioned the property as a possible future source for a major thermal e l e c t r i c generating plant. The area of the exposed portion of the Hat Creek deposit was explored by reconnaissance diamond d r i l l i n g and trenching during 1957 and 1959. The work j u s t i f i e d the subsequent purchase of the property by B.C. E l e c t r i c for two m i l l i o n d o l l a r s . Following an expropriation of the B.C. E l e c t r i c Co. by the B.C. P r o v i n c i a l Government, the ownership of the coal property passed to the B.C. Hydro and Power Authority. No further work was conducted on i t u n t i l 19 74 when 31. the current program of more d e f i n i t i v e i n v e s t i g a t i o n was begun. At present studies are being conducted by various consultants on a conceptual thermal plant design, preliminary assessment of possible open p i t s , environmental impact and alternative coal uses'.1 2. Geology The general geological and economic features of the Hat Creek coal deposits were investigated by Campbell, Jory et a l . (1977) who concluded from th e i r preliminary study that the Hat Creek coal deposits occur within folded and faulted t e r t i a r y s trata of the Cold Water group. This group comprises weakly claystone, shales, s i l t stones, and conglomerates underlying the f l o o r and lower flanks of the v a l l e y of upper Hat Creek. The main coal layer at upper Hat Creek i s one of the thickest i n the world (1500 f t . ) . The deposits probably represent the world's greatest concentration of coal i n such a small area. Investigation of the deposits i s s t i l l i n progress, and much remains to be learned, p a r t i c u l a r l y concerning t h e i r combustion c h a r a c t e r i s t i c s , t h e i r ultimate extent and t h e i r economic a b i l i t y to be mined to the great depths which they reach. 3. Rank The r e l a t i o n s h i p between ash and c a l o r i f i c value of the Hat Creek coal described by Campbell and Jory (1977) i s nearly l i n e a r as shown in Figure 1. The c a l o r i f i c 4000 60CO I2POO CALOAtftC VA4.UE-dTU/La. {Q**Y BASIS i FIGURE 1 : ASH -CALORIFIC VALUE REGRESSION OF HAT CREEK COAL. (Campbell and Jory, 1977) value intercept, for dry, mineral matter-free coal i s approxi- mately 13,000 BTU/lb for coal samples from "holes" 76-135 and 136 which were d r i l l e d during the summer of 1976. If the in s i t u equilibrium moisture content is assumed to be 25% the c a l o r i f i c value of the moist, mineral matter„free coal i s then approximately 9750 BTU/lb making this sample of coal low sub-bituminous B i n rank. The mean c a l o r i f i c values and ash contents of Hat Creek coal samples from d i f f e r e n t zones are shown i n Table 4a TABLE 4a SOME MEAN VALUES OF HAT CREEK COAL. Average CV. Ash Vol. Mat. Fixed C Total S " " 'I'll X CiCH6 s s ( f t ) (BTU/lb) (%) (%) .(%.). (%) A 407 5900 28.9 25.7 25.3 ,0.58 B 2 37 6 300 26.6 25.6 2 7.8 0.66 C 110 4500 38.4 22.4 19.2 0.35 D 26 7 75 80 19.0 2 7.4 33.6 0 .22 Mean* 6300 26.4 25.8 27.8 0.41 * Mean obtained by weighting each zone by the percentage of the coal reserve i t represents. However, i f the rank of the Hat Creek coal were to be determined according to the Standard ASTM procedure D388 (1976) , indiv i d u a l samples would be ranked variously from l i g n i t e to sub- bituminous C depending on the c a l o r i f i c value. Table 4b shows the ASTM c l a s s i f i c a t i o n of coals by rank. It i s obvious that c l a s s i f i c a t i o n i s according to fixed carbon and c a l o r i f i c value expressed i n BTU/lb calculated to the mineral matter_free basis. The higher rank coals are c l a s s i f i e d according to f i x e d carbon on the dry basis, the lower rank coals are classed accordin to c a l o r i f i c value on the moist mineral matter-free basis. 4. Infra-red Spectra Greenslade (1975) evaluated the infra-red spectra of Hat Creek coal i n comparison with two other B.C. coals from Kaiser and Fording deposits. A l l of the main absorption bands Class • Group Fixed Carbon Limits, percent (Dry. Mincra l - Matter-Frec Basis) Volati le Matter Limits, percent (Dry. Mincra l- Matier-Frec Basis) Calorif ic Value L imits. Btu per pound (Moist.*.- t Mineral-Matter-. Free Basis) Agglomerating Character Equal or Greater Than Less Than Greater Than Equal or Less Than Equiil or Greater Than Less Than 1. Mela-anthracite 1. Anthrac i l ic 2. Anthracite 3. Scmianthracitc' 98 92 86 98 92 2 8 2 8 14 | nonagglomeraiing 1. Low volatile bituminous coal 2. Med ium volatile bituminous coal II. Bituminous 3. High volatile A bituminous coal 4. High volatile B bituminous coal 5. High volatile C bituminous coal 78 69 86 78 69 14 22 31 22 31 : : : , 14 000" 13 000° . II 500 10 500 14 000 13 000 II 500 e r a • Commonly agglomerating' -zx O agglomerating ^ 1. Subbilurrtinous A coal III. Subbituminous 2. Suhbituminous B coal 3. Subbituminous f coal 10 500 9 500 - 8 300 11 500 - , 1 0 500 ' 9 500 . - CO I ?- nonagglomeraiing . , , , •.• I- Lignite A . ' IV. L ignit ic i i •. o c 2. Lignite B 6 300 8 300 : 6 300 •Th i s classification does not include a few coals, principal!) nonbamteri vsrieMes. which ha*- unu^uil phy^ica! and chemical propenier and which come within the limits o f fixed carbon or calorif ic value of the high-volatile bituminous and subbituminous ranks. A l l or these coals either contain less than 48 percent dry. mineral-matter-free fixed carbon or have more than 15.500 moist, mineral-mattcr-free British thermal unit> per pound * Moist refers to coal containing its natural inherent moisture hut noi including visible water on the surface of the coa: ' If agglomerating, classify in low-volatile group of the bituminous class * Coals having 69 percent or more fixed carbon on the dry. mincral-matier-frce basis shall be classified according to fived carbon, regardless of calorific value. ' It is recognized that there may be nonagglomeraiing varieties in these groups of the bituminous class, and there are notable exceptions in high volatile C bituminous group. TABLE 4b : ASTM CLASSIFICATION OF COALS BY RANK CO 34. are s i m i l a r to those previously assigned for Pittsburg and Japanese coals by F u j i i (1970) and Osawa (1971) respectively. A l l of the three B.C. coals exhibit s i m i l a r i n f r a - red spectra. In the case of Hat Creek coal, intense absorption bands at the 1700 cm"''' of the C = 0 bond of the carboxyl groups COOH and at the 1600 cm * of the C = 0 bond of the carboxylate and the C = C bond were obtained. This indicates that Hat Creek coal contains a r e l a t i v e l y large number of carboxyl groups. The strong absorption bands -1 -1 obtained at the 1430 cm and 870 cm were explained to be due to the presence of carbonate i n mineral matter while the k a o l i n i t e band i s not present. The degree of surface oxidation of the Hat Creek coal i s indicated by the combination of i n f r a - r e d spectral and s a l t f l o t a t i o n studies. Higher degrees of surface oxidation i n the coal i s accompanied by an increase i n the carbonyl C = 0 groups which r e s u l t i n a decrease i n the f l o t a t i o n rate. 5. Adsorption of Water Pollutants The a b i l i t y of Hat Creek coal to remove dissolved constituents from water has been the subject of much discussion and many claims i n B.C. The e f f i c i e n c y of the coal for removing dissolved organic constituents from sewage seems to be very encouraging, (Coulthard, 1976; Hendren, 1974). This coal demonstrated that i t possessed a good adsorptive capacity for the removal of heavy metal trace elements from water (Coulthard, 1976; Riaz, 1974; and Hendren, 1974) 36. III. EXPERIMENTAL MATERIALS 1. Hat Creek Coal 1.1 Description of the coal deposits The type of coal used i n this study i s of l i g n i t e v a r i e t y , mined from the Hat Creek deposit which i s situated about 200 miles from Vancouver, B r i t i s h Columbia, as shown on the map, (Figure 2) where one b i l l i o n metric tons, or more, of the coal e x i s t s . This amount i s contained p a r t l y within a Crown mineral grant area and coal licences owned by B.C. Hydro. The coal deposit consists of f i v e seams, each several hundred feet thick. Figure 3 i s a cross s e c t i o n a l view showing that the fi v e seams are separated by r e l a t i v e l y t h i n layers of clay, shale, and sandstone (Jones, 1973). 1.2 Sampling locations Two samples of Hat Creek coal were provided for th i s research study by the exploration company (Dolmage, Campbell and Associates, 19 76)*. The samples mined from the area shown i n Figure 4 were c l a s s i f i e d as follows: a) Oxidized, surface coal (S.C.) which was provided from location number (1) shown on the maps i n Figure 5. The 150 kilogram samples was mined manually at the surface. b) D r i l l - h o l e coal or Core coal (C.C.) which was provided from the d r i l l - h o l e marked on the map in Figure 5 as DDH 74-39. The core sample i s a composite of * Direct communication FIGURE 2 : HAT CREEK COAL LOCATION PLAN. (Campbell and Jory, 19 77) 3 ZOO FIGURE 3 : CROSS SECTION VIEW SHOWING THE COAL SEAMS. FIGURE 4 : INDEX PLAN FOR THE HAT CREEK COAL DEPOSITS. -(Dolmage and Campbell Associates) 39. FIGURE 5 : HAT CREEK COAL DEPOSITS, SAMPLING LOCATION PLAN. (Dolmage and Campbell Associates) 40. two d r i l l - h o l e samples. One was c o l l e c t e d at a footage of 33 to 93 feet, while the other sample was c o l l e c t e d at a footage of 98 to 438 feet. 1.3 Coal preparation The 150 kilograms of the oxidized surface sample was received as large lumps and unwashed. The core sample received was crushed and washed p r i o r to shipping from the s i t e . 1.3.1 Crushing of the surface coal The coal was f i r s t crushed in a BICO Jaw Crusher, then •I ii passed through a BICO Pulverizer to give a crushed material with p a r t i c l e sizes ranging from 4 mesh to less than 200 mesh size . 1.3.2 Sieving Series of U.S. Standard Test Sieves were used for mechanical shaking on a "Roto-Tap" shaker. The coal was c l a s s i f i e d into coarse, medium, and fine p a r t i c l e sized samples U.S. sieve numbers 4, 14, 20, 50, 60, 100, 140 and 325 mesh size were mostly used in the size c l a s s i f i c a t i o n . The p a r t i c l e sizes are usually reported, i n this work, as the U.S. Standard Screen Scale Sieve Series. The actual dimensions of screen openings, the equivalent screen s i z e s , and the Tyler mesh numbers are l i s t e d in Appendix A, Table 1. 1.3.3 Washing and Drying The samples were washed by s l u r r y i n g f i r s t i n water followed by decantation, and then oven dried at 41. 10 3 - 105°C for three hours. 2. Activated Carbon Calgon F i l t r a s o r b 400, supplied by Calgon Canada in Ontario was used in some experiments to assess the adsorptive q u a l i t i e s of the Hat Creek coal in comparison to the activated carbon which i s considered a very e f f e c t i v e adsorbent and i s used widely in the wastewater treatment processes. The following materials were used i n minor experiments for comparison purposes: 3. C e n t r a l i a Anthracite It i s anthracite type, mined from a deposit in the State of Washington, U.S.A. 4. Union Bay Coal Also known as Tsable River coal. The coal is mined from the Union Bay deposit on Vancouver Island, B.C. A comparison between the level s of the d i f f e r e n t metal ions in the ash i s shown in Table 5 for the above three coals. TABLE 5. LEVELS OF METALS IN THE COAL ASH* Location Cu Fe Co 1 Pb Mn. Zn Na Cd Cr Hat Creek 79.07 20917.4 16.3 43.5 20.98 848.3 62,9 1758.2 0.0 63 Union Bay 60.00 2922.2 8.8 34.4 11.8 - 96.6 - 3.35 49 Anthracite Washington 25.5 7202.0 9.2 18.3 11.8 - 19 97 - 0.0 72 Note: Mercury for Hat Creek 27-28 ppb, other values in ppm. (mg/1). * The analysis conducted at the geochemistry lab, Geological Science Dept., U.B.C. Sample of commercial coal. 42. 5. Ottawa Sand A special kind of construction sand which i s mostly used for research work i n the f i e l d of i r r i g a t i o n and s o i l studies. 6. Abbots ford Sandy S i l t Loam This sample obtained from Abbotsford, B.C., i s c l a s s i f i e d as an o r t h i c concretionary brown s o i l (Luttmerding, 1966). It i s composed of a mixture of shallow aolian deposits mixed with, or,over g l a c i a l outwash. 43. IV. PROPERTIES OF HAT CREEK COALS 1. MATERIALS. 1.1 Prepared surface coal, p a r t i c l e size 100/140 mesh. 1.2 Unoxidized core coal, p a r t i c l e size 100/140 mesh. 1.3 Calgon activated carbon, p a r t i c l e size 100/140 mesh. 2. METHODS. The following chemical analyses were conducted at the Commercial Testing and Engineering Company, Vancouver Branch,* according to the ASTM standard procedures for coal and coke (ASTM, 19 74). 2.1 Chemical analysis 2.1.1 Proximate analysis (Ode, W.H. i n Lowry, 1963) "This analysis represents the d i s t r i b u t i o n of products obtained during heating under standard conditions, proximate analysis separates the compounds into four groups:- 1) Water or moisture content. 2) V o l a t i l e matter consisting of gases and vapors driven o f f during p y r o l y s i s . 3) Fixed carbon, remaining as the non-volatile f r a c t i o n of the pyrolyzed coal. 4) Ash, derived from the mineral impurities." * 147 Riverside Dr., North Vancouver, B.C., V7H 1T6. 44. The fixed carbon i s a calculated figure obtained by subtracting from 100 the sum of the percentages of moisture, v o l a t i l e matter and ash. 2.1.2 Ultimate analysis (Ode, W.H. in Lowry, 1963) "This analysis expresses the composition of coal in percentages of carbon, hydrogen, nitrogen, s u l f u r , oxygen and ash, regardless of t h e i r o r i g i n . The carbon includes that present in the organic coal substance as well as that in carbonates. The hydrogen includes that of the organic coal substance and the hydrogen present i n the form of moisture and the water of constitution of the s i l i c a t e minerals. A l l the nitrogen i s present as a part of the organic substance. The sulfur normally i s present i n three forms - organic sulfur compounds, py r i t e or marcasite, (FeS2), and inorganic s u l f a t e s . " 2.1.3. Other standard determinations The ash composition, d i s t r i b u t i o n of sulfur forms, and heating value of the coal i n BTU per pound are also determined for the surface and the core samples of the Hat Creek coal. 2.2 Contaminants i n Hat Creek coal This i s expressed, i n t h i s study, as the major water and acid leachates from the coal. The test was c a r r i e d out on 100 gram quantities of each of the surface and the core coal samples. Each coal sample was either leached with one l i t e r of water or a hydrochloric acid solution of IN concentration. Each washing was c o l l e c t e d and a composite sample then analyzed. 45. 2.2.1 Heavy metals (APHA, 1975) Analysis of the following heavy metals i n each washing sample have been car r i e d out with a Perkin Elmer Atomic Absorption Spectrophotometer, Model 306; the following metals were determined: Na, Zn, Pb, Cu, Mn, Cr, Ni, Fe, Ca, Mg, and Ba. 2.2.2 Ammonia and nitrates (APHA, 1975) 100 mis of d i s t i l l e d water was refluxed with 2%, 5% and 10% by weight of each of the surface and core samples for a period of two hours. The coal was then separated by f i l t r a t i o n . The ammonia and n i t r a t e were determined by the automated methods on the Technicon Industrial AutoAnalyser, Model II. 2.3 Surface properties 2.3.1 Surface features of the coal (Goldstein, 1975) The low power l i g h t microscope and the Scanning Electron Microscope (SEM) were used for the preliminary examina- tion of the coal surface. A low magnification of 4.5X was used to photograph the surface features of the p a r t i c l e s . The SEM was used for the examination and analysis of the microstructural c h a r a c t e r i s t i c s of the coal surface. Images with a three dimensional appearance could be obtained which is a dire c t result of the large depth of focus. The coal sections preparation i s described in Appendix B-l-1. 46. 2.3.2 Infra-red absorption The potassium bromide technique was used for the pre- paration of the coal samples. The I.R. spectrum, i n the range of wave numbers between 4000 - 250 cm \ for each of the surface and core coals were recorded and compared. The absorbance for every main band was evalua- ted using the base lin e technique ,The s p e c i f i c extinction c o e f f i c i e n t e for each absorption band was thereby estimated according to Ewing (I960) and F u j i i (1970). A Perkin Elmer Infra-red Spectrophotometer, Model 521, was used for recording the I.R. absorption spectra. A detailed description for a l l of the techniques involved in this analysis i s outlined in Apprendix B-2. 2.3.3 Surface area and pore structure The BET surface area using nitrogen (Brunauer, Emmett 2 and Teller,1938) , measured in m /gram, micropore volume in mis/gram and the average pore diameter in angstrom (°A) have been determined for surface and core coal, and compared with those measured for activated carbon. These measurements were conducted by the Fuel Sciences D i v i s i o n , Alberta Research Council, Edmonton. The Micromeritic Surface Area and Pore Volume Analyzer were used for those measurements. A l l of the samples (-60 .+ 100 mesh) were evacuated to 'v 1 0 T o r r in s i t u overnight at 120°C before nitrogen 47. adsorption measurements. The micropore volume covers the range of pores of diameter between 28 - 400 °A. The BET equation and method of c a l c u l a t i n g the s p e c i f i c surface area are shown in Appendix B-3. 2.3.4 Permeability test (Karol, 1969). A prepared column sample of coal of certain p a r t i c l e s i z e , having a cross section A and length L was subjected to a flow of water under a constant head h. From Darcy's law (0 = KiAt) where i i s equal to the hydraulic gradient h/L, there- fore, the c o e f f i c i e n t of permeability, K, can be expressed in terms of these quantities as follows: The test i s performed by measuring the quantity of water Q flowing through the coal sample of length L, the head of l i q u i d h and the time t. 48. 3. RESULTS AND DISCUSSION 3.1 Chemical properties Table 6 shows the comparison of the surface sample and the core sample which are used for the mechanism studies of the research reported. Surface coal has a r e l a t i v e l y high c a l o r i f i c value of 8526 BTU/lb m.m.m.f.b.* while core coal exhibits a lower thermal value of 7623 BTU/lb m.m.m.f.b. Therefore, both coal samples as tested can be ranked as a l i g n i t e v a r i e t y . Other i n d i v i d u a l samples of the core coal d r i l l e d from the same hole, at d i f f e r e n t footages, were analyzed and the data tabulated in Appendix C-l-1. The table shows a wide range of ash content for the analyzed samples. As the footage in depth increases the thermal value increases to reach a maximum value of 10760 BTU/lb d.b. at footage from 318 to 338 f t f o r a sample having an ash content as low as 16.25% d.b. A minimum c a l o r i f i c value of 2800 was obtained at a depth of 33 to 53 f t where the ash content reaches a maximum value of 61.71% d.b. Consequently, the economic value of Hat Creek coal i s expected to be very low i f used f o r thermal generation. The hardness test was 3.0 on the mohr scale for the oxidized outcrop, while unoxidized samples show a hardness of 4.0, compared to a value of 2.62 obtained for the anthracite coal (Coulthard, 1974). * m.m.m.f.b. moist, mineral matter-free basis. 49. TABLE 6. CHEMICAL ANALYSIS OF HAT CREEK COAL SAMPLES SURFACE COAL CORE COAL Sample 39-401 Footage 33178Width.140' As Received Dry Basis As Received Dry Basis I. PROXIMATE ANALYSIS % Moisture 14.38 - 19.04 - % Ash 22.51 26.29 34.87 43.07 % Volatile 32.19 37.60 23.58 29.12 % Fixed Carbon 30.92 36.11 22.51 27.81 100.00 100.00 100.00 100.00 BTU 6607 7717 4965 6133 % Sulfur 0.38 0.44 0.63 0.78 '••% Alk. as Na20 6.08 0.09 0.42 0.52 II. ULTIMATE ANALYSIS % Moisture 14.38 - 19.04. - % Carbon 41.92 48.96 30.47 37.64 % Hydrogen 2.59 3.03 2.30 2.84 % Nitrogen 0.68 0.80 1.01 .1.25 % Chlorine 0.07 0.08 0.03 0.03 Sulfur 0.38 0.44 0.63 0.78 Ash 22.51 26.29 34.87 43.07 0 (by diff.) 17.47 20.40 , 11.65 14.39 100.00 100.00 100.00 100.00 III. MINERAL ANALYSIS IGNITED BASIS (%) SURFACE ; COAL CORE COAL P2°5 0.04 0. 25 S i 02 85. 22 49. 93 F e2°3 6. 81 12. 31 A1 20 3 8. 27 26.84 T i 02 0. 31 0. 89 CaO 2.68 2. 57 . MgO - 0.48 2.01 S 03 1. 62 3. 48 K2° 0. 08 - 0. 76 N a 2 ° 0. 28 o. 71 Ifndetermined 0.21 0. 25 . Total: 100 .00 100 i.OO 50. This good mechanical property exhibited by the Hat Creek coal i s considered promising for the coal to be u t i l i z e d in leaching processes. The mineral analysis shows a very high l e v e l of s i l i c a i n the surface coal reaching 85.22% i n the ash while core coal contains h a l f of this value. This may be due to the contamination of the surface coal by the s o i l present i n the f i e l d . On the other hand, the core coal seems to be very r i c h in i r o n , alumina and most of the other mineral constituents. 3.2 Contaminants in Hat Creek coal 3.2.1 pH; of the coal The pH measurements of the water leachates from sur- face coal showed a drop i n the pH values to an a c i d i c range of 4.5 - 4.6, i n d i c a t i n g the a c i d i c nature of the surface coa l . This may be attributed to the presence of some oxygen-containing a c i d i c groups. However, core coal does not exhibit any drop in the pH but remains at the neutral l e v e l which indicates the lesser a c i d i c nature of this coal. 3.2.2 Ammonia and n i t r a t e The results summarized i n Table 7 show that 18 mgs NH^-N per 100 grams of coal i s washed out of surface coal compared to only 7 mgs NH^-N per 100 grams of coal leached from a core sample. This confirms that the surface coal con- tains higher ammonia content than the core c o a l . The washed out n i t r a t e s seem to have the same levels i n both coals of 51. TABLE 7. LEACHING OF AMMONIA AND NITRATE FROM HAT CREEK COAL SURFACE COAL CORE COAL Coal added ' • Coal added 2% 5% 10% 2% 5% 10 0, NHj-N ppm 5.7 10.2 16.0 2.2 3.9 11.0 mgs washed out per 100 gm coal 22.0 18.0 15.0 5.0 5.0 10.0 N03-N ppm 0.65 1.31 2.31 0.81 2.5 3.88 mgs washed out per 100 gm coal 2.0 2.0 2.0 3.0 5.0 4.0 D i s t i l l e d water (control) NH3-N = 1.3 ppm (mg/1) N03-N = 0.19 ppm (mg/1) 52. 2 - 4 mgs NO^-N per 100 gram of coal. The high ammonia level in surface coal i s probably due to external contamination in the coal f i e l d . The sorptive capacity of the coals were compared before and a f t e r washing out ammonia. The results are dis- cussed in Chapter V . 3.2.3 Heavy metals The results shown in Table 8 compare the levels of the d i f f e r e n t metals leached out of the coal upon washing with water or acid solution. It i s obvious that more metal ions can be removed through acid washing; this is due to the proton exchange with the metal cations. Water-soluble s a l t s of calcium, i r o n and magnesium were washed out with water from both types of Hat Creek coal. Generally, the core coal leachates contain higher lev e l s of metal ions than surface c o a l . This i s due to the larger quantity of "gangue" materials i n the core coal which contain metal ions such as sodium, manganese, chromium, iron and barium. However, higher lead levels are present in surface coal and this may be p a r t i a l l y due to surface contamina- tion . 3.3 Surface properties 3.3.1 General features of the coal surface The images observed by the low power l i g h t micro- scope reveal the common features of the surface of the coal p a r t i c l e s . 53. TABLE 8. LEACHING OF HEAVY METALS FROM HAT CREEK COAL Metal Ion SURFACE COAL CORE COAL Acid Washing Water Washing Acid Washing Water Washing Na 99.00 29.00 335.00 24.00 Zn 2.80 0.10 3.00 0.05 Pb 0.50 N.D. 0.150 . N.D. Cu 1.50 0.10 2.20 0.18 Mi 6.00 N.D. 25.00 N.D. Cr 1.00 N.D. 3.60 N.D. Ni 0.55 N.D. 1.00 N.D. Fe 145.00 0.20 550.00 2.20 Ca 790.00 5.00 825.00 N.D. Mg 125.00 3.00 155.00 0.25 Ba 3.00 N.D. 25.00 N.D. The results are calculated in terms of mgs metal ions washed out/100 gm coal. N.D. = Not detectable. pH of water washings from surface coal pH of water washings from core coal 54. Figures 6a, 6b and 6c give a comparison between the activated carbon, oxidized surface coal and non-oxidized core coal respectively. The p a r t i c l e s of the surface coal have less fractures and cracks than activated carbon, while the core p a r t i c l e s appeared smoother with a layered shape. Since the fractures expose larger areas of macro- pores and therefore tend towards more surface a c t i v i t y , one can expect that the surface deposit i s l i k e l y to be more active than the non-oxidized core deposit. Nevertheless, the surface coal has less a c t i v i t y compared to activated carbon. The scanned images shown in Figure 7a represent a cross section i n the coal p a r t i c l e s obtained after polishing the surface. The corresponding X-ray energy dispersive analysis for p a r t i c l e under scrutiny is shown in Figure 7b. This analysis reveals that s i l i c o n and to a lesser extent iron and sul f u r are the main elements present in the layered p a r t i c l e s , while lower levels of these elements are present i n the fractured p a r t i c l e s . Also, other elements can be i d e n t i f i e d i n the l a t t e r case, such as sodium, potassium, calcium, titanium and chlorine. 3.3.2 Infra-red absorption The in f r a - r e d spectra of the surface and core samples of Hat Creek coal, of carbon contents 48.96% d.b. and 37.64% d.b. respectively, are compared i n Figure 8. 55. 6 - A A C T I V A T E D C A R B O N 4.6X 6^B S U R F A C E C O A L 4.6X 6 - C C O R E C O A L 4.6X FIGURE 6" LOW POWER LIGHT MICROSCOPE IMAGES OF: 6 -A, ACTIVATED CARBON PARTICLES (8/1*! MESH)• 6-B. OXIDIZED HAT CREEK COAL PARTICLES (8/1'I MESH) FROM SURFACE DEPOSIT (SURFACE COAL). 6 - C NON-OXIDIZED HAT CREEK COAL PARTICLES (8/1*! MESH) FROM 400 FT DEPTH DEPOSIT (CORE COAL), LIGHT MICROSCOPE IMAGE 4.6X SMOOTH LAYERED PARTICLE 20X. FRACTURED PARTICLE 20X. FIGURE 7a- SCANNING ELECTRON MICROSCOPE IMAGES OF POLISHED CROSS SECTION OF DIFFERENT PARTICLES OF OXIDIZED HAT CREEK COAL FROM SURFACE DEPOSIT SHOWING LAYERED AND CRACKED NATURE OF THE PARTICLE SURFACE. MEAN PARTICLE SIZE 8/14MESH  FIGURE 8 : INFRA - RED SPECTRA OF HAT CREEK COALS. A - SURFACE DEPOSITS. B - CORE DEPOSITS. CO The main absorption bands and the s p e c i f i c extinction c o e f f i c i e n t (K) values between 4000 - 250 cm 1 range are l i s t e d i n Table 9. The bands appear broad because of the p a r t i a l or even complete overlapping of the " c h a r a c t e r i s t i c " bands due to the complexity of the coal structure. The -OH absorption band at 3400 cm"1 ( F r i e d e l , 1956 and Osawa, 1971) exists i n both surface and core coal with K 2 " values of 0.30 and 0.26 cm /mg respectively. The bands at 2920 cm assigned for CH^ or and a l i p h a t i c CH stretch ( F u j i i , 1970) have very small i n t e n s i t i e s of 0.06 and 0.08 2 cm /mg i n surface and core coal respectively. This i s usually the case with low rank coals where part of the a l i - phatic CH i s substituted by a hydroxyl OH (F r i e d e l , 1956 and F u j i i , 1970). A shoulder of K value 0.32 cm /mg appears at 1725 cm in the case of surface coal which i s c h a r a c t e r i s t i c of the C = 0 of COOH or the ketonic carbonyl ( F u j i i , 1970; Schitzer, 1972). This shoulder i s p r a c t i c a l l y non-existent i n the case of the core coal spectrum, ind i c a t i n g the absence of -COOH groups and therefore l i t t l e oxidation of the coal sample. The most important absorption band at 1600 cm 1 has 2 a r e l a t i v e l y high K value of 0.55 cm /mg i n the case of 2 surface coal compared to 0.26 cm /mg in the case of core coal. TABLE 9. SPECIFIC EXTINCTION COEFFICIENTS K (cm2/nig)* OF MAIN INFRA-RED ABSORPTION BANDS OF SURFACE COAL AND CORE COAL. Absorption Main Surface Coal Core Coal Band cm-1 Assignment 3700 OH in kaolinite - 0.28 3620 " " - 0.3 3400 OH 0.30 0.26 2920 Aliphatic - CH 0.06 0.08 1725 C=0 unconjugated 0.32 Very weak shoulder 1600 C=0 OH 0.55 0.26 conjugated 1430 - 1450 Aliph.CH and 0.28 0.20 C ' ^ 0 1090 ) ar. C - 0 0.48 1.16 ) C - O - C ) Mineral matter 1035 ) Kaolinite - 0.95 Wt. of sample = 0.8 grams, ar. '.= aromatic. A l l values-are calculated on "As received" basis. It i s recognized that by using a mineral matter-free basis i n ca l c u l a t i n g the s p e c i f i c e x t i n c t i o n c o e f f i c i e n t s , the p o s s i b i l i t y of large va r i a t i o n s w i l l be decreased. 61. This confirms that the oxidized surface coal possesses more carbon-oxygen groups, such as carboxylate COO , also conjugated carbonyl C = 0 HO ( F r i e d e l , 1956 ; F u j i i , 1970 and Schnitzer, 1972). Other weaker bands can be detected in the region between 1430 to 1450 cm * in both coals with s i m i l a r K /0 values. These are assigned for the C structure which can ^ 0 be carbonate, also bands i n that region are related to the a l i p h a t i c CH structure. Considering the mineral matter, the bands at 1055, 1000, 970, 910 cm ^ were assigned to minerals such as k a o l i n i t e ( F r i e d e l , 1956). The spectrum of the core coal exhibits sharp peaks at 1090 and 1035 cm "'"with very high K values of 1.16 and 0.95, respectively, while surface coal shows very weak peaks with lower i n t e n s i t i e s . This can be explained by the presence of a large quantity of "gangue" material (mostly ka o l i n i t e ) in the core samples since the alumina i n the ash is equal to 8.27% d.b. This hypothesis i s supported better by the presence of two sharp absorption bands at 3620 and 3700 cm * i n the spectrum of the core c o a l , while they are non existent i n that of surface coal. These two bands were assigned to the water associated with the mineral k a o l i n i t e (Greenslade, 1975). Moreover, the p o s s i b i l i t y of the presence of a mixed carbonate and k a o l i n i t e "gangue" i n both coals i s supported by the presence of absorption peaks at 1430, 800 62. and 735 cm * which are c h a r a c t e r i s t i c peaks of mineral c a l c i t e . The spectra of activated carbon, shown i n Figure 9 are quite d i f f e r e n t from that of coal. Activated carbon does not exhibit any s i g n i f i c a n t absorption bands on the normal absorbance scale; with 5 times the expansion of the scale, a weak band appears at 1600 cm with very small 2 in t e n s i t y (K value = 0.006 cm /mg). This r e s u l t i s i n good agreement with that obtained by Fr i e d e l i n 1972. 3.3.3 Surface area The results, shown in Table 10, summarize the experimental data which are l i s t e d i n d e t a i l i n Appendix C-l-2. The BET surface areas are calculated by the adsorp- ti o n of nitrogen gas for both Hat Creek coal and activated carbon. The BET equation i s described i n Appendix B-3. The s p e c i f i c surface area measured by t h i s method exhibits very small values for coal i n comparison to activated carbon. Meanwhile, core coal shows about 4 times more surface area than surface coal. Although the micropore volumes follow the same pattern as the surface area values, the average pore diameter of the coal l i e s within the same range as activated carbon. This can be explained by the very large number of micropores present i n the activated carbon which raise the micropore volume. In the case of coal, there are fewer pores with larger pore diameter, of Wave Number , cm"1 ooo I 8 0 0 I 6 0 0 Moo 12oo l ooo FIGURE 9: INFRA-RED SPECTRA OF ACTIVATED CARBON a-water-washed sample b-acid-washed sample c-acid-washed a f t e r adsorption of lead d-water-washed - expanded scale x5. e-acid-washed - expanded scale x5. TABLE 10. SURFACE AREAS, MICROPORE VOLUMES AND AVERAGE PORE DIAMETERS FOR COALS AND ACTIVATED CARBON. BET - Micropore Average pore surface area volume diameter (m2/g) (ml/g) (A) Core sample of coal 11.8 0.0,67 255 Surface sample of coal 3.1 0.042 305 Activated carbon (calgon) 705.9 1.057 310 high average value comparable to that of activated carbon but the surface area and pore volumes have very small values. It has been suggested, not proven, that the areas calculated from the nitrogen isotherm using the BET equation are mostly associated with the external area of the p a r t i c l e s plus that area contained i n the o pores of diameter greater than about 5 A (Marsh, 1965). This explains the very small values of s p e c i f i c surface area obtained for coal. Another p o s s i b i l i t y for the low N 2 area obtained for the coal i s that the g e l - l i k e structure of l i g n i t e may be i r r e v e r s i b l y altered upon drying conducted before the analysis and thus the low nitrogen areas may be apparent. It was seen that coals with a carbon content range of 75-81% tend to have BET nitrogen 7 area of > 10 m , while the carbon dioxide area was i n 2 the order of 100-200 m /gm. on the other hand, the l i g n i t e - v a r i e t y coal with less than 73% carbon content 2 exhibits a n e g l i g i b l e (< 1.0 m /gm) nitrogen area, while a very high carbon dioxide area - reached more 2 than 300 m /gm. 66. 3.3.4 Pore size d i s t r i b u t i o n The pore size d i s t r i b u t i o n curve (Figure 10) was obtained by p l o t t i n g the incremental volume over the incremental diameter against the average pore diameter d (Fornwalt, 1966). The d i s t r i b u t i o n curve f o r the core coal shows a very d i s t i n c t peak corresponding to the t r a n s i t i o n a l pores with diameters between 60 - 300 °A. In comparison, surface coal shows a minor peak in the t r a n s i t i o n a l range and a major peak corresponding to a higher percentage of pores with a larger micropore region of > 200 °A. The points were i n s u f f i c i e n t to complete this peak because the pore volume measurements were taken up to only 372 °A. Activated carbon has the highest peak on the curve within a range of diameters of 50 - 70 °A. •This represents a system approaching micropores. The pore size d i s t r i b u - t i o n of activated carbon, using nitrogen, permits rapid penetration by gases (with t h e i r widely separated molecules) but not by l i q u i d s , e s p e c i a l l y those with long chain molecules (Fornwalt, 1966). This i s mainly the reason f o r the large N 2 area obtained for activated carbon and the n e g l i g i b l e one obtained for coal. AVERAGE PORE DIAMETER , d (A) FIGURE 10 PORE SIZE DISTRIBUTION CURVE FOR HAT CREEK COAL AND ACTIVATED CARBON CALCULATED FROM NITROGEN ADSORPTION ISOTHERM AT 77°K. 68. Therefore, coals with t h e i r highest percent of t o t a l pore volume lay i n the t r a n s i t i o n a l and macropore range. They are, accordingly, expected to be most suitable for use for adsorption of long chain molecules from l i q u i d phases. 3.3.4 Permeability test Table 11 shows the degree of permeability K i n cm/sec at 20°C, which i s calculated for four sizes of Hat Creek coals. These results compare favorably with those for s o i l or sand of comparable sizes (Karol, 1969). The K values for the p a r t i c l e sizes 3 and 60 mesh Tyler proved to give a suitable hydraulic conductivity to pass s a t i s f a c t o r y volumes of wastewater during the loading process, and therefore a l l the column leaching experiments have been conducted using these two granular p a r t i c l e s i z e s . The 150 mesh and the fines show a very low degree of permeability and therefore they were not used i n the adsorption processes during the course of t h i s work. TABLE 11. DEGREE OF PERMEABILITY OF SURFACE HAT CREEK COAL Sieve size - . Permeability K Mesh cm/sec at 20° C 3 1.3 X 10" 2 60 4.4 X 10" 3 150 1.5 X 10" 4 Fines 9.87X 10" 5 69. 3.3.5 Iodine number The iodine number of surface Hat Creek coal was compared with other types of coal of the same rank, activated carbon and construction sand. The summary of the results are reported i n Table 12. TABLE 12. IODINE NUMBER OF HAT CREEK COAL- COMPARED WITH OTHER ADSORBENTS Range of Iodine Number (based on t r i p l i c a t e samples) 1. Activated carbon 750 -• 950 2 . Hat Creek coal 105 -- 158 3. Union Bay coal (Vancouver Island) 110 -- 160 4. Construction sand 1.4 • -3.2 Activated carbon exhibits the largest adsorptive capacity towards iodine which i s found to be numerically equal to the nitrogen area (U.S.E.P.A., 1973). The value for activated carbon i s approximately 7 times greater than that of coal, very s i m i l a r values have been obtained for both Hat Creek and Union Bay coal, while in comparison with construction sand, the l a t t e r has a very small value of iodine number, approximately 60 times less than that of coal. The iodine uptake i s not only a function of surface area and porosity, but depends rather complexly on the iodine reagent interaction with the compounds of the coal as well as the type of the coal used (Roy, 1957). The BET surface areas of coal are very small when compared with values obtained from the iodine numbers. The reason l i e s i n the fact that thermal contraction of coal to l i q u i d nitrogen temperatures makes nitrogen sorption at very low temperatures an activated process. For a l l p r a c t i c a l purposes, the BET surface area can be more or less equated with the external surface presen- ted by the p a r t i c l e s of the test sample. The l i q u i d phase adsorption, which i s our interest, demonstrates c l e a r l y that the iodine number value is by far the better measure of the " r e a l " surface area, which the sample would present to a reagent. "In the case of activated carbon, the reasonable . correspondence between the BET surface area and the iodine values are associated with the fact that activated carbon, unlike coal, offers a r i g i d carbon skeleton and does not therefore thermally contract to such an extent so that pene- tr a t i o n of i t s pore volume at a very low temperature i s much more d i f f i c u l t than at room temperature "(Berkowitz ,119 7.7) * D i v i s i o n , Alberta Research Direct communication. Berkowitz, N. Fuel Science Council, Edmonton, Alberta. 71. V. SORPTlVE aiARACTERISTJ.es . Preface: This part of the research program deals with the study of Hat Creek coal as a possible .adsorbent material for water p u r i f i c a t i o n and the evaluation of i t s adsorptive capacity for the removal of the main pollutants which are not adequately removed by conventional secondary treatment processes. In this work, synthetic wastewaters were used rather than actual wastes in order to control the strength and the composition of the tested materials, also to f a c i l i t a t e the measurements and to avoid the p o s s i b i l i t y of any complexation that may occur between organic and inorganic materials. Table 13 indicates the simulated wastewaters, and the materials used i n the synthetic wastewaters prepared for the experiments. Descriptions of the reagents are included i n Appendix B-4-1. Both batch contact and column adsorption tests were performed to evaluate the adsorptive capacity of oxidized Hat Creek coal, mined from the surf ace , to' remove each material either separately or in some combinations. Several tests were conducted using activated carbon, Abbotsford s i l t loam and construction sand for comparison pur- poses. These materials were described e a r l i e r in Chapter I I I . TABLE 13. SOLUTIONS TESTED Po l l u t i n g Materials in Actual Wastewaters for Examination 1. Heavy metal ions: lead, cadmium, mercury, copper, zinc, and chromium 2. Dissolved organics: (oxygen demanding material) 3. Phosphate ions (PO. ) 4. NO -N 5. NH3-N 6. Phenol 7. Cyanide (CN") Synthetic Wastewater Used for Tests metal n i t r a t e solutions (details i n Appendix B-4-1) beef extract solution (COD: TKN =9:1) sodium phosphate solution sodium n i t r a t e solution ammonium sulfate solution ammonium n i t r a t e solution l i q u i f i e d phenol potassium cyanide solution 73. 1. DESIGN OF EXPERIMENTS (COULTHARD, 1974). 1.1 Batch contact process A series of known concentrations, covering a wide range, were prepared from each material l i s t e d in Table 13. A volume of 100 mis of each concentration was then mixed with d i f f e r e n t per- centages of coal 1, 5 and 10% w/w for each of the four average p a r t i c l e sizes 0.533 mm, 0.2965 mm, 0.117 mm and 0.03414 mm as shown in Appendix B-4-2. The solutions were then shaken continuously at room temperature on a standard mechanical shaker at 150-200 cycles per minute for a contact time of 8 hours. The contact time was determined by performing preliminary experiments i n which fixed volumes of the solution were contacted with a fixed weight of coal for d i f f e r e n t periods of time ranging from 1 hour to 24 hours. A contact time s u f f i c i e n t l y long to ensure a reasonable approach to equilibrium was chosen at 8 hours for a l l materials tested. Details are shown elsewhere (Coulthard, 1974) . The residual concentrations of the material have been determined and the adsorptive capacity of the coal toward such material was calculated in terms of milligrams of material removed per gram of coal. Data from the batch experiments were then u t i l i z e d i n p l o t t i n g the adsorption isotherms. 1.2 Column test .(Coulthard, 1974) This semi-continuous test was conducted to compare the column process to the batch process i n terms of adsorptive capacity. 74. Small columns of dimensions 20 cm X 7 cm I.D., containing . approximately 600 grams of coal were used. Experimentation was carried out on the four p a r t i c l e sizes of coal using the same series of the solution strengths employed in the contact process. The volume of solution was 500 mis applied at a flow rate of 1 ml/min. The effluents were withdrawn from the bottom of the column and subsequently analyzed for retention con- centration . 1.3 Continuous column test (Coulthard, 1974) A larger column of dimensions 2 meters X 15.24 cm I.D., was employed to evaluate the adsorptive capacity of the coal, and i t s l i f e time to remove certain pollutants or combinations under stationary bed-type conditions. About 28 Kgs of coal was contained i n the column which consisted of a granular p a r t i c l e size of 0.533 mm average diameter. The solution containing the material to be adsorbed was continuously applied to the column at a flow rate equivalent to 2 1 Imp gpm/ft to provide 30-35 minutes of contact time. The "break through point" was a r b i t r a r i l y set up at the lower l i m i t of i o n i c concentration recommended by the Public Health Water Quality Standards (B.C. Dept. of Health Service, 1969; C a l i f o r n i a Water Quality C r i t e r i a , 1963). F i l t e r candles were inserted at each 30.5 cm (1 ft) l e v e l in the column beginning at the 15.25 cm (6 in) l e v e l to enable sampling from various depths of the column. 75. A schematic diagram for the column i s shown i n F i g u r e l l . E f f l u e n t samples were co l l e c t e d p e r i o d i c a l l y from d i f f e r e n t levels for analyses. 2. DESCRIPTION OF SORPTIVE TESTS. 2.1 Heavy metals Known concentrations of the 6 heavy metal ions lead, copper, zinc, cadmium, chromium and mercury were prepared for the series of the outlined contact and leaching experiments. The reagents used are included in Appendix B-4-1. The concentration of metals in the charging stock solutions was varied and the lower l i m i t of ionic concentration was guided by the Public Health Drinking Water Standards as shown in Table 14.. TABLE 14. PUBLIC HEALTH DRINKING WATER STANDARDS Chemical Limits mg/1 Permissible (a) Objective U.S.P.H.S.(b\ Lead 0.05 N.D.* 0.05 Zinc 5.00** < 1.0 5.0 Copper 1.00** r < 0.01 1.0 Cadmium 0.01 N.D. 0.01 Chromium 0.05 N.D. 0.05 Mercury • - 0.005 mg/1*** : - - : ' a B.C. Dept. of Health Service, 1969. b McKee and Wolfe, 1963 * Not detectable ** Recommended standard *** U.S.S.R. objective VENT 76. OVERFLOW < TANK INFLUENT PUMP © ^ T © lAAA.-V f v v v v A A A A w v v A A f l A W W A A A A [ W W A A A A , w w fl(AAA | v v w A A A A [ W W XXX^ W W A A A / ) © XX) | W \ , A A A A J vS/vvt AAAA! © © 6* I.D. W v V t A A A A J A A A A J WvS. A A A J I A A A A N W W A A A A S / V W I A A A A J A A A A A A A I ^COAL, particle size 0.533 mm LA, AAA S / v w AAA WW AAAA v /wv AAAA w \ A / AAAA W W AAAA V * i / W ' — A [AAAA j w v v IAAAA IAAAA WWW JAAAA (VN/W SvA SCREEN EFFLUENT - > T O DRAIN © TO © SAMPLING POINTS. COLUMN DIMENSIONS - 2m x 15.25 cm I.D. F I G U R E l1 : S C H E M A T I C D I A G R A M O F T H E C O N T I N U O U S COLUMN P R O C E S S . 77. For example, the lead solution tests contained a series of 0.05, 0.1, 0.2, 0.5, 5.0, 50 and 500 mg/1. The concentrations for the other metals are shown in the tables included in Appendix C-2. In the case of using the larger bed for continuous leaching, a 5 mg/1 lead solution was applied continuously to the 2 column at a flow rate of 1 gpm/ft u n t i l the break through point (e.g. an e f f l u e n t of 0.5 mg/1, Pb) was reached. 2.1.1 S e l e c t i v i t y towards heavy metals The same test coal bed was then used to treat a synthetic e f f l u e n t containing s i x elements i n combination, lead, mercury, chromium, zinc, copper and cadmium, each contributing 5 ppm concentration respectively. The l e v e l of each element in the withdrawn sample was measured, the influent was applied con- tinuously u n t i l the break through point of 0.5 mg/1 was attained. 2.2 Dissolved organics A series of beef extract solutions were prepared for the organic t e s t s . Beef extract i s a material which contains a l l of the organic nutrients necessary as a substrate for the b a c t e r i a l culture. In addition, beef extract solutions may be prepared to desirable and predictable concentrations without contamination from other elements. In this respect, there are, for example, only the BOD^, COD and TOC values, excluding the side effects of other possible toxic compounds which would be experienced in sewage wastewater. Both contact and column adsorption methods were employed. 78. The majority of the experiments, for organics however, were confined to the use of only two p a r t i c l e sizes of coal namely 0.5 33 mm and 0.2965 mm average value. Several experiments carried out with fine p a r t i c l e s i z e s , e.g. 0.03414 mm, e s p e c i a l l y i n the column adsorption process, indicated that the small pores in the coal bed quickly "blocked" with organics and consequently the head loss increased and prevented the passage of any f l u i d through the column bed. Nevertheless the fine size (0.03414 mm) was used successfully i n the contact (batch) pro- cess . Mineral nutrients were added i n the stock solution for some t r i a l s to determine i f these elements (Fe, Ca, Mg, etc.) were in the coal i n s u f f i c i e n t strengths to stimulate a good b a c t e r i a l growth. Some experiments were ca r r i e d out with activated carbon and construction sand to compare t h e i r removal capacities with that of Hat Creek coal. To explore the e f f e c t of heavy metals on organic solutions measured amounts of lead were added to the i n f l u e n t beef extract solutions. Only a few experiments have been conducted owing to the time available. Inoculation of the coal bed: One l i t e r of the beef extract solution was applied to the fresh coal bed with a very slow flow rate 5-6 mls/min. The column was allowed to drain, then washed with clear tap water, drained, and allowed to "mature 79. for three days before application of further organic solutions. . This procedure allows the b a c t e r i a l growths to e s t a b l i s h within the coal and i t s pores. 2.3 Phosphates Both column and contact process were employed to deter- mine the capacity of the coal to adsorb phosphate ions. Tests to study the effect of p a r t i c l e s i z e , coal dosage, contact time and phosphate concentration were carried out. It i s known that most s o i l s have a good capacity to remove and r e t a i n phosphates present in solution. To compare the coal's capacity with s o i l , some leaching t r i a l s with an Abbots ford sandy loam were c a r r i e d out 2.4 Nitrates Standard n i t r a t e solutions of various concentrations were used for both the contact and column process. Some batch tests were also t r i e d using coal samples a f t e r washing out the o r i g i n a l l y present n i t r a t e i n the coal and the results compared with that obtained with the unwashed samples. 2.5 Ammonia A series of experiments have been conducted using both contact and column techniques. Both ammonium n i t r a t e and ammonium sulfate have been u t i l i z e d to provide known ammonia concentrations. I n i t i a l concentrations of ammonia of 50 mg/1 and 10 mg/1 were also employed. Results obtained with both surface and core coal samples were compared to that obtained with activated carbon. 80. 2.6 Phenol A phenol solution containing approximately 5 mg/1 con- centration was used in both the contact and the column experi- ments. Also the e f f e c t of pH change on the removal of phenol was determined, and some tests were conducted using activated carbon for comparison. 2.7 Cyanide A cyanide solution containing approximately 2 mg/1 of cyanide ions was used in both the contact and the column tests. The e f f e c t of the pH was also studied. Some tests were conducted using activated carbon for comparison. 3. ANALYTICAL METHODS. 3.1 Heavy metals The Atomic Absorption Spectrophotometer (Perkin-Elmer Model 303) was used for most of the measurements. The flame atomic technique using a deuterium' lamp for the background correction'was used for a l l heavy metals, except mercury, which required a flameless or cold vapor technique for i t s release ( J a r r e l Ash report No.Hg-1, 1970). In this technique the mercury samples were a c i d i f i e d with ^SO^ and l a t e r oxidized with K Mn 0^. The permanganate additive was neutralized with hydroxylamine hydrochloride (HONO^ CI) and aerated after addition of stannous chloride (SnCl). The mercury released was analyzed i n a flameless c e l l on a J a r r e l Ash Atomic Absorption Spectrophotometer. 81. The standardized instrument settings and detection l i m i t s for each metal were as shown i n Appendix B-4-4. The samples con- taining the metals were a c i d i f i e d by adding enough n i t r i c acid to lower the pH to below 2 before analyses. Samples with low concentration levels below the detectable l i m i t s of the instruments were concentrated by evaporation. 3.2 BOD5 and COD These analyses were conducted i n accordance with the chemical methods described with the A.P.H.A. Standard Methods for the examination of water and wastewaters, (14th Ed., 1975). 3.3 Total organic carbon These analyses were determined by automated method on a Beckman Total Organic Carbon Analyzer, Model 915. 3.4 Phenol and cyanide These analyses were carried out by the Pesticide Laboratory, B.C. Ministry of Agriculture i n accordance with the A.P.H.A. Standard Methods, 1975. The following analyses were determined by automated methods on a Technicoh Industrial Auto Analyser II. 3.5 Ammonia Nitrogen (NH^-N) Ammonia was determined by means of the Berthlot Reaction i n which a green colour i s developed with phenol and sodium hypochlorite. The colour i n t e n s i t y i s read at 630 nm. The detection l i m i t i s 0.2 mg/1 NH7-N. 82 . 3.6 Nitrate-Nitrogen (NOj-N) The n i t r a t e i s reduced to n i t r i t e by hydrazine and a copper c a t a l y s t . The n i t r i t e then forms a pink dye by d i a z o t i z a t i o n . The colour i s read at 520 nm. The detection l i m i t i s 0.02 mg/1 NCyN. 3.7 Orthophosphate Phosphorus (0-P0 4"P) : The orthophosphate reacts i n acid s o l u t i o n with ammonium molybdate and ascorbic acid to give molybdenum blue which has an absorption maximum at 660 nm. The detection l i m i t i s 0.2 mg/1 0-P04-P. 3.8 Total-N and Total-P The sample i s automatically digested with concentrated F^SO^ containing selenium and p e r c h l o r i c a c i d . Organic nitrogen is converted to ammonia, and organic phosphorus to orthophosphate which i s then determined simultaneously by the Berthlot and molybdenum blue procedures respectively. The detection l i m i t i s 0.05 mg/1 N and P. 83. 4. RESULTS AND DISCUSSION General Adsorption isotherms: The sorptive capacity of the coal can be measured by determining the adsorption isotherms (Culp, 1971) which are considered the most convenient form for representing the experimental data obtained from the batch tests for the various substances. The adsorption isotherm i s the r e l a t i o n s h i p , at a given temperature, between the amount of a substance adsorbed and i t s concentration i n the surround- ing solution. In d i l u t e solutions, such as wastewaters, the values are plotted on a logarithmic scale usually y i e l d i n g a straight l i n e . In t h i s connection, a useful empirical formula i s the Freundlich equation which i s not derived from t h e o r e t i c a l concepts such as the Langmuir and BET equations, but i s none- theless useful i n r e l a t i n g the amount of impurity i n the solution to that adsorbed as follows (Hassler, 1974). where 1 X/m = K C n X = amount of substance adsorbed m = weight of coal or carbon X/m = amount of substance adsorbed per unit weight of coa K and n = are constants (log K i s the intercept § ~ i - s the slope) C = unadsorbed concentration of substance i n the solution 84. A reading, therefore, taken at any point on the isotherm gives the amount of substance adsorbed per unit weight of coal which is the adsorptive capacity at a p a r t i c u l a r concentration. The effectiveness of the removal i s measured i n t h i s work by two parameters. a) The milligrams of substance removed per gram of coal applied. b) The percentage removal e f f i c i e n c y which i s the amount removed compared to the amount i n the o r i g i n a l solution. The c a l c u l a t i o n of these values i s based on the s e n s i t i v i t y of the measuring instrument used for the analysis as well as i t s detectable l i m i t f or each substance. For example, with weak solutions, the s e n s i t i v i t y of the instrument would not allow detection of metal ions l e f t i n the solution and therefore the detectable amount removed was found to approach 100% i n the weak solutions for a l l of the heavy metals tested. 4.1 Heavy Metals 4.1.1 Batch Tests Complete randomized design were applied i n the experiments for batch tests (Leclerg, 1966) i n Which four independent variables were considered; these are: type of heavy metal ions, solution concentration, coal dosage and p a r t i c l e size of coal. 85. The dependent variable i n a l l experiments i s the adsorptive capacity of the coal i n mgs metal ions removed per 1 gram of coal. A t o t a l of 648 isotherm tests are included i n t h i s experimental design; each test deals with one v a r i a b l e at a time while the others remain constant. The r e s u l t s obtained from the tests are tabulated i n d e t a i l i n Appendix C-2-1, Table 1 to Table 20 i n c l u s i v e . The a p p l i c a b i l i t y of the Freundlich isotherm was tested for each of the 648 sorption tests using l i n e a r regression analysis. Slopes, intercepts and c o r r e l a t i o n * c o e f f i c i e n t s were then calculated for the isotherms and the data i s included in Appendix C-2-2. The isotherms obtained with lead, mercury, copper and zinc show l i n e a r r e l a t i o n s h i p s i n Figure 12a, and therefore they can be interpreted by using the Freundlich isotherm equation. Cadmium and chromium behave d i f f e r e n t l y ; r e l a t i v e l y poor c o r r e l a t i o n c o e f f i c i e n t s are obtained for t h e i r isotherm data while the l e v e l l i n g out of the points at equilibrium concentration higher than 100 mg/1 indicates a saturation stage i s probably reached as shown i n Figure 12b. This may be due to the i n s u f f i c i e n t coal dosage used i n t h i s test (1% by wt). Therefore, f o r cadmium and chromium adsorption systems, a Freundlich isotherm may not be applied for interpretation of the data obtained. 85a. Hg o r*-.98061 Pb * r8- .98764 Co • rs- .89472 Zn A r3-.88908 1 1 1 .01 .1 1.0 io. EQUILIBRIUM C0NC. mg/ l 100. 1 0 0 0 FIGURE ]2A- ADSORPTION ISOTHERMS FOR REMOVAL OF HEAVY METAL IONS BY COAL. 85b. .01 .1 I.O 10. 100. 1 0 0 0 EQUILIBRIUM CONC. m g / l FIGURE 12B- ADSORPTION ISOTHERMS FOR REMOVAL OF HEAVY METAL IONS BY COAL. 86. The maximum adsorptive capacities for a l l metals at an i n i t i a l concentration of 500 ppm were estimated by extrapolation of the isotherm l i n e . Some values are compared i n Table 15. A l l r e s u l t s show that the mercury isotherm l i n e has the steepest slope i n d i c a t i n g the highest adsorptive capacity as well as the greatest e f f i c i e n c y i n column operation, while the chromium isotherm l i n e has the least slope and correspondingly the poorest e f f i c i e n c y of removal. Lead exhibits a very high removal e f f i c i e n c y and i s categorized as second after mercury. Copper, zinc and cadmium can be categorized together as they have intermediate adsorptive a f f i n i t i e s towards coal and exhibit s i m i l a r values. Therefore, the six heavy metals may be l i s t e d i n sequence according to t h e i r a f f i n i t y towards coal as follows, s t a r t i n g at the highest a f f i n i t y : Hg > Pb > Cu > Zn > Cd > Cr. 4.1.2 Comparison with activated carbon Figure 13 shows a comparison between the three adsorp- t i o n isotherm l i n e s obtained for the adsorption of lead by oxidized surface coal, unoxidized core coal and Calgon activated carbon. The data are tabulated i n Appendix C-2-3. When the maximum adsorptive capacity is measured at 50 ppm, the oxidized coal exhibits the greatest adsorptive capacity of 217 mgs lead 87 TABLE 15. COMPARISON OF THE ADSORPTIVE CAPACITIES OF SURFACE COAL TOWARDS SIX METAL IONS Contact time = 8 hrs Coal dosage =1% Particle size = 0.03414 mm Metal ion Maximum adsorptive capacity (x/m)5no* mgS metal ion/gram coal Correlation coefficient 2 for the isotherm r data Mercury Lead Copper Zinc Cadmium Chromium 6123 110 70 36 19 8 0.9806 0.9876 0.8947 0.8891 0.7947 0.8478 * Cx/m)50Q = maximum adsorptive capacity obtained by extrapolation of the isotherm line to i n i t i a l concentration of 500 mg/1. FIGURE 13 : ADSORPTION ISOTHERMS FOR REMOVAL OF LEAD BY HAT CREEK COAL AND ACTIVATED CARBON. co 39. per gram coal while unoxidized coal shows about h a l f of this value i n the order of approximately 125 mgs lead per gram coal. This indicates that surface oxides on the coal l i k e l y play an important role in the adsorption mechanisms concerning heavy metals. Therefore i n t e r e s t was focussed i n th i s study on determining the role of surface oxides i n removing lead ions from solutions by coal. In comparing Hat Creek coal with the activated carbon, the l a t t e r exhibits very poor adsorptive capacity towards lead, only 19.3 mgs lead ions per gram of coal. Therefore activated carbon w i l l not be competitive with coal in adsorption of heavy metals from a solution. 4.1.3 Variables influencing adsorption A q u a l i t a t i v e evaluation of the e f f e c t s of some of the experimental variables on the adsorption e f f i c i e n c y was made using the data shown in Appendix C-2-1. 4.1.3.1 Contact time Preliminary batch tests were conducted for exposure periods of between 1 hour and 24 hours to determine the optimum contact time. A l l results are included i n Appendix C-2-4:l. Figure 14 shows the adsorption of lead as a function of contact time. A rapid approach towards equilibrium was evident. Reduction of the ef f l u e n t concentration was continued as the contact time increased u n t i l at about 8 hours, when the reduction obtained was the same as those obtained at a longer time of exposure. Therefore, 8 hours was considered s u f f i c i e n t l y long to ensure a reasonable approach to equilibrium, and was 90, 50 B"=p ADSORBENT: oxidized Hat Creek coal DOSAGE : 1 % w/w AVG. COAL SIZE: 0.533mm dia. INFLUENT CONC: 50 mg/1 6 8 10 CONTACT TIME . hrs. equilibrium time 8 hr. 16 FIGURE 14 : EFFECT OF CONTACT TIME ON ADSORPTION OF LEAD. 91. adopted for a l l further batch testing. 4.1.3.2 Coal dosage The minimum amount of coal necessary for the e f f e c t i v e removal of heavy metals from a known volume of solution of cer- tain concentration was determined. The test results l i s t e d in Appendix C-2-4-2 show that more reduction in the residual concentration i s obtained by increasing the coal dosage with a greater increase in the removal e f f i c i e n c y . The increase i n e f f i c i e n c y i s more s i g n i f i c a n t at high influent concentration, mostly about 50 ppm. Figures 15a and 15b show the e f f e c t of a coal dosage on the remaining concentration and the removal e f f i c i e n c y of copper by coal. The e f f i c i e n c y of removal of copper from a solution concentration of 500 ppm increases from 32.9% when 1% w/w coal i s used to over 92% when the coal dosage i s increased to 5% w/w. The same conclusions were obtained with other heavy- metals tested except with mercury where the e f f e c t of carbon dosage i s not s i g n i f i c a n t because of the great a f f i n i t y of mercury to be adsorbed with a minimum e f f i c i e n c y . o f not less than 90% at a l l concentration l e v e l s . 4.1.3.3 Concentration of solute The dependence of adsorption capacity of coal upon the concentration of the metal ions i n the solution phase i s expressed by data summarized i n Table 16 for the adsorption of mercury. For a l l metals, i t i s obvious that the adsorptive capacity of coal 92. COAL DOSAGE (% w/w) FIGURE 15a : EFFECT OF COAL DOSAGE ON ADSORPTION OF COPPER. 93. Influent Solution Concentration i mg/1 • FIGURE 15b : CONTACT PROCESS, COPPER. EFFECT OF COAL DOSAGE. coal p a r t i c l e size:0.2965mm. contact time:8 hours. 94. TABLE 16. EFFECT OF SOLUTE CONCENTRATION ON THE ADSORPTIVE CAPACITY OF MERCURY. Contact Time: 4 hours Coal dosage: 1% w/w Mean coal p a r t i c l e s i z e : 0.2965 mm. Influent Solution Cone. mg/1 Efflu e n t Cone. mg/1 mg Hg Removed per gm Coal % Removal 0.1 <0.031 0.0069 >69 0.5 <0.04 0.046 >92 5 0.112 0.4888 9 7.76 50 0.35 4.965 99.3 100 0.5 9.95 99.5 250 12.56 23.744 94.98 500 56 44.4 88.8 95. increases with increasing the equilibrium concentration of the metal ions. The rate of increase d i f f e r s for d i f f e r e n t metal ions, as shown i n results included i n Appendix C-2-4-3. In the case of mercury the rate of increase i s l i n e a r as shown i n Figure 16a which indicates the di r e c t p r o p o r t i o n a l i t y of the increase i n coal capacity with the increase of metal con- centration. The results confirm that a multiple increase of 5 times the concentration of mercury w i l l be equivalent to 5 times the increase i n the adsorptive capacity of coal. A s i m i l a r l i n e a r r e l a t i o n s h i p i s obtained i n the case of adsorption of lead. With other metals, such as copper, zinc and cadmium, a non-linear increase i n capacity with increasing concentration is obtained which i s shown in Figure 16b for copper. Cadmium and zinc show the same shape of a curved l i n e . Also this graph shows that the increase i n the solute concentration i s accom- panied by a gradual drop i n the removal e f f i c i e n c y of such metals, while i n the case of mercury no appreciable drop i n e f f i c i e n c y i s noticed. Chromium exhibits a d i f f e r e n t behavior as i t has the poorest adsorptive capacity among the metals examined. The results indicate that the adsorptive capacity continues to i n - crease with an increase i n the concentration up to 200 ppm, a f t e r which a s i g n i f i c a n t drop in capacity was noticed. Therefore, the relationship between solute concentration and adsorptive capacity can be considered rather than a system-specific which exhibits d i f f e r e n t behaviors in d i f f e r e n t adsorption systems. 96 0 60 100 150 200 250 300 350 400 400 450 ^ Influent Solution Concentrat ion . m g / | . FIGURE 16 ! EFFECT OF METAL ION C0CENTRATI0N ON ADSORPTION. a - MERCURY. b-COPPER. coal size:0.2965, contact time:4hrs. 97. Apparently, the a f f i n i t y of the metals towards coal controls the nature of such a r e l a t i o n s h i p . For example, metals with the highest a f f i n i t y exhibit a l i n e a r r e l a t i o n s h i p . 4.1.3.4 P a r t i c l e size of coal The isotherm tests conducted with four d i f f e r e n t p a r t i c l e sizes of coal ranged from granular 0.533 mm average to less than 0.03414 mm. Generally, a l l the results (Appendix C-2-4-4) show that reduction in the p a r t i c l e size of coal would increase the adsorptive capacity. However, the breaking up of large p a r t i c l e s to form smaller ones quite probably serves to open some tiny channels in the coal which then become available for adsorption, thus s l i g h t l y increasing the dependence of equilibrium capacity on p a r t i c l e size above a simple v a r i a t i o n with the inverse of the diameter (Weber, 1963). Figure 17a shows that the e f f e c t of p a r t i c l e size i s less s i g n i f i c a n t at lower concentrations. The inverse rela t i o n s h i p between the p a r t i c l e size and the adsorptive e f f i c i e n c y i s i l l u s t r a t e d i n Figure 17b. Higher equilibrium concentrations are obtained when larger p a r t i c l e sizes of coal were used. Also the data show that the e f f e c t of the p a r t i c l e size on the adsorption process is not s i g n i f i c a n t when higher carbon dosages are used. The obtained r e l a t i o n s h i p , shown on the above mentioned figures, indicates that the v a r i a t i o n should be with the r e c i p r o c a l of some higher power of diameter rather than a simple power. This means that i n t r a p a r t i c l e FIGURE 17 : EFFECT OF PARTICLE SIZE OF COAL ON ADSORPTION, a - LEAD. b - MERCURY. 99. transport i s involved rather than a simple mechanism of adsorption on s p e c i f i c external s i t e s (Crank, 1956). However, upon s t a t i s t i c a l analysis of a l l factors considered, the e f f e c t of p a r t i c l e size i s r e l a t i v e l y the least s i g n i f i c a n t parameter. The point i s shown c l e a r l y in the table of analysis, included i n Appendix C-2-5. ' 4.1.4 S t a t i s t i c a l analysis The 4-way analysis of variance technique (Leclerg 1966) was applied to test the s i g n i f i c a n c e of the main variables (described in Section 4.1.3) and t h e i r i n t e r a c t i o n . A summary of t h i s analysis i s included i n Appendix C-2-5. The results show that the main variables are highly s i g n i f i c a n t . In addition, a highly s i g n i f i c a n t two-way and three-way i n t e r a c t i o n between variables i s shown, which are very d i f f i c u l t to interpret s t a t i s t i c a l l y and u sually lead to misleading conclusions. Therefore, i t i s not recommended by s t a t i s t i c i a n s * to consider the r e s u l t of a s t a t i s t i c a l analysis i n the discussion of t h i s work. Neglecting the i n t e r a c t i o n problem, the results of the analysis regarding the main e f f e c t s are i n very good agreement with the expected conclusions from the experimental data. Kozac, A., Professor of S t a t i s t i c s and Biometrics, Dept. of Forestry, U.B.C., personal communication. 100. 4.1.5 Column adsorption tests In this semi-continuous experiment, the same magnitude and order of metal ion concentrations was employed as i n the batch tests. The detailed tables of results including the test of the e f f e c t of d i f f e r e n t variables on the process are l i s t e d i n Appendix C-2- 6. Further tables and the corresponding graphs may be found elsewhere (Coulthard, 1974). The graphical representation of the data obtained for mercury when 500 mis of solution of d i f f e r e n t concentrations was applied through the coal bed, are shown i n Figure 18 . The results and graphs obtained with the other heavy metals are very s i m i l a r to that shown for mercury. A l l experimental results show that the column process i s the most e f f e c t i v e method to be applied for the adsorption of metal ions by coal. A l l metal ions were removed with an e f f i c i e n c y approaching 100% for a l l i n i t i a l concentration levels. A comparison between the adsorption e f f i c i e n c y of the six metals i s summarized i n Table 17. It i s obvious that the order of a f f i n i t y of the s i x metals from the column test i s very s i m i l a r to that obtained with batch tests. While mercury and lead have the highest a f f i n i t y , chromium exhibits the lowest one and the other metals range between these two. 101. Influent Solution Cone. . m g / | . FIGURE 18 : COLUMN ADSORPTION PROCESS , MERCURY. 2 flow rate:0.3gpm/ft , contact time: 30 minutes, coal p a r t i c l e sizes:0.533,0.2965,0.117&0.03414 mm TABLE T7. COLUMN ADSORPTION PROCESS COMPARISON BETWEEN ADSORPTION OF DIFFERENT HEAVY METALS. Volune of Solution = 500 mis Rate of Flow =0.3 gpm/ft2 Contact Time = 30 minutes Depth of Column = 9 inch (600 gms Coal) 0.296S mm Heavy j 2 3 4 5 6 totals x Tested MERCURY LEAD COPPER CADMIUM ZINC CHROMIUM Solution C R Cone, mg/1 t Removal Ce Removal Ce % Removal Ce % Removal Ce . % Removal Ce % Removal b.i >0.002 >98-100 <0.018 >91-100 . - <0.003 > 98.5 - <0.02 >80.0 0.2 - - <0.018 >95.5-100 - .'• • • <0.003 > 98.5 - v - - - 0.5 0.0055 98.9 <0.02 >98-100 <0.048 >90.4-100 <0.004 > 99.2 0.057 88.60 <0.02 >96.0 5.0 >0.002 99.96 <0.02 >99.8-100 . 0.056 98.88 <0.03 > 99.7. 0.067 98.66 <0.045 >99.0 50.0 0.008 99.98 <0.02 > 99.98 0.087 99.83 <0.03 > 99.97 0.050 99.90 0.08 99.84 100.0 0.0088 99.99 - • ; -. • 0.156 99.84 - - , - 0.059 99.94 0.16 99.84 250.0 0.0110 99.99 - - 0.139 99.94 - • - 0.075 99.97 0.08 99.96 500 0.0045 100.0 <0.02 >99.99 3.401 99.34 <0.03 > 99.997 2.39 99.52 0.27 99.95 * C e " equilibrium concentration mg/1 SENSITIVITIES: Pb • Hg - 0.06 0.002 Cu Zn = 0.003 ) = 0.01 ) mg/1 Cd » 0.00S Cr = 0.05 ) t—1 o 103. In column adsorption tests, the time of contact i s of greater importance than solute concentration or p a r t i c l e size as shown i n the analysis l i s t e d i n Appendix C-2-6. This gives a great advantage for the coal when used i n practice for wastewater treatment. This short term column test allowed only a rough evaluation of the method's effectiveness. The throughput volumeof 500 m i l l i l i t e r s was not s u f f i c i e n t to estimate the adsorptive capacity and service l i f e of the coal i n the bed and therefore the longer term experiments were conducted. 4.1.6 Long term column adsorption The results reported i n Appendix C-2-7 are a record for the d a i l y effluent concentration of lead influent and the corresponding effluent at each 1 foot l e v e l throughout the bed depth, beginning at the 15.25 cm l e v e l . The data displayed in Figure 19 show the b e n e f i c i a l effectiveness of the coal to adsorb lead ions by operating continuously for approximately 32 days. During that period of time, 1007 Imp gallons of , solution reduced the lh f t l e v e l e f f l u e n t concentration to 0.03 mg/1 of lead which i s well below the drinking water standard of 0.05 mg/1, recommended by both B.C. guidelines and APHA. The adsorption capacity during t h i s period was evaluated as 9.66 mgs lead ions per gram of coal on the basis of the break through point at 0.5 mg/1 eff l u e n t concentration from the 6" l e v e l . The e f f i c i e n c y of removal was high and approaching more than 80% in value. The d e t a i l s of t h i s estimation i s described i n Appendix C-2-7. 2 4 6 8 IO 12 14 |6 18 20 22 24 26 28 30 DAYS OF OPERATION FIGURE 19 REMOVAL OF LEAD THROUGH COAL COLUMN diam.6"(15.24cm.) x 2m. length. o 4.1.7 S e l e c t i v i t y i n adsorption of mixed metals A mixture of the six metals, consisting of about 5 mg/1 of each were applied through the same bed, previously used for the adsorption of lead. Results from monitoring the equilibrium concentrations during a period of operation of 19 days continuous operation are shown i n Appendix C-2-8, while some of the data are displayed in Table 18. Surface coal appears to have a s p e c i f i c s e l e c t i v i t y towards each metal ion when they are present i n combinations. A comparison between the eff l u e n t concentrations of each metal at the 45 cm l e v e l after 19 days i s represented by a bar graph shown in Figure 20. The graph shows that coal exhibits the highest s e l e c t i v i t y towards mercury, then lead, while zinc seems to be the least s e l e c t i v e metal. Here the sequence i s as follows: Hg > lead > chromium > copper > Cd > Zn. This r e s u l t i s i n accordance with that obtained by.Riaz for the sequence of Pb > Cu > Zn, (Riaz, 1974). The sequence of a f f i n i t y of the six metals combined towards coal i s generally in accordance with that obtained on an i n d i v i d u a l basis which was previously discussed i n Section '4.1.1. The only exception i s with chromium which exhibits much higher adsorption when i t i s i n the mixed state than i n a case of the ind i v i d u a l state. The reason for t h i s behavior was not studied during t h i s work, but i t may be suggested to be due to some synergistic e f f e c t when the chromium ions are mixed with the other metal ions. TABLE 18. LONG TERM ADSORPTION PROCESS THROUGH LARGER COLUMN. COMPARISON BETWEEN THE ADSORPTION OF DIFFERENT HEAVY METALS. DAYS OF OPERA- TION 19 DAYS. Column diameter 6" (15.24 cm) Coal depth 2 meters Coal size 0 .533 mm Sampling Point 1 Mercury 2 Lead 3 Chromium 4 Coppsr 5 Cadmium 6 Zinc Influent 6.0 5.790 6.040 5.986 5.48 5.56 6." Level 1.780 6.200 3.87 . 6.204 5.73 5.97 lh f t Level 0.08 0.306 0.441 1.59 5.42 6.58 2h f t Level 0.023 0.G234 0.098 0.0717 0.220 0.761 3^ ft Level 0.0124 0.0127 0.057 0.0431 0.0016 0.033 4% f t Level 0.009'! 0.037 0.0528 0.0013 0.072 ?fc f t Level 0.0068 • • '- 0.034 0.0604 '.' 0.00087 0.0475 Bh f t Level 0.0062 - • 0.032 0.085 - 0.072 7 f t Level 0.0066 0.0151 0.0304 0.066 - 0.129 Values i n mg/1. MERCURY LEAD CHROMIUM COPPER CADMIUM ZINC FIGURE ,20 : SELECTIVITY IN ADSORPTION OF MIXED METALS BY COAL, operation:19days ,1.5ft.(46cm.)level, colurhn-..size: 1 5. 24cm. I, D .X2m. length. coal particle" size:0.533mm. 108. It i s obvious that the presence of other metals i n the solution detract from the removal capacity f o r the single metal. A much more rapid break through of these metals was noticed. As a general conclusion, the coal seems to r e t a i n i t s c a p a b i l i t y of reducing the eff l u e n t concentration of d i f f e r e n t metals i n the mixture to a l e v e l comparable with that of single metals. 4.2 Dissolved organics • 4.2.1 Contact process The tables of r e s u l t s , included i n Appendix C-3-1 are represented i n Figures 21a and b which show the adsorption isotherm regression lines f o r Hat Creek coal i n comparison to activated carbon for the removal of BOD,, and COD respectively. The isotherms are the Freundlich type, therefore, the empirical Freundlich formula can be applied i n t h i s case up to an equilibrium concentration of 400 mg/1 BOD,, and the adsorptive capacities for d i f f e r e n t systems are estimated by the extrapolation of the isotherm l i n e to the i n i t i a l concentration C^ as shown i n Figures 21a and b. Table 19 compares the estimated capacities for coal and activated carbon i n terms of BOD^ and COD. The above r e s u l t s show that granular activated carbon has approximately 6 times the adsorptive capacity of granular coal with the same p a r t i c l e s i z e , while the powdered coal seems to have a comparable capacity with granular activated carbon as measured on a COD basis. 109. IOO IOOO [OOCO Cf -RESIDUAL BO09< mg/| FIGURE 21a .-ADSORPTION ISOTHERMS FOR REMOVAL OF BOD5 BY COAL. contact time : 4 hours. 110. IOOO 580.6 165.6 0 Activated Carbon mssh -| * Hat Creek Coal - < 150.mesh • a - y 8 m e s h IOOO C f - RESIDUAL COD mg/l 1 ' I 1 M 1 IOOOO FIGURE 21b : ADSORPTION ISOTHERMS FOR REMOVAL OF COD BY COAL. contact time : 4 hours. 111. TABLE 19. COMPARISON OF ADSORPTIVE CAPACITIES OF COAL AND ACTIVATED CARBON Adsorbent Estimated adsorptive capacity mgs/gm adsorbent COD Activated carbon 4/8 mesh 753.3 Hat Creek coal 4/8 mesh 66.4 165.6 Hat Creek coal < 140 mesh 5126.0 580.6 Also, the reduction of the coal p a r t i c l e size seems to have a great e f f e c t on the increase of the capacity to remove BODj. from organic solutions. 4.2.2 Column process taining coal of the 0.533 mm and 0. 2.965 mm p a r t i c l e sizes are l i s t e d in Tables 1 and 2 respectively i n Appendix C-312. The B0D5 and COD values for the 0.296 5 mm size coal bed are displayed graphically i n Figure 22a. •. ' J v V " ' The results indicate c l e a r l y that BOD,, and COD values can be lowered s u b s t a n t i a l l y with a granular coal media bed. However, i t i s necessary to allow the bac t e r i a to develop for a short period of time as shown by the comparison of values for analysis of the f i r s t l i t e r of application to that of subsequent sampling analysis. The e f f i c i e n c y of removal of BOD,, reaches up to 90% while 75 to 80% for COD values as shown i n The results of the adsorption experiments on columns con- lOOO Particle size; .2965 mm Row ; 5-7ml/min COO in influent 7CCf- KX8- '••ueiov**' 1 THROUGHPUT V O L U M E FIGURE 22a : REDUCTION OF BOD^ & COD BY LEACHING OF BEEF EXTRACT SOLUTION THROUGH COAL COLUMN SIZE s 7cm.I.D. X 20cm. length. 113. THROUGHPUT VOLUME FIGURE 22b ! EFFICIENCY OF REMOVAL OF BOD5&COD BY LEACHING OF BEEF EXTRACT THROUGH COAL COLUMN SIZE : 7cm.I.D. X 20cra. length. 114. Figure22b; continuing e f f i c i e n t levels are shown to continue up to 2 8-30 l i t e r s of volume throughput. Nevertheless, the e f f i c i e n c i e s s l i g h t l y declined from the maximum levels due to the formation of multiple layers of b a c t e r i a l slime indicated by a leakage of the BOD^ and COD (appreciable values i n the effluents) i n addition to the gradual decrease i n the hydraulic conductivity. To improve t h i s condition, backwashing with tap water was used, but i t does not bring the column back to i t s f u l l o r i g i n a l effectiveness. A comparison of the results for the 0.5 33 mm and the 0.2965 mm p a r t i c l e sizes of coal indicates that the larger coal size i s advantageous because i t allows for lower head loss and consequently better hydraulic conductivity. However, one must recognize the lower organic removal capacity at the high flow rate, as shown for the 50 ml/min rate, compared to the 5 to 7 ml/min flow rate. The cumulative e f f e c t of a bed loading and the corresponding cumulative removal i s shown i n Figures23a and b for BOD,, and COD respectively for the two sizes of c o a l . It would appear that both columns have the capacity to accept much higher t o t a l load before they reach a saturated condition. A " l e v e l l i n g out" of the curve would indicate the saturated conditions. The r e l a t i o n s h i p between BODj. and COD cumulative for the two coal sizes i s p l o t t e d graphically i n Figure 23c which shows an almost l i n e a r r e l a t i o n s h i p . The l i n e a r regression analyses of the data for a coal size of 0.533 mm i s as follows: I i I I 1 ' '"1 1 • 'I TOTAL B O D 5 APPLIED, gm FIGURE 23a ; CUMULATIVE REMOVAL OF BODg LEACHING OF BEEF EXTRACT SOLUTION THROUGH : COAL COLUMN (20cm X 7cmI.D„). 116. T O T A L COD APPLIED . gms. FIGURE 2 3b 117. FIGURE 23c : RELATIONSHIP BETWEEN BODcAND COD. CUMULATIVE REMOVAL. 118. BOD5 value = 0.01485 + 1.91085 COD value ( r 2 = 0.9969) For a coal size of 0.2965 mm the re l a t i o n s h i p would be B0D5 value s-0.29356 + 2.052 COD value Cr 2 = 0.99017) In both cases, i t i s noted that the two l i n e s have very s i m i l a r slopes and intercepts. Therefore these constants can be used to correlate approximately the BOD^ to the COD values. 4.2.3 Mixed organics and toxic metals To investigate the e f f e c t of mixed organics and toxic metals in sewage e f f l u e n t , beef extract sol u t i o n was mixed with 0.2 mg per l i t e r of lead. This concentration of lead applied i n th i s experiment was based on the average lead concen- t r a t i o n i n Iona Sewage e f f l u e n t . I t i s evident from the results shown i n Table 20 that BOD^, COD and lead were removed to a s a t i s f a c t o r y l e v e l . During the inoculation "run" the lead was removed almost completely, reaching a l e v e l i n the effluent of < 0.05 mg/1. Also removal e f f i c i e n c y f o r B O D a n d COD seems to be higher than that previously obtained for only dissolved organics. Enhancement of the dissolved organic removal, i n the presence of metal ions, can be due possibly to a co-adsorption phenomenon which i s a re s u l t of a cooperative action of adsorbates i n which solutes are able to enhance the adsorption of certain other solutes (Hassler, 1974). 4.2.4 Comparison of coal with sand The value of coal as an adsorbent i s compared with that of construction sand which i s considered as a porous medium TABLE 20. COLUMN LEACHING OF DISSOLVED ORGANICS REMOVAL OF BODg, COD AND LEAD (20 cm X 7 cm I.D.) COLUMN Coal Size: 0.533 mm Rate of Flow: 6-8 ml/min. FIRST RUN VOLUME = 2 LITERS SECOND RUN VOLUME = 2 LITERS REMARKS Influent Effluent •I (1) E f f . (2) E f f . (3) E f f . (4) E f f . (5) Influent E f f l u e n t E f f . II (1) (2) E f f . E f f . (3) (4) E f f . (5) Service Time BOD5 Test 1 hr 2hr 3hr 4hr 5hr 1 hr 2hr 3hr 4hr 5hr B0D_ mg/1 125 85 78 95 15 200 117 128 142 46 A b a c t e r i a l inocula- t i o n of the column BOD. with 1 l i t e r of about Removed mg/1 330 * 205 245 252 235 315 580 * 380 463 452 438 534 300 mg/1 beef extract followed by washing & % Removal 62 74 76 71 96 66 80 78 76 92 drying preceded the f i r s t run. COD TEST COD mg/1 296 208 208 232 144 400 320 296 265 173 COD 855 947 Removed mg/1 683 * 392. 4P0 480 456 544 1120 * 720 800 824 % Removal 57 70 70 66 79 64 71 74 77 85 LEAD TEST Pb mg/1 Pb Removed mg/1 % Removal 0.2 0.03 0.03 <0.02 <0.02 <0.02 0.05 0.17 0.17 >0.18 >0.18 >0.18 0.2*0.15 85 85 > 90 > 90 > 90 75 0.03 <0.02 <0.02 <0.02 0.17 >0.18 >0.18 >0.18 85 > 90 > 90 >• 90 Since maximum s e n s i t i v i t y of the machine i s 0.02 mg/1 the percentage de- tectable removal expected to be lOOi f o r a l l con- centrations below 0.02 mg/1 Pb. * Concentration of the infl u e n t solution applied. 120. The results of comparison for reduction of BOD̂ . and COD are shown in Table 21 and the corresponding graph 24. The results c l e a r l y indicate the superior value of coal over that of sand, e s p e c i a l l y a f t e r the inoculation period which allows for development of a good b a c t e r i a l culture on the coal surface compared to the sand. This may be due to the presence of mineral nutrients as well as the carbon as a major constituent of the c o a l , while the major constituent i n sand is s i l i c a which.does not allow the b a c t e r i a l development as s i g n i f i c a n t l y as i n the case of coal. In addition, the coal has a larger i n t e r n a l surface area due to i t s numerous fractures and porosity while the sand p a r t i c l e s do not possess these properties. The results obtained may be compared to experiments conducted by the FMC Corporation (19 71) which shows that the coal bed had l i t t l e adsorption compared to activated carbon but had an e f f e c t i v e b i o l o g i c a l capacity a c t i v i t y and correspond- ingly an increase in i t s adsorptive capacity to a highly acceptable l e v e l . 4.3 Phosphates 4.3.1 Contact process The r e s u l t s from the various batch tests conducted under d i f f e r e n t conditions are shown in Tables 1 to 6 i n c l u s i v e in Appendix C-4-1. The e f f e c t of the contact time was f i r s t studied at 1 hour, 3 hours and 6 hours. The results indicate that 6 hours 121. TABLE 21. COMPARISON BETWEEN HAT CREEK COAL AND CONSTRUCTION SAND FOR REMOVAL OF DISSOLVED ORGANICS. Coal Size: 0.2965 mm Sand Size: From 60 to <300 mesh First Run: 1 l i t e r (Inoculation) Second Run: 2 liters Times, hrs 3 hrs 6 hrs Coal Sand Coal Sand I: BOD TESTS - BOD of the Influent mg/1 310 312 326 295 - BOD of the Effluent mg/1 245 196 52 • 44 22 194 252 - BOD Removed mg/1 65 116 274 282 304 101 43 - % Removal 21 37 84% 87% 93% 34% 15% II: COD TESTS - COD of the Influent mg/1 640 648 620 635 - COD of the Effluent mg/1 494 471 176 150 120 467 454 - COD Removed mg/1 146 177 444 470 500 168 181 - % Removal 30 27 72% 76% 86% 27 29 60 h 40 20 I- O-COAL x-SAND THROUGHPUT VOLUME , litres FIGURE 24 s COMPARISON BETWEEN THE EFFICIENCY OF REMOVAL OF DISSOLVED ORGANICS BY COAL AND SAND BEDS. 123. contact i s s u f f i c i e n t to attain equilibrium in the adsorption system, and therefore a l l isotherm tests for phosphate have been conducted at 6 hours contact. Regarding the e f f e c t of p a r t i c l e s i z e , the larger p a r t i c l e sizes of coal exhibit poor adsorptive capacity for phosphate. However, with f i n e r s i z e s , the capacity gradually increases as shown i n Figure 25, also the e f f i c i e n c y of removal reaches approximately 70% when a 1% addition of coal of < 0.03414, mm (140 mesh) p a r t i c l e size was used. For the same coal s i z e , other adsorption isotherms have been constructed using d i f f e r e n t amounts of coal -- 0.5%, 1% and 51 w/w. The results are in Table 22, and indicate that by increasing the amount of coal added to 5% w/w, ef f e c t i v e removal could be obtained up to more than 90% with concentra- tions of 5 mg/1 and 10 mg/1 of phosphate in the so l u t i o n . This i s considered an excessive amount of coal for the contact process in a commercial application. 4.3.2 Column process The column adsorption process i s more a t t r a c t i v e for the removal of phosphates. The tables of results are included in Appendix C-4-2 and are represented by the break through curves shown i n Figure 26, respectively which are obtained with coarse and fine coal sizes. The break through point for the larger p a r t i c l e s i z e , e.g. 0.533 mm i s reached at a much lower volume, while the smaller size gives better e f f i c i e n c y of removal. 10 EQUILIBRIUM SOLUTION CONG (mg;/)) FIGURE 25 : ADSORPTION ISOTHERMS FOR REMOVAL OF PHOSPHATE BY COAL. contact time = 6hours. coal dosage - ]%w/w. M TABLE 22. EFFECT OF PERCENTAGE COAL ON THE REMOVAL CAPACITY OF PHOSPHATE Time: * 6 hrs Coal Size: 0.03414 mm av. BATCH PROCESS • * Coal Added Influent _ 2 n cone.mg/1 & 5 mg/1 . • 10 mg/1 50 mg/1 Effluent mg Removed % cone per mg/1 gm coal Removal Effluent mg Removed % cone per mg/1 gm coal Removal Effluent mg Removed % cone per mg/1 gm coal Removal Effluent mg Removed % cone per mg/1 gm coal Removal 0.5 0.92 0.216 54.0 2.94 0.412 41.2 6.25 0.75 37.5 39.53 2.094 20.2 1.0 0.858 0.1142 57.1 - 1.56 0.344 68.8 3.46 0.654 65.4 38.0 1.2 24.0 5.0 0.46 0.0308 77.0 0.43 0.0914 91.4 0.64 0.1872 93.6 • 13.45 0.731 73.1 '9ZI 127. The very fine p a r t i c l e size < 150 mesh i s not p r a c t i c a l i n column test since i t allows very poor hydraulic conductivity. 4.3.3 Comparison between coal and s o i l The Abbotsford sandy loam described e a r l i e r i n Chapter IV, of similar texture to coal, was subjected to both contact and leaching t r i a l s to compare the value of s o i l to coal for phosphate adsorption. Results from the contact process summarized i n Table 23, show that there i s not a great difference in t h e i r adsorptive c h a r a c t e r i s t i c s . Meanwhile, the column process shows c l e a r l y that s o i l i s d e f i n i t e l y superior to coal as shown in Figure 27. In the case of s o i l , a break-through point of 7 5% removal i s reached aft e r Sh l i t e r volume of throughput with an adsorptive capacity of 3.4 mgs phosphate removed per gram s o i l . In comparison, only 0.815 mgs phosphate is removed per gram of coal. 4.4 Nitrates Neither the contact process nor the column process are encouraging for the removal of nitrate-nitrogen. The re s u l t s of the contact process, shown i n Table 24a indicate that none of the coal p a r t i c l e sizes were e f f e c t i v e . In fact there i s an accretion of NO^ into the solution for each of the various s i z e s . An increase of 2 mg/1 or more was experienced in the smaller sizes and t h i s value increased with the increasing percentage of coal added. This indicates that n i t r a t e s are removed from the o r i g i n a l coal. The average quantity of TABLE 23. CONTACT PROCESS - FZHDVAL OF PHOSPHATE COMPARISON BETWEEN HAT CREEK COAL AND ABBOTSFORD SANTO LOAM. Time of Contact: 3 hours Influent Solution V HAT CREEK COAL Size 0.03414 imi (<150 mssh) ABBOTSFORD SANDY LOAM Size 150-250 mesh Cone ppa (C2-.1) Coal or Sand Effluent cone mg/1 ag Reroved per gm coal % Removal Effluent cone mg/1 mg Removed per PE loam % Removal O.S 3.25 0.35 35.00 3.09 0.382 33.20 5 - 1.0 2.51 0.249 49.80 1.35 0.365 73.00 5.0 0.73 •• 0.0854 .85.4 <0.31 >0.094 >94.00 0.5 41.37 1.726 17.26 42.9 1.42 14.2 50 1.0 38.92 1.108 22.2 38.9 1.11 22.2 5.0 18.48 0.6304 63.04 14.4 0.712 71.2 FIGURE 27 : BREAK-THROUGH CURVES FOR PHOSPHATE REMOVAL BY COAL AND ABBOTSFORD SANDY LOAM. CO TABLE 24a. CONTACT PROCESS NITRATE-N REMOVAL Influent cone. = 10 mg/1 Contact % Coal Size 0.533 mm Coal s i z e 0.2965 nm Coal s i z e 0.117 mm Time Coal. L • N0~-N N0 3~ N03"-N N0 3~ N03~-N N0 3~ mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 1% 2.41 10.67 2.48 10.98 2.56 11.34 1 hr. 5% 2.56 11.34 2.64 11.69 2.72 12.05 1% 2.48 10.98 2.51 11.11 2.43 10.76 3 hrs. ; ; ; 5% 2.61 11.56 2.67 11.82 2.77 12.27 INFLUENT CONC. 50 mg/1 NO ~ : ~~ ~ 1% 11.3 50 11-4 50.5 3 hrs. ; . 5% 11.2 49.6 11.9 52.7 131. nitrate-nitrogen leached out from Hat Creek coal was determined e a r l i e r i n Chapter V, an average of 2 - 4 mgs of NO^-N was found to be leached from each 100 gram of co a l , this i s equiva- lent to 2 - 4 mgs/liter. The results of the column process, table 24b, show that at the beginning, a s l i g h t physical adsorption of NO^ by coal, but only a f t e r 2 l i t e r s of volume throughput. The removal capacity i s n i l . The i n a b i l i t y of the coal to adsorb n i t r a t e s may be explained by the great s o l u b i l i t y of the n i t r a t e anions which make i t d i f f i c u l t to be separated from i t s solutions and adsorbed on the coal surface. Also, by the p o s s i b i l i t y of releas- ing n i t r a t e s , being present in the coal, into the solution due to i t s high s o l u b i l i t y . 4.5 Ammonia 4.5.1 Contact process Table 25a shows the adsorption of ammonia with d i f f e r e n t percentages of both the surface coal and the activated carbon, when the i n i t i a l ammonia concentration i s 50 mg/1. Both adsorbents exhibit poor adsorptive capacity which do not exceed 0.5 mg/gm adsorbent with not higher than 30% removal e f f i c i e n c y . S l i g h t l y higher values were obtained with activated carbon. Table 25b gives a comparison between the non-oxidized and oxidized coal for the removal of ammonia. The results TABLE 2 4 b. COLUMN TEST NITRATE REMOVAL Coal size Influent cone. Flow rate = 0.2965 mm = 10 mg/1 N03~. = 8-10 ml/min. Throughput Volume Liters N03-N mg/1 N03 mg/1 NO, Removed % Removal 0.5 1.8 8.14 1.6 16.0 1.5 2.0 8.86 1.14 2.0 2.31 10.2 133. TABLE 25a. REMOVAL OF AMMONIA COMPARISON BETWEEN ACTIVATED CARBON AND HAT CREEK COAL CONDITIONS OF EXPERIMENTS Material used for stock solution = NH NO Initial concentration Contact time Mean particle size = 50 ppm = 24 hrs = 0.9 - 1 mm Code Samples Cone ppm Removed ppm Removal mgs Removed per gm Carbon 0 - NH, 50.0 0.5% ac 1.0% ac 2.0% ac 5.0% ac 47.75 43.25 42.0 35.0 2.25 6.75 8.00 15.00 4.5 13.5 16.0 30.0 0.4500 0.675 0.400 0.3000 0 - NH.. 50.0 0.5% sc 1.0% sc 2.0% sc 5.0% sc 47.5 46.75 44.75 40.5 2.5 3.25 5.25 9.5 5.0 6.5 10.5 19.0 0.50 0.33 0.26 0.19 NOTE ac = activated carbon sc = surface coal TABLE 25b. BATCH PROCESS REMOV/li OF AMMONIA BY COAL Type of % AMMONIUM NITRATE' AMMONIUM SULFATE Coai Coal Effluent mgs Removed % Effluent mgs Removed Added Cone per gm coal Removal cone per gm coal Removal w/w mg/1 mg/1 - 0 9.25 - - 9.5 - - NON- 0.5% 5.9 0.67 36.2 7.2 0.46 24.2 OXIDIZED 1.0% 5.9 . 0.34 36.2 4.6 0.49 51.6 CORE 2.0% 3.25 0.3 64.9 2.53 0.35 73.5. COAL 5.0% 3.78 ' 0.11 59.1 2.3 0.14 75.8 SURFACE 0.5% 9.53 _ 9.3 0.04 2.1 COAL 1.0% ••10.15 AMMONIA LEACHED 10.1 mm m (OXIDIZED) 2.0% 11.0 OUT INTO THE 14.0 mm 5.0% 14.75 . SOLUTION 12.35 AMMONIA LEACHED OUT INTO THE SOLUTION 135. indicate that the non-oxidized coal removes ammonia more e f f i c i e n t l y than surface coal when either NH^NO^ or (NH^^SO^ solution i s used as synthetic waste. With higher quantities of surface coal applied, the ammonia l e v e l increases i n the effluent even higher than the o r i g i n a l concentration. This confirms the suggestion that some soluble components, containing ammonium ions, were leached from the surface coal and add to the l e v e l o r i g i n a l l y present. The leaching of ammonium ions from coal as studied during this period, and the results shown i n Chapter V indicates that the ammonia leached from the surface coal i s i n the order of 16 mg/1 which i s equivalent to 18 mgs NH^-N per 100 grams of coal, while an average of 7 mgs NH^-N was leached from the non-oxidized core coal. This explains the very poor adsorptive qua l i t y of the surface coal for ammonia. 4.5.2 Adsorption of ammonia with leached coal After leaching ammonia from the surface and core coal, the coals were dried and used i n a batch test to check the e f f e c t of removal of the o r i g i n a l l y present ammonia i n coal on improving the adsorption behavior towards ammonia from waste- water. Table 25c shows that in both types of coal the adsorp- tive capacity and the removal e f f i c i e n c y are increased by washing the coal. A 30% removal was obtained when the ammonia solution was treated with 5% coal without any further release 136. of ammonia into the solution. In comparison, about 6 3% removal was obtained when 51 of core coal was used. TABLE 2 5c. ADSORPTION OF AMMONIA WITH WATER WASHED COAL. - P a r t i c l e size of coal 48/100 mesh; Contact time = = 14 hours - Volume of solution - 100 cc. - Influent concentration =7.55 mg/1 NH3-N Coal sample % coal added w/w Eff l u e n t Removed cone. NH,-N mg/1 mg/1 NH3-N % E f f i c i e n c y of removal Surface coal 1 5.75 1.80 24 5 5.30 2.25 30 Core coal 1 3.75 3.80 50 ' 5 2.80 4. 75 6 3 4.5.3 'Column process Table 25d shows that much high e f f i c i e n c y of removal i s achieved by a column leaching process rather than the con- tact process. Up to 95% removal can be obtained using core coal, while surface coal y i e l d s a lower e f f i c i e n c y , about 61% . In comparison, the activated carbon has the highest e f f e c t i v e - ness where more than 99% removal i s shown. 137. TABLE 25d. COLUMN .TEST FOR REMOVAL OF AMMONIA - P a r t i c l e size of coal 14/20; Contact time = 30 min. 2 - Flow rate 1 gpm/ft (15 ml/min). - O r i g i n a l i n f l u e n t concentration =9.5 mg/1 NH^-N Volume AMMONIUM SULFATE Type of coal throughput E f f 1 . cone. l i t e r s mg/1 % Removal Non-oxidized 1 0.7 92.6 core sample 2 0.6 93.7 3 0.8 91.6 4 0.45 95.0 Oxidized surface 1 3.9 59.0 coal 2 3.75 60 .5 3 3.6 61.0 4 3.7 61.0 Activated carbon 1 < 0.1 > 99.0 2 < 0.1 > 99.0 3 < 0.1 > 99 .0 4 < 0.1 > 99.0 4.6 Phenol Several batch and column adsorption tests were conducted to check the adsorptivity of the surface coal toward phenol in comparison to activated carbon. The results from the batch test are summarized in Table 26a, ind i c a t i n g that phenol i s r e a d i l y removed by surface coal; 80% removal was obtained when 2% coal of size 100/150 mesh was used i n a solution containing 4.12 mg/1 of phenol. TABLE 26a. REMOVAL OF PHENOL (BATCH PROCESS) Initial concentration of phenol solution = 4.12 mg/1 Mean particle size of coal or carbon = 14/20 mesh (0.9-1 mm) Contact time =24 hours Volume of solution = 100 cc Absorbent added % w/w Phenol cone. mg/1 Phenol Removed % mgs removed Removal per gm coali 0 Activated carbon 0.5% 4.12 0.02 4.10 99.5 0.820 Surface coal 0.5% (14/20 mesh) 2.0% (14/20 mesh) 2.0% (100/150 mesh) 2.73 1.69 0.81 1.39 2.43 3.31 33.9 59.0 80.3 0.278 0.122 0.166 139. In comparison, activated carbon i s superior since i t s e f f i c i e n c y for the removal of phenol i s more than 99%. Regarding the column adsorption t e s t , 4 l i t e r s of solution were applied through a column (20 cm X 7 cm I.D.) at 2 a flow rate of 1 gpm/ft . The results obtained from this test are shown in Table 26b, and confirm that both surface and core coal have appreciable adsorptive capacity towards phenol, although surface coal has a greater e f f i c i e n c y reaching more than 91% af t e r passing through 3 l i t e r s . In comparison activated carbon s t i l l possesses a superior e f f i c i e n c y of 99.9% for the removal of phenol. 4.7 Cyanide Table 2 7a shows the r e s u l t of the batch test for the removal of cyanide which indicates that cyanide i s removed rea d i l y by surface coal with a very high e f f i c i e n c y from 90 - 96% while i n comparison activated carbon completely removes the cyanide from solutions. The results of the column adsorption tests i n Table 27b show that the surface coal exhibits higher e f f i c i e n c y than the core coal for the removal of cyanide from solutions. Nevertheless, activated carbon exhibits superior a c t i v i t y . The higher e f f i c i e n c y of surface coal more than core coal for removal of phenol and cyanide may be at t r i b u t e d to the presence of surface oxides (oxygen-containing functional groups) which are l i k e l y to play a role in the adsorption mechanism. This point was not investigated during this portion of the research. TABLE 26b COLUMN ADSORPTION PROCESS- REMOVAL OF PHENOL Column size (20 cm X 7 cm I.D.) 2 Flow rate = 1 gpm/ft (165 ml/min) Particle size of adsorbent = 14/20 mesh Contact time = 2-3 min Influent = 4.08 mg/l phenol Volume throughput liters 1 ACTIVATED CARBON SURFACE COAL . CORE COAL " E f f l . cone, mg/l Removal E f f l . cone. mg/l % Removal E f f l . cone. mg/l Removal 0 4.08 • " - 4.08 - 4.08 - 1 0.02 99.5 0.56 86.3 • 0.58 85.8 2 0.07 98.3 2.00 51.0 1.43 65.0 3 0.025 99.4 0.35 91.4 1.91 53.2 4 0.005 99.9 0.50 87.8 2.50 38.7 141. TABLE 27a REMOVAL OF CYANIDE (CONTACT PROCESS) Initial concentration of cyanide Mean particle sizes Contact time Volume of solution Influent concentration = 1.66 mg/1 = 14/20 and 100/150 mesh = 24 hours = 100 cc. = 1.66 mg/1 phenol Adsorbent added % w/w Phenol cone. mg/1 Phenol Removed % mgs removed Removal per gm coal 0 Activated carbon 0.5% (14/20) 1.66 N.D. Al l removed > 99.9 0.330-0.332 Surface coal 0.5% (14/20 mesh) 0.14 2.0% » 0.16 2.0% (100/150 mesh) 0.07 1.52 91.6 1.5 90.4 1.59 95.8 0.304 0.075 0.080 142. TABLE 27b COLUMN ADSORPTION PROCESS Column size (20cm X 7 cm I.D.) 2 Flow rate = 1 gpm/ft (165 ml/min) Particle size of adsorbent - 14/20 mesh Contact time = 203 min Influent concentration = 1.46 mg/1 CN Volume ACTIVATED CARBON SURFACE COAL CORE COAL throughput E f f l . E f f l . E f f l . liters cone. % cone. % cone. % mg/1 Removal mg/1 Removal mg/1 Removal o 1.46 • - 1.46 .- 1.46 - . 1 0.054 96.3 0.02 98.6 0.24 83.6 2 0.054 96.3 0.77 47.2 0.62 57.5 3 0.071 95.1 0.54 63.0 0.54 63.0 4 0.074 94.9 0.03 97.9 0.12 91.8 VI. MECHANISM STUDIES. A. Mechanism of Adsorption of Heavy Metals by Coal Preface: Coal i s a very complex humic material, therefore i t s high a c t i v i t y in removing heavy metals from solutions i s not expected to be a simple mechanism, because i t may involve one or more of the following mechanisms i n combination: ion-exchange, surface adsorption, chelation, coagulation or peptization reactions (Mortensen, 1963). During the course of t h i s study the interest was focussed on the ion-exchange type of mechanism. A c h a r a c t e r i s t i c of low rank coals such as Hat Creek, and related humic materials i s that much of the oxygen associa- ted with t h e i r structure i s present as carboxyl and phenolic hydroxyl groups (Brooks, 1957). The study of the ion-exchange mechanism i s directed toward providing s u f f i c i e n t evidence for the involvement of the acid groups of coal i n the i n t e r a c t i o n with heavy metals and therefore the following approaches were considered: 1. Microscopic Approach. The Electron Microprobe and the Scanning Electron Microscope were both used to confirm that the adsorbed lead ions would be s i t e d on the organic part of the coal and not on the s i l i c o n contained i n inorganic minerals. 2. Spectroscopic Approach. The Infra-Red absorption spectroscopy was applied, using a semi-quantitative technique, to show the i n t e r a c t i o n of the acid groups i n the coal with the adsorbed metal ions. The same technique i s also employed to check the proximity of the carboxyl groups present i n the coal. The infr a - r e d spectra of the anhydride form of the coal are compared with those obtained a f t e r adsorption of lead, the s i m i l a r i t y between them would indicate the p o s s i b i l i t y of a complex formation between two adjacent carboxyl groups and the metal ion. Chemical Approach. 3.1 Measuring the number and the nature of the active s i t e s available for cation exchange reaction with the metal ions. Both the exchangeable cations and the t o t a l exchange capacity (CEC) of the coal are determined and used i n t h i s study. 3.2 A quantitative determination of the r a t i o between the number of lead ions adsorbed and the corres- ponding number of hydrogen ions released. 3.3 A quantitative determination of the number of carboxyl and phenolic hydroxyl groups present i n the coal, as well as the number of these groups which are involved i n the int e r a c t i o n with the metal ions. An evaluation of the r e l a t i o n between these values and the values obtained by the lead ions which reacted and released hydrogen as described in the previous 3.2 Section. 145. A l l of the above studies are correlated and used to suggest an overall mechanism which may be expected to take place during the adsorption of metal ions by coal carbon. 1. MATERIALS 1.1 The Hat Creek coal samples These were prepared as described previously i n Chapter III and IV. The following samples were used: a) Water-washed oxidized surface coal (W.W.S.) b) Acid-washed oxidized surface coal (A.W.S.) c) Water-washed unoxidized core coal (W.W.C.) d) Acid-washed unoxidized core coal (A.W.C.) 1.2 Calgon Activated Carbon samples These included: a) Water-washed activated carbon (W.W.A.) b) Acid-washed activated carbon (A.W.A.) 1.3 Stock solutions of lead n i t r a t e of 500 mg/l and 5000 mg/l concentration respectively to provide the lead ions required for the adsorption process. 2. METHODS 2.1 Electron Microanalysis The Electron Microprobe and the Scanning Electron Microscope, were used to obtain an elemental mapping for the di s t r i b u t i o n of the adsorbed lead ions with respect to other elements across the surface of the coal p a r t i c l e s . 146. A description of the two instruments and the theory of t h e i r operation are included in Appendices A, and B - l . A very important feature of these methods i s that the coal samples are analyzed non-destructively without damaging the features of the surface. The special technique used for the preparation of the coal specimen for such analyses i s described in Appendix B-l (Goldstein, 1975). Micrograph pictures obtained by the low power microscope are used to choose the suitable coal p a r t i c l e s used in the study of the mechanism. Then the Scanning Electron Microscope micrographs are used to describe the features of the coal p a r t i c l e s under scrutiny. A set of electron images were produced which show the elemental d i s t r i b u t i o n or mapping across certain areas of the specimen. Each image gives the concentration of a p a r t i c u l a r element i n the given area. In places of high concentration of elements, the picture w i l l be nearly white, i t w i l l be gray when the element concentration i s lower and black when the element i s absent. The adsorption of lead ions on the surface of the coal particles:The coating material (carbon) was f i r s t removed from the surface by washing thoroughly with ethyl alcohol, then with acetone, and f i n a l l y a i r dried. Each specimen under scrutiny was then soaked in a 200 cc solution of lead n i t r a t e at a con- centration of 500 mg/1 at room temperature. A contact time of 147. 72 hours allowed the specimen to reach an equilibrium state. Each specimen was then removed from the s o l u t i o n , washed thoroughly with d i s t i l l e d water, dried i n a i r for about 2 days before s t a r t i n g the electron microanalysis. 2.2 Infra-red Spectra A solution of lead n i t r a t e containing 500 mg/l concen- t r a t i o n was shaken with \% w/w coal or carbon of a p a r t i c l e size of 50/100 mesh for a contact time of 8 hours, then the coal p a r t i c l e s were rinsed with d i s t i l l e d water and a i r dried. : KBr p e l l e t s technique (Lowry, 1963 and F u j i i , 19 70) described i n Appendix B-2-2 was applied. The i n f r a - r e d absorption spectra were then recorded between the region of 200 to 900 cm"'*". The s p e c i f i c extinction c o e f f i c i e n t f or the a c i d i c groups were evaluated using the base l i n e technique described in Appendix B-2-3 (Ewing, 1960 and F u j i , 1970). Another set of coal samples was prepared by adsorbing barium ions on the coal from a saturated s o l u t i o n of 1 N barium acetate. The coal was refluxed i n the barium acetate solution for 4 hours. The in f r a - r e d spectra of these samples were com- pared with those obtained when lead was adsorbed. Preparation of the acid anhydride of co a l . The coal was heated at 170°G for about 50 hours (Wright and Schnitzer, 1961). The samples were cooled c a r e f u l l y i n a desiccator. Infra-red spectra of the anhydrides were then measured on potassium bromide discs. 2.3 Chemical Methods 2.3.1 The determination of exchangeable cations and t o t a l exchange capacity (Black, 1965). . 148. Cation exchange capacity (C.E.C.) denotes the t o t a l cations that can be replaced from a given substance under a given set of conditions. Usually, i t i s expressed as m i l l i - equivalent/100 grams. The exchange capacity depends on the pH of the solution used i n the determination. For t h i s reason, neutral solutions at pH = 7 are used throughout, by leaching with a neutral ammonium acetate. With th i s s a l t , the exchange capacity of humic substances can be determined reasonably accurately even when the substance contains soluble s a l t s and calcium carbonate. The amount of NH^ adsorbed from neutral ammonium acetate merely represents the amount of cations the coal i s capable of holding in replaceable form at pH = 7. Through this analysis both the exchangeable cations Na, K, Mg and Ca and the t o t a l exchange capacity were calculated. The detailed technique and method of c a l c u l a t i o n are included i n Appendix B-5. This method is based on the assumption that a complete replacement of a l l exchangeable cations i s c a r r i e d out by cations (in this case ammonium ions NH^+) which are not present in the sample (Kelley, 1948). 2.3.2 Determination of the r a t i o of adsorbed lead ions to hydrogen ions released from coal. A lead n i t r a t e s o l u t i o n con- taining 500 mg/1 leadwas shaken with \% w/w of coal or carbon of a p a r t i c l e size of 50/100 mesh for 8 hours. The mixture was then f i l t e r e d and the pH of the clear f i l t r a t e measured and 149. used to calculate the hydrogen ions released upon the adsorp- tion of lead. The remaining lead ions i n the solution af t e r the int e r a c t i o n were measured using the Atomic Absorption Spectro- photometer. The r a t i o of the lead ions adsorbed and the corresponding hydrogen ions released was calculated and i s reported as follows. 2.3.3 Determination of acid groups. The f i l t e r e d coal from the above described procedure was then rinsed with d i s t i l l e d water and a i r dried. The acid groups (carboxyls and phenolic hydroxyls) were then determined for the coal and the carbon samples before and af t e r lead adsorption, using the following techniques: 2.3.3.1 Total a c i d i t y (Schafer, 1970; Schnitzer and Gupta,. 1965) . To 200 milligrams of each coal sample, previously ground to pass a 200 mesh sieve s i z e , 20 mis of 0.25 N Barium hydroxide solution was added. Simultaneously, a blank was set up consisting of 20 mis of 0.25 N BaCOH^) only. The a i r i n the flask was displaced by nitrogen and the system was shaken for 24 hours at room temperature. Following t h i s , the suspension was f i l t e r e d , the residue washed thoroughly with CC^-free d i s t i l l e d water and the f i l t r a t e plus washings t i t r a t e d potentiometrically (glass- calomel) with a standard 0.5 N HC1 solution to a pH of 8.4. The t o t a l acid i s then calculated as follows: 150. (Titer of blank - titer of sample)X N acid X 1000 Weight of sample, mg = m.eq. Total Acidity/gram of organic matter 2.3.3.2 Carboxy groups Two methods were employed and compared: (A) . Barium Acetate Method (Schafter, 19 70) Coal (125 mgs) was refluxed in a i r with barium acetate (50 mis) (the pH being adjusted to 8.25) for 4 hours. The acid released was t i t r a t e d poteniometrically under nitrogen i n the presence of coal, with a l k a l i (0.05 N) u n t i l the pH value , 8.25 was restored. A glass-calomel electrode combination, used i n con- junction with a pH meter, served as the measuring system. The carboxyl groups were then calculated as follows: T i t e r for sample - t i t e r for the blank »» \. „ „ ~ v mnn —»—f-r—jr— s N base X 1000 Weight of sample, mgs = m.eq. COOH groups/gram of organic matter. (B) Calcium Acetate Method (Schnitzer and Gupta, 1965) Coal (200 mgs) was mixed with 10 mis of 1 N calcium acetate solution and 40 mis of CC^-free d i s t i l l e d water, then the mixture was shaken for 24 hours at room temperature, f i l t e r e d and the residue was then washed. The f i l t r a t e and washings t i t r a t e d potentiometrically with standard 0.1 N NaOH to pH 9.8. A blank consisting of 10 mis calcium acetate and 40 mis of d i s t i l l e d water was run simultaneously. The carboxyl groups were calculated as follows: 151. T i t e r of sample - t i t e r of blank v X T v , n n n • uj„i„-u4- ^ — z r r — x N base x 1000 Weight or sample, mgs = m/eq/COOH groups per gram coal. Therefore, phenolic hydroxyls are evaluated as the difference between the t o t a l a c i d i t y and the carboxyl COOH. 2.3.4 Lead ions exchanged with calcium or barium during the determination of the acid groups It i s possible during the measurement of residual a c i d i c groups a f t e r the lead adsorption t e s t that part of the previously adsorbed lead ions on the coal w i l l be released into the system. This i s due to the i r exchange with Ca or Ba ions used to perform the te s t . The Atomic Absorption Spectrophotometer was used f o r the lead analysis, therefore, the percentage of released lead ions would be as follows: mgs lead released from 1 gram coal inn to t a l mgs of adsorbed lead/gram coal x lead released. 152. 3. RESULTS AND DISCUSSION 3.1 Microscopic Studies The X-ray images shown i n Figure28a reveal the di s - t r i b u t i o n of carbon, s i l i c o n , oxygen and calcium across a layered p a r t i c l e of oxidized coal; the d i s t r i b u t i o n of the adsorbed lead i s shown by a dense pattern of white dots. The lead obviously located on areas containing carbon and not on those areas containing s i l i c o n , indicated that the mineral matter does not pa r t i c i p a t e i n the adsorption mechanism. Figure28b shows a d i f f e r e n t shape of p a r t i c l e for the Hat Creek coal where the mineral matter appears i n segregated form, not mixed with the organic part i n which the organic carbon i s located i n two streaks. The patterns of the carbon and lead d i s t r i b u t i o n , represented by trace, indicate that the lead i s predominantly adsorbed on the carbon and not on the mineral part that contains s i l i c o n . However, the lead d i s t r i b u t i o n i s not uniform, some areas appear to have more lead adsorbed than others. It was found that high levels of lead are shown on areas containing both carbon and oxygen dn the same s i t e , while less adsorption was noticed on s i t e s containing only carbon. It i s expected, therefore, that lead i s more read i l y adsorbed on functional groups containing oxygen such as carboxyl or phenolic hydroxyl groups. This w i l l be further confirmed by additional studies in the following sections of this chapter. 153. ADSORBED LEAL) 290X OXYGEN 290X. FIGURE 28a- A SET OF X-RAY IMAGES SHOWING THE ELEMENTAL MAPPING AND THE DISTRIBUTION OF ADSORBED LEAD ACROSS CERTAIN AREAS OF A LAYERED PARTICLE OF OXIDIZED H.C. COAL FROM SURFACE DEPOSIT, 154. AEI WITH Y-AXIS DISPLAY ACROSS THE GIVEN AREA 620X CARBON 620X ADSORBED LEAD 620X FIGURE 2 8b _ A S E T 0 F X " R A Y IMAGES ACROSS AN AREA OF SPECIMEN OF SURFACE H.C. COAL CONTAINING TWO LAYERS OF CARBON IN SEGREGATED FORM AND NOT DISPERSED WITH THE INORGANIC MINERALS. RED TRACE SHOVS THE CARBON DISTRIBUTION GREEN TRACE SHOWS THE ADSORBED LEAD DISTRIBUTION 155. A dispersed form of mineral matter, f i n e l y mixed with the carbon was noticed i n the structure of some coal p a r t i c l e s as shown by the X-ray images i n Figure 29. It can be seen that some adsorbed lead i s interspersed with the s i l i c o n , but t h i s i s no doubt due to intimately mixed carbon and s i l i c o n p a r t i c l e s . In the X-ray images the intimately mixed p a r t i c l e s are not e a s i l y d i s c e r n i b l e . Figures 30a and 30b show the electron micrograph images on a sample of non-oxidized core coal which s t i l l confirms the adsorption of lead on an area containing carbon. The s i m i l a r i t y obtained between the sulf u r and the carbon d i s t r i b u t i o n i n t h i s p a r t i c l e can be explained by the occurrence of organic forms of s u l f u r . The Absorbed Electron Images (AEI) of a cracked p a r t i c l e of core coal shows some i n t e r f a c i a l deposition of lead on the boundaries between the carbon and s i l i c o n ; but, i n general, the d i s t r i b u t i o n of lead follows to agreat extent the d i s t r i b u t i o n of carbon. The fact of adsorption of lead on carbon i s further confirmed by applying the microprobe study on two p a r t i c l e s of surface and core coal. Figure 31 shows the X-ray images where both p a r t i c l e s do not appear to have any appreciable s i l i c o n but consist mostly of coal. The lead appears to be r e a d i l y adsorbed on carbon i n both p a r t i c l e s . In comparison with activated carbon, the pattern of the d i s t r i b u t i o n of the adsorbed lead i s completely d i f f e r e n t than those of either carbon or s i l i c o n across the p a r t i c l e . The X-ray images in Figures 32a and"32b show that the adsorbed lead AEI 500X CARBON 620X ADSORBED LEAD 500X FIGURE 29- ELEMENTAL MAPPING ACROSS FRACTURED PARTICLE CROSS SECTION OF OXIDIZED HAT CREEK COAL FROM SURFACE DEPOSIT AFTER ADSORPTION OF LEAD, 157. FIGURE 30a- ELEMENTAL MAPPING OF LAYERED PARTICLE CROSS SECTION OF NON- OXIDIZED HAT CREEK SURFACE DEPOSIT AFTER ADSORPTION OF LEAD IONS, 158. SULFUR 290X SILICON 290X FIGURE 30b- ELEMENTAL MAPPING ACROSS AN AREA OF CRACKED PARTICLE OF NON- OXIDIZED H,C. COAL FROM CORE DEPOSIT, FIG. 7a & b ARE THE ABSORPTION ELECTRON IMAGES BEFORE AND AFTER ADSORPTION OF LEAD SHOWING THAT LEAD MAY HAVE INCORPORATED ITSELF NEAR THE BOUNDARY INTERFACES BETWEEN CARBON AND SILICON, Al AEI 620x A2 SILICON 620) A3 CARBON 620 x A4 LEAD 620x FIGURE 31" COMPARISON BETWEEN ELEMENTAL MAPPING OF PARTICLE CROSS SECTION OF SURFACE DEPOSIT AND CORE DEPOSIT OF HAT CREEK COAL SHOWING PURE CARBON SECTICW OF THE PARTICLE WITH NO SILICON DETECTED AND THE ADSORBED LEAD DISTRIBUTION FOLLOWS THE CARBON DISTRIBUTION, (A surface c o a l . ; B= core c o a l ) Cn A - A1 AH 290X A2 SILICON 290X B - Bl AEI 290X B2 A3 CARBON 290X A4 ADSORBED LEAD 290X aUCON 290X B4 ADSORBED LEAD 290X FIGURE32a"ELEMENTAL MAPPING FOR AREAS OF TWO DIFFERENT ACTIVATED CARBON PARTICLES A 8 B, BOTH SHOWING THAT THE DISTRIBUTION OF ADSORBED LEAD IONS DOES NOT FOLLOW THE CARBON DISTRIBUTION AND LEAD APPEARS AS BLACK SPOTS SUPERIMPOSED ON THE SURFACE. 0\ O SEM LEAD 5600x B 2 SEM 5600 x B3 SEM 1500x FIGURE 32b•ADSORPTION OF LEAD ON THE ACTIVATED CARBON PARTICLES, A l TO A 4 - "LEMENTAL MAPPING USING THE ELECTRON MICROPROBE SHOWING THAT LEAD DOES NOT ADSORB, B] TO B 4 - SEM IMAGES SHOWING THAT LEAD IS PHYSICALLY ADSORBED ON THE SURFACE OF THE PARTICLE 162 . is p r e c i p i t a t e d in a certain form on the surface of the p a r t i c l e This p r e c i p i t a t i o n appears as black dotes on the surface. The scanning of this area, using the Scanning Electron microscope, reveals a hexagonal shape of c r y s t a l s p r e c i p i t a t e d . The phenomenon can be explained more l i k e l y as a surface phenomenon exhibited by the activated carbon where i t s large surface area and i t s greater micropore volume are both contributing to enhance the c r y s t a l l i z a t i o n of the lead n i t r a t e into hexagonal cr y s t a l s upon evaporation of the solution. These cry s t a l s are therefore p r e c i p i t a t e d on the surface of activated carbon. It i s suggested that a true chemisorption i s not l i k e l y taking place in this case. 3.2 Infra-red spectra Infra-red spectroscopy i s used as another useful diagnostic tool to ascertain the i n t e r a c t i o n of the adsorbed heavy metal ions with the acidic function groups of c o a l , mainly carboxyls - COOH and phenolic hydroxyls - OH. Water washed and acid washed samples of surface and core coal have been used i n t h i s study. The results are summarized in four groups of i n f r a - red absorption spectra in the region of 1900 to 800 cm ^ which are shown in Figures 33A, B, C, and D. Each group consists of four i n f r a - r e d spectra named as follows: FIGURE 33A : INFRA-RED SPECTRA OF WATER-WASHED OXIDIZED SURFACE COAL SAMPLES,SHOWING THE CHANGES IN THE ABSORPTION BANDS AT 1720,1600&1100 cm" 2 K(cm /gm.)at 1720 1600 1100 a- o r i g i n a l coal 0.3] 0.43 0.42 b- a f t e r adsorption of lead (lPb/2coal) 0.11 0.65 0.25 c- a f t e r adsorption of barium (]7.2Ba/lcoal) 0.07 0.82 0.]7 d- a c i d anhydride d e r i v a t i v e 0.44 0.49 0.4 4 164, 20 0 0 180 0 W a v e Number , cm"' 16 0 0 1 4 0 0 120 0 ' 0 0 0 FIGURE 33B INFRA-RED SPECTRA OF ACID-WASHED OXIDIZED SURFACE COAL SAMPLES,SHOWING THE CHANGES IN THE ABSORPTION BANDS AT 1720,16005.1100 cm"1 K(cm^/gm.)at a- o r i g i n a l c o a l b- a f t e r adsorption of lead (lPb/2coal) c- a f t e r adsorption of barium (17.2Ba/lcoal) d- a c i d anhydride d e r i v a t i v e 1720 1600 1100 0.41 0.50 0.70 0.33 0.45 0.30 0.0 0.54 0.30 0.48 0.48 0.72 FIGURE 33 C:INFRA-RED SPECTRA OF WATER-WASHED,NON-OXIDIZED CORE COAL SAMPLES,SHOWING THE CHANGES IN THE ABSORPTION BANDS AT 1720,1600,llOOcm-1• K(cm2/gm)at 1720 1600 1100 a- o r i g i n a l coal — 0.60 0.81 b- a f t e r adsorption of lead (lPb/2coal) 0.13 0.23 0.76 c- a c i d anhydride d e r i v a t i v e 0.26 0.34 0.69 WAVE NUMBER .cm 1 8 0 0 1 6 0 0 1400 1200 10 0 0 Ha FIGURE 33D : INFRA-RED SPECTRA OF ACID-WASHED,NON-OXIDIZED CORE COAL SAMPLES,SHOWING THE CHANGES IN THE ABSORPTION BANDS AT 1720,1600,1100cm-l. K(cm2/crm)at a - o r i g i n a l coal a f t e r adsorption of lead (lPb/2coal) c-acid anhydride derivative d- a f t e r adsorption of barium (17.2Ba/lc0al) 1720 1600 1100 0.25 0.51 0.76 0.13 0.32 0.72 0 .20 0.55 0.66 0.27 0.84 167. Spectrum "a" -- o r i g i n a l coal sample. Spectrum "b" coal sample a f t e r adsorption of lead.' Spectrum "c" coal sample aft e r adsorption of barium. Spectrum "d" anhydride form of the coal sample. It i s obvious that the main changes, upon adsorption of metal ions, occur i n the 1700 cm 1 to 1600 cm 1 and in the 1400 to near 1100 cm - 1 regions. Therefore, the s p e c i f i c e x t i n c t i o n c o e f f i c i e n t "K" i s calculated for each spectrum mentioned above for the absorption bands at near 1100 , 1725 and 1600 cm the K values are l i s t e d on each figure mentioned above, while d e t a i l e d tables, including the corresponding values of the absorbance, are outlined i n Appendix C-5. This in f r a - r e d analyses cannot be considered a quantitative method for coal because of the high overlapping and broadening of the peaks which make i t very d i f f i c u l t to draw an accurate base l i n e for measuring the band i n t e n s i t i e s . Therefore, a l l the calculated K values during t h i s course of study should be considered as approximate values. Upon adsorption of metal ions by water-washed surface coal (Figure 33A) the 1720 cm"1 band decreases (K 1720 drops from 2 0.31 to 0.11 cm /mg) while the 1600 band increases (K 1600 increases from 0.43 to 0.65). These changes are also accom- panied by a decrease i n the i n t e n s i t y of the 1100 cm 1 band (K 1100 drops from 0.42 to 0.25 cm /mg) and also a s l i g h t increase in the 1400 band. In the case of adsorption of the 168. barium ions, the changes are much greater and the 1720 band (assigned for COOH) almost disappears. These changes are l i k e l y due to the conversion of -COOH to COO" carboxylate form to which metal ions are expected to be bonded by ele c t r o - valent bonding. These results are in a good agreement with that ob- tained by Schnitzer, 1969 for metal-soil humic acid complexes. The great decrease in the in t e n s i t y of the 1100 cm 1 band i s l i k e l y due to the p a r t i a l p a r t i c i p a t i o n of phenolic -OH groups in the int e r a c t i o n with the metal ions. Since the broad band exists in the region between 1100 - 1200 cm 1 in a l l the i n f r a - red spectra values of humic materials they are assigned as due to phenoxy C-0 vibrations of phenolic -OH groups (Schnitzer, 196 4; Wright, 1960). Spectrum "a" i n Figure 33B shows that washing the coal with acid, increases the intensity of the 1720 cm 1 and the 1100 cm"1 bands and th i s i s due to the conversion of the carboxylate form to the acid form COOH. Also, a sharpening of the 1100 i s noticed which may be due to the dissolution of some of the "gangue" mineral matter which absorbs i n f r a - r e d at the same wave length leaving the organic matter band with less broadening. Spectra "b" and "c" of Figure 33B indicate that the changes in the main bands are the same as in the case of water, washed coal, and therefore confirms the involvement of both carboxyl and to some extent phenolic hydroxyl i n the mechanism of adsorption of metal ions by coal. 169 A greater decrease i s noted in the 1720 cm ^ band where the K 1720 drops from 0.41 to almost zero, while K 1100 decrease 2 from 0.7 to 0.3 cm /mg. In addition, the new band starts to appear at the 1400 cm \ i s also assigned for carboxylate forma- tion (COO") (Schnitzer, 1971). Accordingly, acid washed coal may be expected to exhibit more r e a c t i v i t y than water washed coal due to the increased a v a i l a b i l i t y of the free COOH groups upon a c i d i f i - cation. Figures 33C and D are the i n f r a - r e d spectra of water washed and acid washed core coal samples respectively. Spectrum "a" in Figure 33C shows that the core coal does not contain any appreciable free carboxylic groups com- pared to the oxidized surface coal. However upon acid washing a very s l i g h t shoulder at the 1720 cm 1 appears which i s mainly due to carbon oxygen double band (C =0) stretching v i b r a t i o n . This indicates that there are very few COO groups in the structure of the core coal which i s considerably less oxidized than the surface coal. By adsorption of the metal ions, the changes obtained in the main in f r a - r e d absorption bands of the spectra are com- pl e t e l y d i f f e r e n t than those obtained in the case of surface coal. Spectra "b" and "c" in Figures 33C and D show a great decrease in the i n t e n s i t y of the 1600 cm 1 band (K 1600 drops 2 from 0.6 to 0.23 cm /mg while no appreciable change in the K 1100 is noticed. A sharp decrease i s also noticed in the 170. K 3450 values from 0.63 to 0.25 cm^/mg. This band i s usually- assigned to hydrogen bonded -OH, while in the case of surface coal no change in the 3450 can be noticed. This change can be explained by the p a r t i c i p a t i o n of the phenolic hydroxyl -OH groups in the mechanisms of the adsorption of metal ions by core coal to a higher degree than that in the case of surface coal, where the carboxyl groups show the greater involvement in the mechanism. A formation of coordinate covalent bonds, involving oxygen, phenolic OH groups, and the metal ions i s expected in this case. However, i t should be mentioned that i t i s possible that decreases in absorption in t h i s frequency region are o f f s e t by increased absorption a r i s i n g from OH groups of water or other sources. 3.2.1 Proximity of carboxyls in coal Spectra marked "d" in Figures 33A, B, C and D describe the spectra obtained for the anhydride form of each coal sample under scrutiny. These shoulders at 1775, 1800 and 1190 cm - 1 assigned to stretching v i b r a t i o n of anhydride form of humic acids (Wood, 1961). The peaks near 1100 cm 1 , in the spectra of the anhydride form are mainly due to the increase of the C-0 bond formation. In both types of coals, acid anhydrides may already be formed, therefore, there i s l i k e l y to be a substantial 171. portion of the COOH and phenolic -OH groups already present in the coal, which are l i k e l y to occupy positions adjacent enough to each other to form 5-membered c y c l i c anhydrides of the following (Wood, 1961). Type I: By interaction of 2 adjacent -COOH groups Type I I : By interaction of one COOH with an adjacent phenolic OH group to form either c y c l i c esters or open chain a l i p h a t i c esters Ar I O I c = o I C H 3 The increase in in t e n s i t y of the 1720 cm x band after anhydride formation i s probably due to the ester forma- tion. Between 10-90% of the COOH groups i n eight d i f f e r e n t humic acid preparations were found to form c y c l i c anhydrides (Butler, 1966). From this r e s u l t , i t appears that a sub- s t a n t i a l portion of the COOH groups i n coal may occupy positions 1-7-2. close enough to each other to form metal complexes which have a c y c l i c structure s i m i l a r to that of the c y c l i c anhydride; this i s further supported by the great s i m i l a r i t y obtained between the i n f r a - r e d spectra of the coal treated with the metal ions and that of the acid anhydride form of the coal. More study and research are required to prove this hypothesis on a quantitative basis and to determine the per- centage of the COOH forming a c y c l i c anhydride. 3.3 Cation exchange capacity The results shown in Table 28compare the value of the exchangeable Ca, Mg. K and Na cations with the t o t a l cation exchange capacity (CEC) for coal and activated carbon. It i s obvious that acid washed coal possesses the highest CEC value at 132.5 m.eg./lOO gm coal, value of 0.3 m.eq/100 gram i s obtained for the four exchangeable cations mentioned above. This r e s u l t shows that surface coal can be ranked as a good cation exchange material. Its r e a c t i v i t y i s therefore mainly attributed to the available cation exchange si t e s which do not include exchangeable cations of Na, K, Ca or Mg ions but may be mainly due to an organic type of cation exchange which exists in the organic part of the coal. This type of cation exchange makes the coal capable of forming complexes, or chelates, upon interaction with the metal ions. 173. TABLE 28. EXCHANGEABLE CATIONS AND TOTAL EXCHANGE . .CAPACITY OF HAT CREEK COALS AND ACTIVATED CARBON Material Exchangeable Cations Total cation exchange m.eq/100 gm capacity (CEC) tr • i. t _ m _ . _ - t f i r\ r\ Ca Mg K Na Total m.eq/100 gm Water washed o, surface coal 9.24 4.52 0.218 0.97 15 84.8 Acid washed surface coal 0.14 0.06 0.046 0.04 0.3 132.5 Water washed core coal 19.84 7.81 0.557 8.81 > 37 38.7* Water washed activated carbon 7.11 2.76 0.091 3.92 14 14.4* * Acid washed samples for core coal and activated carbon do not have any s i g n i f i c a n t differences i n the CEC values than that of the water washed samples. This fact has been previously proven for s o i l (Kelley, 1948) where the part played by organic matter in cation exchange was traceable to the so-called humic acids. Water washed surface coal exhibits s l i g h t l y lower values of CEC than the acid washed coal, i n d i c a t i n g that washing with acid helps to increase the r e a c t i v i t y of the coal through the introduction of more H + protons into the organic molecules. The core coal exhibits much lower values for the exchangeable cations and the t o t a l CEC compared to that of surface coal. A value of 37 m.eq/100 gm i s obtained for the exchangeable cation while 38.7 m.eq/100 gm i s the t o t a l CEC of the core coal. These results indicate that the exchangeable reac- t i v i t y of the core coal i s only due to the cations of Ca, Mg, K and Na which are l i k e l y present in the mineral part of the coal. No substantial organic cations seem to be involved. In comparison, activated carbon possesses the least value for exchange r e a c t i v i t y (CEC = 14.4 m.eq/100 gram) which is mostly the inorganic exchangeables of Ca, Mg, Na and K. This explains the low e f f i c i e n c y exhibited by activated carbon for the removal of heavy metal ions i n com- parison with the superior e f f i c i e n c i e s of the Hat Creek coal. 175. 3.4 Molar r a t i o between reacted lead and released hydrogen Detailed results of the lead adsorption experiments and the corresponding pH reductions are included i n Appendix.C-6. The s t a t i s t i c a l calculations and the percentage e r r o r s , which are calculated from duplicate experiments, confirm the high r e l i a b i l i t y of the measurement with an error ranging from 0.4 to a maximum of 2 1 . Table 29 summarizes the calculated molar r a t i o between the reacted lead and released hydrogen. A sample c a l c u l a t i o n of this r a t i o i s described i n Appendix C-6. It i s usually known that the magnitude of the pH reduction attained upon the addition of metal ions to aqueous solutions of humic substances i s often taken as a q u a l i t a t i v e indicator of complex formation, (Schnitzer and Khan, 1972). The greatest reduction i n pH i s obtained with acid P b + + - washed surface coal which leads to a molar r a t i o of — — - = 1/2. H This means that surface coal has the highest binding capacity towards metal ions to form a stable complex with a dis- placement of 2 H ions for each lead ion adsorbed. In the case of water washed surface coal, the drop P b + + in pH obtained i s much less and — ^ r - r a t i o i s equal to 1/1. H p b++ In comparison, the molar r a t i o — v — obtained when H water washed core coal i s used, i s i n order of 1/0.05 which indicates that there i s no appreciable hydrogen reduction on the addition of metal ions and therefore the p o s s i b i l i t y for complex TABLE 29. MOLAR RATIO OF ADSORBED P b + + and EXCHANGEABLE H + (Details i n Appendix C-6) Material Pb + + pH reduction — r — * H V v -.. 1. Surface coal water washed 1.535 1 :0.89 acid washed •1.810 1.07:2.0 2 . Core coal water washed 0.555 1 :0.055 acid washed 1.5 30 0.8 :2 - — = r a t i o between the adsorbed lead ions and the corres- + H ponding exchanged hydrogen which are replaced by lead ions and released i n the sol u t i o n . 177. formation i s very small, and a rather ordinary s a l t formation i s the predominant mechanism i n this case. Acid washing of the core coal seems to increase greatly i t s a b i l i t y for complex formation and in this case a higher magnitude of pH reduction i s obtained with a corres- Pb ponding — — r a t i o equal to 0.8/2 H 3.5 Acid groups in coal. Acid groups are defined as the carboxyl COOH plus the phenolic hydroxyl -OH. The l a t t e r i s considered to be the difference between the measured t o t a l a c i d i t y and the measured carboxyl groups. The values of the t o t a l a c i d i t y and carboxyl groups are presented both in mi l l i e q u i v a l e n t s per gram of coal and also i n terms of millequivalent per unit BET surface area for int e r p r e t a t i o n of the results with reference to the surface area available. The effects of some variables such as type of c o a l , type of washing applied and the magnitude of the change i n the acid groups which occur upon lead adsorption are determined s t a t i s t i c a l l y using a three way analysis of variance technique also the comparison with activated carbon i s ca r r i e d out using a two way analysis of variance methods as the factor of the e f f e c t of lead adsorption i s not included i n this case. A l l the obtained results and t h e i r s t a t i s t i c a l analysis are included i n Appendix C-7. 178. 3.5.1 Carboxyl groups Table 30agives a summary of the carboxyl groups of coal and carbon samples in m i l l i e q u i v a l e n t per unit BET surface area. It i s obvious that, acid washed surface coal has the highest number of carboxyl groups and therefore i s expected to be the most e f f i c i e n t i n the in t e r a c t i o n with metal ions. This r e s u l t i s i n good agreement with that obtained from other studies of the mechanism discussed in this chapter. The three way analysis of variance gives the s i g n i f i - cance of the e f f e c t of d i f f e r e n t variables on the values of the carboxyl groups. The F values included i n Appendix C-7,-1 show that carboxyl groups vary s i g n i f i c a n t l y when d i f f e r e n t coal samples are used. As an example, surface coal possesses the highest number of carboxyl groups, approximately 8 times more than core c o a l , while activated carbon has a n e g l i g i b l e carboxyl value which i s approximately 500 times less than that of core coal. The s t a t i s t i c a l analysis also show that acid washing affects in a highly s i g n i f i c a n t manner the number of carboxyl groups in coal. The number of carboxyl groups increases a f t e r acid washing due to more conversion of COO to the free carboxyl COOH. This fact has been proven also in other sections of this chapter. It i s important to prove through t h i s study that upon adsorption of lead ions the carboxyl groups o f coal decrease s i g n i f i c a n t l y and this confirms the view that the carboxyl 179. TABLE 30a. MEAN VALUES OF CARBOXYL GROUPS IN COAL AND CARBON IN M.EOUIV/UNIT "BET" AREA. EFFECT OF WASHING AND ADSORPTION OF LEAD.* Surface coal Core coal Activated Carbon Water washed Untreated 0.717 0.0696 0.0001 Treated with lead 0.662 0.0854 N.D. Acid washed Untreated 0.861 0.1081 0.0002 Treated with lead 0.713 0.0928 N.D. N.D. Not detectable * - A l l values quoted i n m i l l i e q u i v a l e n t s per unit B.E.T. area. - Methods outlined i n section 2, pp.146. - The rel a t i o n s h i p between the carboxyl groups i n coal and the lead ions adsorbed i s shown i n section 4, pp. 188. 180. groups are highly involved in the adsorption mechanism of metal ions by coal. The F-test also showed s i g n i f i c a n t interaction between the type of washing and the treatment with lead ions. This can be explained by the increase of the free carboxyl group obtained as a r e s u l t of acid washing which w i l l enhance the i n t e r a c t i o n with the lead ions and therefore create an increase in the adsorptive capacity as expected. Also, the in t e r a c t i o n between the type of coal and the treatment with lead i s conclusive i n a f f e c t i n g the carboxyl values in a way which can be explained by the d i f f e r e n t levels of carboxyl groups obtained from the two coals and the activated carbon tested. This consequently would a f f e c t the adsorption capacity obtained for each type of material. 3.5.2 Phenolic hydroxy1 -OH Two way and three way analyses of variance have been applied to the data obtained for t o t a l a c i d i t y and the calculated phenolic -OH values for the two types of coal, as well as the activated carbon. A l l results are included i n Appendix C-7-2. The type of coal r e f l e c t s s i g n i f i c a n t l y the values of the phenolic -OH groups. Surface coal s t i l l possesses the highest number of phenolic -OH groups reaching about 1.8 milliequivalents per unit BET surface area. In comparison, core coal has only 0.4 m.eq./unit BET area, while activated carbon seems to have no appreciable value; a calculated value being as low as 0.0006 m.eq./unit BET area i s obtained, as shown in Table 30b. TABLE 30b. MEAN VALUES OF PHENOLIC -OH (TOTAL ACIDITY — CARBOXYL COOH) FOR HAT CREEK COALS AND ACTIVATED CARBON. EFFECT OF TREATMENT WITH LEAD. VALUES IN M. EOUIV/UNIT "BET" AREA. Surface coal Core coal Activated Carbon Water washed Untreated Treated with lead Acid washed Untreated Treated with lead N.D. Not detectable 1.8 30 2 .182 1.940 1.919 0.339 0.276 0.271 0.375 0.0006 N.D. 0.0016 N.D. 182. Acid washing has a non-significant e f f e c t on the values of phenolic -OH in contrast to the e f f e c t obtained on the carboxyl groups discussed e a r l i e r . After adsorption of lead, no appreciable reduction i n the phenolic -OH values are noticed. This cannot be inter- preted as the phenolic -OH does not p a r t i c i p a t e in the i n t e r - action with metal ions since there are other factors which s t i l l control the calculated values of the phenolic -OH. Some of these factors are as follows: 1) The p o s s i b i l i t y that the decrease i n the number of phenolic -OH groups obtained upon i n t e r a c t i o n of the metal i s o f f s e t by the presence of OH groups of complexed hydroxylated metal and aluminum compounds already present in the coal. This i n t e r p r e t a t i o n i s i n agreement with that obtained from the in f r a - r e d spectral studies-where the i n t e n s i t y of OH absorption near the 3450 m * band remains undiminished a f t e r - metal adsorption. 2) The p o s s i b i l i t y of physical adsorption of barium hydroxide during the determination of t o t a l a c i d i t y gives r i s e to the values higher than the true values; this e f f e c t is therefore impossible to exclude . (Schaffer, 1970). 3) The p o s s i b i l i t y of the exchange of some adsorbed lead ions by barium ions used i n the t e s t , and therefore, the measured value of t o t a l a c i d i t y would be very s i m i l a r before and after treatment with lead. 183. The following Section 3.6 w i l l show the extent of exchange obtained during the t o t a l a c i d i t y test and carboxyl group tests using barium hydroxide and barium and calcium acetate respectively. 3.6 Lead exchanged with barium or calcium during the acid group tests. The released lead ions during the t o t a l a c i d i t y and the carboxyl group measurements are determined and shown in Appendix C-7-3 (Table 1). The highest l e v e l of exchange of lead i s obtained during the determination of carboxyl groups using the reflux- barium acetate method. Up to 2 3.5% of the adsorbed lead i s released.„ during the t e s t . This means that the carboxyl COOH values for coal treated with lead does not represent only the unreacted carboxyl because some of the barium ions are also consumed i n the exchange with the adsorbed lead and therefore the values from this test are expected to be higher than the true values. During the calcium acetate test for the carboxyl group, only 3.241 lead i s released and therefore the carboxyl values obtained from this test can be considered as the closest to the true carboxyl values and therefore, i t i s possible to use these values in the estimation of the number of carboxyl groups actually p a r t i c i p a t i n g in the i n t e r a c t i o n with lead, from which an approximate mechanism of reaction can be suggested. Table 30c. Released lead ions during the total acidity a.-:d carboxy group measurements. Coal S a c p l e a Total A c i d i t y U s i n g Ba(OH)„ Lasd Released ng/1 ias/ga c o a l Carboxyl Groups Usir.g Barium A c e t a t e Using Calcium Acetate • Lead R e l e a s e d Lead R e l e a s e d ng/1 mg/gm c o a l mg/l mg/gra c o a l Blank (no coal added) N.D. 3.5 N.D. 0.5 N.D. 1 Water-washed coal Original Treated with Lead 1 25 N.D. 3.07 6.93 3.5 30 N.D. 7.76 17.52 0.5 12 3.05 6.89 2 Acid-washed coal O r i g i n a l Treated with Lead 0.5 29 N.D. 3.54 8.69 N.D. 36.0 N.D. 9.59 23.53 N.D. 1.32 3.24 * The percentage of lead released lead released (mfl/gm coal) lead absorbed (mg/few coal) x 100 oo 184. During the t o t a l a c i d i t y determination, the lead released i s in the order of 7-9% from that already adsorbed, and this makes i t d i f f i c u l t to calculate the true number of phenolic -OH groups which i n t e r a c t with lead. Therefore, the i n f r a - r e d spectra may be taken as the only evidence for the contribution of the phenolic -OH groups i n the mechanism. 4. SUGGESTED MECHANISM FOR ADSORPTION OF LEAD BY COAL The main approaches used i n this research, to study the nature of the mechanism involved i n the adsorption of metal ions by coal, would provide strong evidences f o r the int e r a c t i o n of the organic acid groups of the coal, mainly carboxyls and phenolic hydroxyls, with the metal ions,to form metal complexes and/or simple carboxylates. The evidences, derived from the res u l t s obtained i n Section 3, can be summarized as follows: 1) Electron micro study. Lead ions are predominantly adsorbed on areas containing carbon and oxygen and not on mineral matter containing s i l i c o n . 2) I.R. spectral study: (a) Upon adsorption of lead ions by coal the 1725 and 1100 _cm 1 bands decrease i n i n t e n s i t y while the 1600 and 1400 cm 1 bands increase i n d i c a t i n g the conversion of COOH to COO" groups to which p o s i t i v e l y charged metal ions are probably bonded 185. by electrovalent linkages. It i s concluded that phenolic -OH i s l i k e l y p a r t i c i p a t i n g and the metal ions are probably banded i n this case to -OH by coordinate covalent bands, (Schnitzer, 1969). . (b) The formation of an acid anhydride form i s indicated and therefore, adjacent carboxyl and/or phenolic groups are confirmed to be i n the structure of the coal which raises the p o s s i b i l i t y of complex forma- tions . (c) The s i m i l a r i t y of the spectrum of the c y c l i c acid anhydride form to the spectrum obtained after adsorption of lead gives evidence that a metal complex si m i l a r to a c y c l i c anhydride form might be formed. 3) Chemical study (a) The high value of the cation exchange capacity CEC obtained for surface coal highly exceeds the t o t a l exchangeable cations of Ca, Mg, K and Na. This indicates the presence of other exchangeable si t e s in the coal, which are l i k e l y the organic a c i d i c func- t i o n a l groups. (b) The chemical analysis confirms that oxygen containing functional groups (carboxyls and phenolic hydroxyls) are abundant in Hat Creek coal e s p e c i a l l y the oxidized surface coal. (c) The number of lead ions adsorbed, hydrogen ions released and carboxyl groups blocked are correlated for acid washed surface coal. The r e s u l t i s , approximately, 186. one lead ion interacts with two carboxyl groups (measured by the calcium acetate method) releasing 2H + into the solution. 4) Possible clay - interference This section w i l l discuss the p o s s i b i l i t y of any interference in the adsorption mechanism by the presence of clay minerals present i n the coal. (a) Clay-minerals, mainly k a o l i n i t e and bentonite (Monto- m o r i l l o n i t e and i l l i t e ) d i f f e r greatly i n t h e i r surface properties. K a o l i n i t e possesses a very small 2 surface area of 5-20 m /g and a low capacity to adsorb cations. Montomorillonite has a large surface area of 2 700-800 m /g and a high cation adsorption capacity, perhaps 10-15 times that of k a o l i n i t e (Brady, 1974). In comparison, humic substances have a cation exchange capacity (C.E.C.) which fa r exceeds even that of montomorillonite. The following values show a comparison between the C.E.C. of clays and humic substances as given by Brady (1974) Material C.E.C. (m.eq/100 gm) K a o l i n i t e 8 Montomorillonite 100 Humic substances 150-200 A measurement of oxidized acid washed Hat Creek coal gives a C.E.C. value of 132 m.eq/100 gms. 187. The mineral matter content i n the oxidized coal samples (water and acid washed) used i n studying the mechanism was determined using a low temperature- ashing technique. An average value of 30% (d.w.b.) mineral matter was found i n the samples tested. The X-ray d i f f r a c t i o n analysis was used to i d e n t i f y q u a l i t a t i v e l y the type of minerals. A range of 70-80% (d.w.b.) of the minerals i s present as quartz (SiC^), while less than 20-30% (d.w.b.) i s present as k a o l i n i t e . No detectable bentonite was noticed. Therefore, k a o l i n i t e is the only detectable clay mineral found in the coal, i t represents not more than 6-9% (d.w.b.) of the coal sample. Because of the poor surface a c t i v i t y of k a o l i n i t e as described previously, the contribution of t h i s k a o l i n i t e i n retaining of metal ions i s presumed to be n e g l i g i b l e compared to that of the organic portion of the coal. The absence of bentonite from the tested samples further confirms that clay interference i s n e g l i g i b l e . A d i r e c t p r o p o r t i o n a l i t y i s shown between the amount of carboXyl groups of the coal and the lead ions removed as previously described in d e t a i l s in this chapter (section 3-4 and 3-5 and data included in Appendix C-6 and C-7. This p r o p o r t i o n a l i t y i s tested and outlined for both surface and core coal samples in the following table. 188. + + Propor. (B)Pb adsorbed Constant m. eq/gm coal (A) - (B) 0.392 5.67 0.426 6.26 0.158 5.20 0.393 3.24 The above data show that the amount of lead adsorbed i s d i r e c t l y proportional to the amount of carboxyl groups o r i g i n a l l y present i n the coal sample the r a t i o of -COOH to P b + + are ranged between 5-6 for a l l coal samples except for the acid washed core sample which has a value of about 3.2. This can be explained by s i g n i f i c a n t p a r t i c i p a t i o n of the phenolic -OH groups in this sample i n the in t e r a c t i o n with lead ions. If clay were responsible for any lead retention the pro p o r t i o n a l i t y , explained above, would not be so evident. (d) The electron microprobe study shows c l e a r l y that lead ions are predominantly adsorbed on areas containing carbon and oxygen and not on mineral matter containing s i l i c o n . The s i l i c o n i s also one component of the k a o l i n i t e found i n the coal samples. As a conclusion, the above evidences confirm c l e a r l y that clay-mineral i n the coal does not contribute s i g n i f i c a n t l y i n the removal of lead ions and therefore the main adsorption CA) -COOH Coal Sample m.eq/gm coal S.W 2.222 S.A 2.670 C.W 0.821 C A 1.275 189. mechanism takes place through the organic acid functional groups without any interference of the clay mineral of coal. Suggested mechanism: The above mentioned evidences confirm the fact that chemisorption rather than physical adsorption i s involved in the adsorption of lead by coal, and a mechanism of cation exchange nature i s assumed to be the predominant mechanism in which carboxyls and p a r t i a l l y phenolic hydroxyls are bonded with the metal ions by electrovalent and coordinate covalent bonds respectively to form metal complexes with the coal. These conclusions were previously confirmed f o r the i n t e r a c t i o n of humic acids extracted from either l i g n i t e or s o i l with divalent metal ions (Schnitzer and Skinner, 1965). Accordingly,three types of mechanisms may be suggested to take place during the adsorption of lead ions by coal : It was suggested e a r l i e r that Type I mechanism i s the predominant one at high metal ion concentration with a development of electrovalent bonds, while Type II or III mechanisms are the predominant ones at low metal ion concen- t r a t i o n with the development of coordinate covalent bonds (Gamble and Schnitzer, 1970). In the case of coal, Type I i s suggested to be l i k e l y the most predominant one i n the case of acid washed oxidized surface coal. While Type II or III are suggested to be the predominant ones when core coal i s used. 190. TYPE I ': TWO ADJACENT CARBOXYL GROUPS. 0 - Pb TYPE II : CARBOXYL GROUPS IS ORTHO TO A PHENOLIC GROUP. TYPE III s TWO ADJACENT CARBOXYL AND ONE ORTHO PHENOLIC HYDROXYL. 1912 B. Mechanism of Adsorption of Dissolved Organics by Coal Preface : E a r l i e r work, discussed in Chapter VI has shown that Hat Creek coal i s e f f e c t i v e in the removal of biodegradable dissolved organic materials from solutions. This part of the research deals with the investigation of a mechanism for the removal of dissolved organics on the coal surface and to estimate the magnitude and the e f f e c t of b i o l o g i c a l a c t i v i t y in f i x e d coal beds for removal of the organics. A material balance study on the coal bed system was u t i l i z e d to estimate approximately the biooxidizable f r a c t i o n of the organic substrate. 1. MATERIALS 1.1 Adsorbent . Granular Hat Creek surface coal is used in a l l of the experi- ments. Two p a r t i c l e sizes of coal were used: 1. 0.5 33 mm average s i z e . 2. 0.2965 mm average s i z e . 1.2 Adsorbate * "0X0" Beef Bouillon cubes were used as an organic substrate. The B0D5 and COD obtained by disso l v i n g a cert a i n weight of cube i n water was ca l i b r a t e d for a p a r t i c u l a r con- centration. * Supplier: 0X0 Foods D i v i s i o n , Brooke Bond Foods Limited, B e l l e v i l l e , Canada. 192. However, "0X0" cubes contain other non-dissolved or p a r t i a l l y dissolved biodegradable organic or inorganic matter such as spicy materials, starches, f l a v o r i n g agents, synthetic colors, etc. These materials were responsible for most of the problems encountered during the course of the experiments. 2. DESIGN OF EXPERIMENTS Three sets of experiments were conducted using fixed bed techniques under saturated (anaerobic) conditions. Several small columns of size 20 cm X 7 cm I.D. were used. 2.1 Using a coal bed with average coal p a r t i c l e size of 0.2965 mm The bed was previously inoculated with two l i t e r s of the same substrate, drained, and l e f t for 72 hours to enhance the b a c t e r i a l growth on the coal surface. Then the i n f l u e n t with certain levels of BOD,. , COD and TOC were leached-through continuously at a flow rate of 50 ml/min to allow a contact time of 18 minutes along the column. Grab.samples were c o l l e c t e d p e r i o d i c a l l y for analysis. A f t e r passing 40 l i t e r s of the s o l u t i o n , the bed was "blocked" due to the increase i n the head loss. Backwashing was conducted using 20 l i t e r s of sodium hydroxide solution of pH = 11 (FMC Corporation, July, 1971). Composite samples from the washings were analyzed for BOD,., COD and TOC. After r i n s i n g and draining the bed, further volumes of substrate were leached continuously and the e f f l u e n t samples were analyzed. 19 3. 2.2 Using coal bed with an average coal size of 0.5 3 3 mm Applying the above mentioned technique with a larger size of coal in order to overcome the "blocking" problem which occurred i n the case of using the smaller size of coal . 2.3 E f f e c t of inoculation A t h i r d coal bed with average coal size of 0.533 mm was set up and run anaerobically without an i n i t i a l inocula- tion u n t i l a break through point was reached. 2.4 A n a l y t i c a l methods 2.4.1 Total carbon (TC) and inorganic carbon (TIC) analyses were conducted on the Beckman Total Organic Carbon Analyzer Model 915. 2.4.2 BODg and COD analyses were conducted by chemical methods i n accordance with the APHA Standard Methods, 14th e d i t i o n , 1 9 75. 194. 3. RESULTS AND DISCUSSION The results shown i n Appendix C-8, Table 1 indicate c l e a r l y that TOC, COD and BOD,, values can be lowered by more than 50% using a coal media bed of p a r t i c l e size 0.2965 mm. The e f f i c i e n c y of removal declined s l i g h t l y due to the develop- ment of anaerobic conditions throughout the column. Multiple layers of b a c t e r i a l slime were formed on the coal surface which led to a leakage (increase) i n the TOC, BOD,, and COD values of the effluent i n addition to a gradual decrease of the hydraulic conductivity; backwashing with 4 runs of 5 l i t e r s each of sodium hydroxide solution (pH = 11) removed the p h y s i c a l l y adsorbed organic materials from the coal sur- face. The washed materials were evaluated i n terms of BOD,., COD and TOC as shown i n Table 2, Appendix C-8. The"results indicate that the f i r s t f i v e l i t e r s of wash solution removed most of the organic matter. Further washing was continued u n t i l no further change i n the BOD,., COD, TOC was obtained. This indicated that most and possibly a l l of the p h y s i c a l l y held materials were removed. Meanwhile, a control experiment was conducted to evaluate the organic components which might be washed from the coal with the organic materials of the substrate. This value was subtracted from a l l of the washing analyses to obtain the net value of the organic matter of the subtrate which was adsorbed by the co a l . Table 31 shows that no more than approximately 103 mg of organic components of the coal were leached out by sodium hydroxide. TABLE 31. MATERIAL BALANCE FOR CALCULATION OF THE BIO-OXIDIZABLE FRACTION . OF THE ORGANIC SUBSTRATE Average Particle Size of coal = 0.2965 mm - ON TOC BASIS ON COD BASIS ON B0D5 BASIS mgs mgs mgs 1. Total amount applied 3280 8840 6280 2. Amount removed by the coal 1680 4480 3640 3. Organics washed out by backwashing 1015 2155 1215 4. Amount washed from the coal surface by NaOH (Control) 103 — — 5. Estimated physically adsorbed fraction (3)-(4) 912 2155 1215 6. Estimated bio-oxidized or consumed fraction through bacterial action (2)-(5) s 768 2325 2425 PERCENTAGE PHYSICALLY ADSORBED 54% 48% 33% ' PERCENTAGE BIO-OXIDIZED 46% 52% 67% 196. E a r l i e r work showed that the surface of the coal p a r t i c l e s provided an enriched micro-environment for the microbial metabolism which enhanced the b i o l o g i c a l a c t i v i t y and the b a c t e r i a l growth on the surface. Therefore, bio- l o g i c a l degradation or biooxidation of part of the organic matter could be expected. In order to estimate the bio- oxidized organics, an o v e r a l l material balance on the coal bed was determined. The results shown i n Table 31 indicate that 46% of the TOC was oxidized i n a 60 mesh size coal bed, while 54% was p h y s i c a l l y adsorbed. On the COD basis, 52% was biooxidized while the highest value obtained was on the BOD,, basis reaching 67%. T h i s indicates that b a c t e r i a l bio- degradation i s the dominating process on the surface. Other forms of organics found i n the "OXO" substrate were not re a d i l y biodegradable such as f l a v o r i n g agents, c y c l i c organic compounds, spices etc. These materials are d i f f i c u l t to oxidize by b a c t e r i a l action and th i s fact also explains the r e l a t i v e l y lower values obtained for oxidized fractions i n terms of TOC and COD. 3.1 E f f e c t of backwashing on the regeneration of coal beds. A second batch of organic s o l u t i o n was run through the backwashed columns and the cumulative TOC, COD and BODj. effluent from 16 l i t e r s applied on the spent coal are represented i n Figures 34a, b and c respectively. A l l figures show a lin e a r relationship between the load applied and the t o t a l amounts  •861 B O D R E M O V E D DURING TEST PERIOD, . G R A M S 200 removed by the coal under this l i m i t e d loading. From these r e s u l t s , i t i s obvious that NaOH can be a good regenerant for spent coal since the adsorptive quality of the coal i s regained p a r t i a l l y a f t e r backwashing. Table 3, Appendix C-8 summarizes the reduction in TOC, COD and BOD,-. When a larger size of coal (0.533 mm diameter) was used, a better hydraulic conductivity was obtained allowing a longer time period for effluent applica- tion before "blocking" occurred. P r i o r to applying the e f f l u e n t , the coal bed was seeded with two l i t e r s of substrate solution and l e f t for three days drainage. This period of inoculation aids in the i n i t i a t i o n of b a c t e r i a l growth and as a consequence more b i o l o g i c a l a c t i v i t y i s expected by continuous running of the substrate solution through the bed, r e s u l t i n g in a con- tinuous improvement i n the e f f i c i e n c y of removal due to the b i o l o g i c a l oxidation. This means that the nine l i t e r s applied in this experiment were not enough to give adequate time for b a c t e r i a l growth and metabolism on the coal surface. However, other workers have proved that continuous throughput improves the e f f i c i e n c y (F.M.C. Corporation, 1971), also aerobic conditions give better removal than anaerobic conditions. These factors should be taken into consideration in future work when studying the e f f e c t of inoculation of the coal bed on the removal e f f i c i e n c y of organics. A series of experiments using the 0.533 mm size coal were conducted but without i n i t i a l inoculation and the results comoared with that obtained with the inoculated beds. The 201, comparison i s shown in Figure 34d and v e r i f i e s that inoculation gives better e f f i c i e n c y for reduction of TOC, COD and BOD,. l e v e l s . An appreciable gradual drop i n the e f f i c i e n c y was observed when a non-inoculated column was used; by running eight l i t e r s through the column an average of 28% reduction of TOC was achieved, while only 15% for B0D5 and 25% for COD. These values are about one-half the e f f i c i e n c i e s obtained with the inoculated bed. Backwashing with NaOH was applied on the inoculated bed with the larger coal size and a material balance ca l c u l a - tion on the t o t a l organic carbon showed that about 43.5% of the organic matter i s oxidized while 56.5% i s adsorbed. In comparison, these results are very s i m i l a r to those obtained by using the f i n e r p a r t i c l e size of coal of 0.2965 mm. 3.2 Suggested mechanism for reduction of dissolved organics by coal One possible explanation of the observed phenomonen may be that shown in Figure 35. I t i s assumed for t h i s explanation that two b i o l o g i c a l l y active films surround each coal p a r t i c l e . The i n t e r i o r f i l m i s anaerobic, the external f i l m i s aerobic. Adsorbable molecules pass through the films to the coal surface where p a r t i a l anaerobic degradation may take place, forming low molecular weight degradation products such as organic acid, and alcohols, which have an inherently low r e l a t i v e energy for adsorption, this w i l l diffuse through the external boundary f i l m to the bulk solution. I f an aerobic state i s maintained TOTAL ORGANIC CARBON REMOVED MGS. 10 co cn O o o o o o o o o o o o> o o 'ZOZ 203. EVENT S E Q U E N C E S ' I. DIFFUSION OF LARGE ADSORBING ORGANIC MOLE- CULE (A) TO SURFACE OF CARBON. 2. ANAEROBIC DEGRADATION Or LARGE MOLECULE (A) TO SMALL MOLECULE (f). 3. DIFFUSION OF SMALL NON-ADSORBING ORGANIC MOLECULE (B) AWAY FROM SURFACE OF CARBON. 4. AEROBIC DEGRADATION OF SMALL MOLECULE (§) TO C 0 2 AND H 2 0. FIGURE 35— S C H E M A T I C I N T E R P R E T A T I O N O F T H E M O D E O F I N SITU B I O L O G I C E X T E N S I O N O F A D S O R P T I O N C A P A C I T Y (From: FMC Corporation) 2 0 4 . in the outer layer of the boundary f i l m on the coal and in the solution phase, aerobic microorganisms are expected to grow and oxidize the outward d i f f u s i n g products of the anaerobic decomposition. This i s consistent with the observation that the effluents from the anaerobic coal beds used f o r th i s research contain appreciable leakages to TOC, COD, and BOD^ which were due to non-adsorbable organic matter, e i t h e r from the additives found i n the "0X0" beef cubes or from the anaerobic decomposition of the substrate. This in t e r p r e t a t i o n i s of course speculative. 205 . VII • APPLICATIONS IN SEWAGE TREATMENT Preface The o v e r a l l objective of this program of research and experimentation was to apply the coal sorption process to the treatment of municipal and i n d u s t r i a l sewage for the removal of undesirable dissolved pollutants. Many of the pollutants, which are of organic or inorganic nature, are d i f f i c u l t to remove during the primary and secondary treatment of sewage. Therefore in this chapter the applied aspects of the research are focussed upon the following sewage e f f l u e n t s : 1) Municipal sewage effluent emanating from the City of Vancouver was investigated for the removal of major dissolved pollutants such as BOD,., COD, phosphorus, nitrogen, organic carbon and lead. 2) Industrial sewage effluent was obtained from an o i l re f i n e r y to investigate the removal of the major pollutants such as phenol, cyanide, ammonia and dissolved organics. In each case both batch, continuous, and long-term experiments were conducted to evaluate the adsorptive capacity and the service l i f e of Hat Creek coal to treat such e f f l u e n t s . Tentative calculations for the design of a coal bed based on the test data obtained indicated the design parameters which should be considered. 206. 1. MATERIALS . 1.1 Hat Creek coal Oxidized coal from the surface deposit was used in most of the experiments. Unoxidized core coal and activated carbon were used occasionally for comparison. The descrip- tions of these materials were previously mentioned i n Chapter I I I . 1.2 Municipal sewage ef f l u e n t Samples of primary treated sewage were obtained from the Greater Vancouver Sewerage and Drainage D i s t r i c t at the sewage treatment plant on Iona Island. This effluent flows at a rate of 70 MGD and had been subjected to settlement and removal of the s o l i d s . 1.3 Industrial sewage eff l u e n t This was a refin e r y wastewater supplied by the B.C. Petroleum Corporation. The eff l u e n t had been previously passed through a t r i c k l i n g f i l t e r . Both the municipal and the i n d u s t r i a l effluents were stored in a 34°F cold room p r i o r to the laboratory experiments. 2. METHODS 2.1 Batch tests The methods used were described i n Chapter VI. Several coal p a r t i c l e sizes were t r i e d during these tests. 2.2 Column tests The method was described e a r l i e r i n Chapter VI. Small 20 7. columns of size 20 cm X 7 cm I . D . f i l l e d with granular coal of sizes 4/14, 6/20 and 14/20 were used for the tests. 2.3 Design applications The following long-term leaching processes were performed on a semi-pilot scale for the express purpose of obtaining s u f f i c i e n t data for the tentative c a l c u l a t i o n of the size of the coal bed required and the rate of consumption of the coal to treat certain sewage e f f l u e n t s . 2.3.1 Removal of lead from the a r t i f i c i a l sewage e f f l u e n t Three columns of 4.76 cm I.D. and 35 cm, 70 cm and 140 cm lengths respectively were constructed and f i l l e d with fresh washed Hat Creek coal of 4/14 mesh s i z e . A 5 mg/l lead solution was fed to each column at a rate of approximately 1 gal (Imp.) per minute per square foot of surface area 2 (gpm/ft ). Daily e f f l u e n t grab samples were c o l l e c t e d from each column and analyzed for the residual lead. Leaching continued u n t i l a "break through point" of 0.5 mg/l of lead appeared in the effluent solutions. 2.3.2 Removal of dissolved organics from Iona sewage eff l u e n t A continuous column process was set up at the Greater Vancouver Sewerage and Drainage D i s t r i c t sewage treat- ment plant on Iona Island to provide for a steady supply of fresh sewage to the coal bed column. A larger column (described e a r l i e r in Chapter VI, Figure 11 ) of dimensions 2m X 15.24 cm I.D., containing approximately 23 kgs of Hat Creek coal of p a r t i c l e size 6/20 208. mesh was employed. The sewage ef f l u e n t was f i r s t pumped through the bed continuously under fixed-bed flow conditions. Aft e r 4 days of operation, the head loss increased greatly due to fouling from the sediment and subsequent blocking of the bed. The flow was then reversed to an expanded-type flow at a steady flow rate ranging between 300 - 315 mls/min which 2 i s equivalent to 1 gpm/ft of area, allowing 30 minutes con- tact time. Grab samples were c o l l e c t e d p e r i o d i c a l l y from the 0, 0.5, 1 and 2 meters levels along the bed. The samples were then analyzed for B0D5, COD, TOC and occasionally for pH as well as t o t a l and v o l a t i l e residue. The break through point was a r b i t r a r i l y set up at BODg concentration of 50 mg/1 i n the e f f l u e n t . 2.3.3 Removal of phenol, cyanide and ammonia from the re f i n e r y effluent A mixture of cyanide,phenol and ammonia, approximating concentrations of 1,2 and 50 mg/1 respectively was used as a synthetic waste e f f l u e n t . The e f f l u e n t was f i l t e r e d through the larger column (2 m X 15.24 cm I.D.) containing approximately 18 kgs of coal. Water washed surface coal from the Hat Creek deposit of p a r t i c l e size 4/14 mesh was used. The flow rate was 2 adjusted at 300 - 350 ml/min which i s equivalent to 1 gpm/ft at a contact time of approximately 30 minutes. Grab samples were c o l l e c t e d p e r i o d i c a l l y from the 0, 1ft (30.5 cm), 3ft (91.4 cm) and 5%ft (167.8 cm) lev e l s respectively and analyzed. The break through point was set 209 . at 1/10 o£ the applied influent concentrations which are equivalent to approximately 0.2 mg/l of phenol, 0.1 mg/l of cyanide and 5.0 mg/l of ammonia. The a n a l y t i c a l methods used for a l l of the above analyses were previously described i n Chapter VI. 3. RESULTS AND DISCUSSION 3.1 Municipal sewage The Iona sewage samples used i n these tests appeared to be d i l u t e d with storm water. The BOD,, and COD values shown in Table 1 , Appendix C-9-1 are r e l a t i v e l y low com- pared to a dry weather sample obtained e a r l i e r i n the season with a BODg analysis of 160 mg/l. 3.1.1 Batch tests Two sets of experiments were applied using two di f f e r e n t coal sizes of 48/60 mesh and < 150 mesh respectively. The test results are summarized i n Tables 1 and 2 included in Appendix C-9-1. Apparently a 1% w/w addition of coal i s quite e f f e c - t i v e , y i e l d i n g a BOD^ reduction from 103 to 11 BOD,, i n the f i r s t hour of contact. The removal i s greater than 89% r i s i n g to more than 94% in 24 hours of contact, while a 5% w/w addition of coal did not improve the removal value. Similar results with s l i g h t l y lower removal values are shown for the COD analysis. The nitrogen content may account for this 210. change. The t o t a l nitrogen removal shows a more encouraging resu l t than that for previous n i t r a t e removal. This i s likely- due to an ammonia content i n the sewage which formed a c a t i o n i c r a d i c a l (NH^ +); t h i s r a d i c a l was then read i l y adsorbed on the coal surface more so than the anionic NO^ which i s quite soluble and less l i k e l y to adsorb on the coal surface. Also, the re s u l t s show that lead ions are removed completely from the sewage to a non-detectable value when 1% coal i s added. Figure 36 gives a comparison between the e f f i c i e n c y of removal of a l l the mentioned pollutants by the coal. 3.1.2 Column test This process gives a better removal of pollutants than the batch t e s t s . The contact time in the column was approxi- mately 25 minutes which is considered s l i g h t l y lower than that used in the large scale applications with activated carbon when the contact time usually ranges from 35 - 50 minutes. Af t e r 8 l i t e r s of continuous application of the sewage to the column, the coal appears to be continuing i t s normal rate of removal of d i f f e r e n t pollutants, namely BOD,., COD, T-N, T-P, O-P and lead as shown in the data l i s t e d in Table 1, Appendix C-9-2. It appears that a greater throughput volume should be applied to reach the break through point before the column becomes exhausted. C O N T A C T . TIME , HOURS- FIGURE 36 : EFFICIENCY OF REMVAL OF POLLUTANTS FROM IONA SEWAGE EFFLUENTS. 212. It seems fortunate that t o t a l nitrogen i s removed which may contain ammonia i n larger proportions. The NO^-N value is not as serious a factor i n Iona sewage since i t i s at very low concentrations. Both the 0-P and T-P are removed almost equally by column leaching but the removal declined s l i g h t l y a f t e r 8 l i t e r s of a p p l i c a t i o n . However, the highest e f f i c i e n c y of removal was obtained for lead i n both the contact and the leaching process. More than 80% of the lead was removed, calculated on a detectable basis. However t h i s should, in essence, approximate a 100% removal value. Figure 37 gives a comparison of the e f f i c i e n c y of the coal to remove each pollutant under observation from the municipal sewage. 3.1.3 Design applications 3.1.3.1 To remove lead ions from Iona sewage The long-term experiment, described i n section 2.3.1, was conducted for 58 days (1129 hours) of continuous leaching using the three coal bed depths of 30, 60 and 120 cm respec- t i v e l y . The columns and capacity data are tabulated i n Appendix D-l. Table 1, while the break through curve for the 30 cm column i s shown in Figure 38 i n d i c a t i n g that the break through point at 0,5 mg/1 of retained lead i s reached after passing approximately 380 gals of flow through the 30 cm column. FIGURE 37 : EFFICIENCY OF REMOVAL OF ORGANIC & INORGANIC POLLUTANTS FROM IONA SEWAGE BY COAL. FIGURE 38 : BREAK-THROUGH CURVE AT 30cm LEVEL FOR LEACHING OF LEAD SOLUTION THROUGH COAL BED. 215. According to the Bohart Adam design rel a t i o n s h i p (Eckenfelder, 1970) i f the service time to reach the break through point i s plotted vs. depth of the bed in feet for the three columns, a straight l i n e i s obtained as shown i n Figure 1 i n Appendix • D-l as an evaluation of the design parameters of a coal bed. The application of the Bohart Adams relationship i s u t i l i z e d to estimate the size of the bed required as well as i t s performance. A tentative c a l c u l a t i o n based on the available data and the application of the Bohart Adams rel a t i o n s h i p , to treat Iona sewage e f f l u e n t , i s out- l i n e d in d e t a i l in Appendix D-l. The estimated size and performance of t h i s bed are found as follows: Iona flow 70 MGD Influent lead concentration 0.2 mg/l Effluent lead concentration (break through point) 0.05 mg/l 2 Flow rate 1 gpm/ft Contact time 30 minutes Estimated bed area 1.1 acre Estimated bed depth 5 f t (152.4 cm) Amount of coal in bed = 5000 short tons (2273 metric tons) Amount required for renewal per day = 1 metric ton/day Total lead removed = 48 kgs/day E f f i c i e n c y of the bed =70% 216. To obtain more r e l i a b l e values for design purposes larger scale p i l o t experimentation i s required. The larger scale would minimize the " s c a l i n g up" e f f e c t which i s hazar- dous in forecasting the results of such large beds as that envisioned for 70 MGD based on small column r e s u l t s . 3.1.3.2 To remove dissolved organics from Iona sewage The coal bed was operated continuously for 20 days (471 hours) although two interruptions occurred due to reversing the d i r e c t i o n of the flow and to backwashing the bed respectively. ; The throughput volume was approximately 1790 gallons of sewage flowing at an average rate of 315 ml/min which i s 2 equivalent to 1 gpm/ft of area for an allowable contact time of 30 minutes. A l l the obtained results are l i s t e d i n Tables 1, 2, 3, 4, included in Appendix D-2.. : ; - i which show the e f f e c t of treatment on the sewage for the reduction of s o l i d s , B0D5, COD and TOC respectively at three , leve l s of 0, 0.5, 1 and 2 meters depth of c o a l . The e f f e c t s of the treatment on reducing the p o l l u - tion parameters of the sewage are summarized as follows: a. pH With the coal treatment, a substantial decrease i n the pH value of the o r i g i n a l sewage was noticed. The neutral pH value of 6.84 for the sewage was dropped to an a c i d i c value of 5.1 at the 2 meter l e v e l i n the bed. 217. b. Solids Solids include the t o t a l residue, v o l a t i l e residue and fixed residue. The res u l t s i n Table 1, Appendix D-2 show no substantial reduction of the value of s o l i d s . Although during the f i r s t day of operation, an increase rather than a decrease i n the t o t a l and v o l a t i l e residue was obtained, this i s l i k e l y due to the leaching of some water-soluble components from the coal. A f t e r the f i r s t day, no further increase i n the t o t a l or v o l a t i l e residue was noticed. However a s l i g h t reduction of 39% in the v o l a t i l e residue was obtained. c. BOD5 The reduction of BOD^ by treatment with coal i s ] ' considered s a t i s f a c t o r y . The results included i n Appendix D-2 Table. 2 show that after the leaching of 976 gallons through the bed the e f f i c i e n c y of removal does not decrease and i t remained at a high value of 88% at the 2 meter l e v e l under expanded-flow conditions. A f t e r backwashing, the bed maintained an e f f i c i e n c y of 75% for the f i r s t 200 gallons of sewage app l i c a t i o n , a f t e r that the e f f i c i e n c y i s decreasing to a value of 38% after the application of 1790 gallons. The adsorptive capacity of the coal to remove BOD^ was estimated from the analysis obtained from the ef f l u e n t from the 0.5 meter l e v e l . The results shown i n Table 5 indicate that more than 1377 gallons of sewage were passed 218. through before reaching the break through point at 50 mg/l BOD,, i n the e f f l u e n t . A cumulative e f f i c i e n c y of removal of approximately 5 7% was calculated at this point. During this period more than 390 grams of BOD,, was removed. The adsorptive capacity, under these conditions, was found to be equivalent to 95 mgs BOD,, removed per 1 gram of coal. During the running periods some grab samples exhibited unexpected very low removal of BOD,.. This can be explained as due to the leakage of BOD,, (a sudden increase in the BOD,, l e v e l due to the presence of b a c t e r i a l slime), also due to a channeling e f f e c t through the coal p a r t i c l e s . Therefore, i t is d i f f i c u l t to u t i l i z e such data to scale up the coal bed to a larger size for the treatment of such a magnitude as 70 MGD of Iona e f f l u e n t . Larger experiments should be conduc- ted with deeper coal beds allowing longer contact time and a steady continuous flow would be advisable to obtain more r e l i a b l e results and to reinforce the encouraging results obtained during this experiment, d. COD Table 3 Appendix D -2 shows that the COD removal follows the same pattern as the BOD,, removal. At the 0.5 meter l e v e l , the average removal e f f i c i e n c y was 47% while i t reached 63% and 79% at the 1 meter and 2 meter leve l s respec- t i v e l y . Backwashing does not restore the o r i g i n a l e f f i c i e n c y of the bed as happened i n the case of BOD^. An estimated adsorptive capacity was calculated a f t e r passing approximately 1790 gallons through the f i r s t 0.5 meter l e v e l and was found to equal approximately 130 mgs of COD removed, per gram of coal. e. TOC A very poor e f f i c i e n c y was shown for the TOC removal as presented in Table 4 , Appendix D-2. A range of 25 to 661 removal e f f i c i e n c y was obtained during the bed operation. Larger contact time may be required to improve the adsorption e f f i c i e n c y . The poor e f f i c i e n c y can be attributed to the p a r t i a l contribution of some soluble organic components of the coal with the measured TOC values causing an increase of the TOC concentration i n the e f f l u e n t . Additional research work i s required to confirm this assumption. 3.2 Industrial sewage This includes the treatment of an o i l ref i n e r y wastewater e f f l u e n t using contact and column methods to remove mainly phenol, cyanide, ammonia and other dissolved organics. The results obtained with the oxidized surface coal, unoxidized core coal and activated carbon are compared. 22 3.2.1 Batch tests • The results of Table 1, included i n Appendix D-3 indicate that phenols are reduced to s a t i s f a c t o r y l e v e l with the core coal, a 77% removal was obtained when 1% w/w coal was contacted by shaking with the wastewater, while the oxi- dized surface coal showed a lesser e f f i c i e n c y of 49%. In comparison, 0.5% w/w activated carbon reduced the phenol l e v e l to non-detectable l i m i t s . Regarding the cyanide, i t was d i f f i c u l t to determine the effectiveness of eithe r type of coal for removal because of the low l e v e l o r i g i n a l l y present i n the sewage which does not exceed 0.01 mg/l CN". This l e v e l i s considered quite low for detection purposes. Table 2, Appendix D-3 shows that no appreciable reduction in the ammonia or the Kjeldahl t o t a l nitrogen was achieved using either activated carbon or coal. Surface coal was the lea s t e f f e c t i v e . By increasing the quantity of coal applied to more than 1%, an increase i n the le v e l of both NHj-N and K-N, even higher than the o r i g i n a l , was observed. This may be due to the leaching out of some nitrogeneous components from the surface coal. The t o t a l residue and v o l a t i l e s o l i d s were removed to a certain extent when coal was used in small qua n t i t i e s . However, with higher quantities (2% and 4% w/w) the t o t a l residue l e v e l increased more than the o r i g i n a l l e v e l as shown in Table 3 by the negative signs. This may be due to the leaching of c o l l o i d a l or dissolved components from the coal upon shaking with the e f f l u e n t , which adds to the t o t a l and the v o l a t i l e residue l e v e l s . In comparison, activated carbon i s not very e f f e c t i v e in the removal of s o l i d s as shown in Table 3, Appendix D-3. The e f f i c i e n c i e s of removal of organic matter represented by BOD^, COD and TOC by c o a l , i n comparison with activated carbon, are shown in Table 4, Appendix D-3. The activated carbon is the most e f f e c t i v e for reduction of BODj. since 82% removal was obtained when 0.5% activated .'• carbon was used, while 26% and 30% removal was obtained using the same quantity of the surface coal and the core coal respectively. Meanwhile, r e l a t i v e l y better effectiveness of surface coal was noticed for the removal of BOD^ than that of the core coal. The non-oxidized coal was found to be the most e f f e c t i v e for COD and TOC removal, with 0.5% coal added 60% removal of COD and 45% removal of TOC was obtained. The e f f i c i e n c i e s i n both cases increase by increasing the percen- tage of coal added, reaching an e f f i c i e n c y of removal more than 80% for COD and 50% for TOC. Table 5-, Appendix D -3 shows that o i l and grease are e f f e c t i v e l y removed by both types of coal while a r e l a t i v e l y high e f f i c i e n c y (up to 80%) i s exhibited by the core coal. 222. E f f e c t of treatment on pH: Table 6 , Appendix D-3 shows that the o r i g i n a l refinery effluent had a neutral to a very s l i g h t l y a l k a line pH 7,62 to 8.2. The treatment with activated carbon does not change the pH of the e f f l u e n t , but a very s l i g h t change in the pH, on the a c i d i c side, was observed when non-oxidized coal was used. , The treatment with oxidized surface coal affects greatly the pH of the e f f l u e n t . The pH decreased to decidely a c i d i c , up to 3.65 upon the addition of 4% w/w coal. This again confirms the presence of a c i d i c compounds i n the coal which are leached out i n the e f f l u e n t , changing i t s colour to dark yellow upon treatment with the coal. 3.2.2 Column tests These experiments were conducted using a flow rate 2 of 165 ml/min which i s equivalent to 1 gpm/ft but provides only 2-3 minutes of contact through the 20 cm depth of c o a l . This short contact time does not seem to be suitable for p r a c t i c a l use, at least 25 - 30 minutes of time should be allowed. The results from column tests after running 10 , l i t e r s of effluent through beds of surface coal and core coal are l i s t e d in Table 7, Appendix D-3. Generally, the removal of d i f f e r e n t pollutants seems to follow the same pattern as in the case of batch tests. The t o t a l residue does not reduce e f f i c i e n t l y , although the t o t a l suspended solids are removed to a high degree. The BOD,, is also reduced with both types of coal, with a r e l a t i v e higher e f f i c i e n c y when oxidized coal i s used as shown in Figure 39. Total carbon i s reduced to less than one t h i r d of the o r i g i n a l value. High e f f i c i e n c y for removal of phenol, o i l and grease was also observed. 3.2.3 Design application The synthetic waste mixture (phenol, cyanide and ammonia) was passed through the coal bed continuously for 17 days. During this period more than 950 gallons of the eff l u e n t were leached through the bed. The results of monitoring from 3 sampling points on the bed and the calculated cumulative removal for the phenol, cyanide and ammonia are shown i n Tables 1, 2 and 3 respectively included in Appendix D-4. The bed continued operation u n t i l the break through concentrations of 0.2 mg/1 phenol, 0.1 mg/1 cyanide and 5 mg/1 ammonia were reached. The break through l i n e s for phenol and cyanide are shown in Figures l a and l b , Appendix D-4 respectively. Using the data obtained from the three levels on the coal bed, the Bohart Adams re l a t i o n s h i p , explained i n Appendix D-l was applied to obtain the design parameters of a coal bed to treat a refin e r y e f f l u e n t at the rate of 8 gpm (Imp.)/1000 Bbl of crude with an inflow rate of 2 1 gpm/ft . The de t a i l s of the tentative c a l c u l a t i o n s , based IGlNAL: 5 7 PPM AL VOLUME P A S S E D T H R O U G H COLUMN(L) FIGURE 39 s LEACHING OF REFINERY WASTE EFFLUENT THROUGH COAL COLUMN, CHANGES IN BOD* on phenol removal and cyanide removal are found i n Appendix D-4. As a conclusion for both c a l c u l a t i o n s , the suggested 2 bed size to treat refinery wastes, at a rate of 8 : gpm/ft /1000 Bbl, to remove phenol and cyanide should be 29 X 49 X 5 f t 3 deep (7000 f t ). This bed would serve for one year for phenol and 1.5 years for cyanide to reach the determined break through concentrations. A larger p i l o t experiment should be conducted to confirm these encouraging r e s u l t s . Also, the adsorptive capacities of the coal towards phenol, cyanide and ammonia, calculated from the empirical formula and those obtained from the applied research are compared and found to be as follows: Absorptive capacity of coal mgs material removed/gram of coal Calculated from B.A.* Obtained experimentally formula Phenol 0.4139 0.3149 Cyanide 0.2333 0.2861 * * Ammonia N.A. 2.25 Material removed Bohart Adams Not applied 226. VIII.. SUMMARY AND CONCLUSIONS Hat Creek coal samples used i n t h i s work are ranked as l i g n i t e v a r i e t y . The coal has macroporous structure, the highest percentage of pore volume lay in the t r a n s i t i o n a l and macropore range (60-300 °A) , while activated carbon has a microporous structure with pore diameters of range 50-70 °A. The coal has an iodine value equal to one-seventh of that of activated carbon but 60 times more than that of sand. Oxidized surface coal has r e l a t i v e l y more fractured surface, larger pore diameters and more available a c i d functional groups (carboxyl COOH and phenolic -OH) than in the case of the non oxidized core coal. Coal possesses good sorptive q u a l i t y towards the s i x heavy metals tested. Ninety-nine percent or more of the following heavy metals were removed from s o l u t i o n , namely mercury, lead, copper, zinc, cadmium and chromium. The coal i s most se l e c t i v e to adsorb mercury followed by lead, while the least s e l e c t i v i t y i s exhibited towards chromium. Eighty to ninety percent of the BOD and COD values can be reduced by coal. Phosphate was not removed e f f e c t i v e l y , but using powdered coal between 50-80% of the phosphate was removed by a contact process. The best results for phosphate removal were obtained with s o i l which exhibits a higher a b i l i t y to hold phosphate. Hat Creek coal does not appear to have any value for the removal of n i t r a t e and very l i t t l e value f o r ammonia; meanwhile, phenol and cyanide are removed s a t i s f a c t o r i l y . The adsorptive capacity of the coal increases by: a. increasing the solute concentration i n the solution. b. increasing the contact time t i l l approaching equilibrium state. c. increasing the coal dosage. d. decreasing the p a r t i c l e size of the coal, although granular coal i s more e f f i c i e n t for use i n continuous column contacting rather than batch processes. Clay-minerals i n coal consist mainly of k a o l i n i t e (6-9% d.w.b. of the coal ) , while bentonite i s not detectable. Enough p r a c t i c a l evidences are provided to show that the k a o l i n i t e doesn't s i g n i f i c a n t l y p a r t i c i p a t e with the organic matter 228. in the int e r a c t i o n with the metal ions. Therefore no interference i n the adsorption mechanism studied i s expected due to clay minerals. 9) The adsorption of metal ions by coal i s l i k e l y taking place through a chemisorption mechanism where the carboxyl COOH and/or the phenolic hydroxy1 -OH groups of the coal inter a c t with the adsorbed lead ions to form metal complexes. 10) There are proximate carboxyl groups i n the coal structure which can allow a complex formation by the int e r a c t i o n of the two adjacent COOH with the metal ion to form a compound s i m i l a r to the acid anhydride form. 11) Coal removes dissolved organics through the combined eff e c t of physical adsorption and b i o l o g i c a l oxidation of the organic substrate by the micro-organisms available on the coal surface. 12) Data obtained from the application of actual wastes are in good agreement with those obtained from the standard laboratory tests used with synthetic wastes. 13) Hat Creek coal can be evaluated as a s a t i s f a c t o r y and valuable material f o r the p u r i f i c a t i o n of sewage wastewaters. 229 . IX. RECOMMENDATIONS FOR FUTURE RESEARCH The results of this research indicate that much research i s s t i l l needed to enable coal to be used e f f i c i e n t l y for the removal of pollutants from wastewaters. Some suggested lines of study are: 1. A study to improve the c a p a b i l i t y of the coal surface to adsorb more e f f i c i e n t l y phosphates, ammonia and n i t r a t e s . 2. Evaluation of the adsorptive capacity of the coal to remove pesticides. 3. Determination of the role of other functional groups in coals such as quinones and nitrogen containing groups in the mechanism of int e r a c t i o n with heavy metals. 4. Moisture-mineral matter-free coal i s recommended for use in the future investigation of mechanisms. This w i l l allow more accurate i d e n t i f i c a t i o n of the functional groups using i n f r a - r e d spectroscopic as well as microscopic methods. 5. More investigation i s required to determine quanti t a t i v e l y the number of carboxyl groups present i n adjacent positions and the extent of t h e i r p a r t i c i p a t i o n in forming metal complexes i n the coal. .230. 6. More studies are recommended for the i d e n t i f i c a t i o n of the type of complexes formed with metal ions, and the nature of the chemical bonds formed. 7. The p o s s i b i l i t y of using the powdered coal as a coagulant and sedimentation aid i n addition to heavy metal removal i n the primary treatment of raw sewage with the determination of the e l e c t r i c a l surface charge of the coal surface (zeta p o t e n t i a l ) . 8. Determination of the technical and economic f e a s i b i l i t y of procurement and disposal of the coal. More . research studies i n the regeneration of the coal a f t e r use and the p o s s i b i l i t y of using the spent coal as a source of energy are strongly recommended. Incineration or l a n d f i l l i s a p o s s i b i l i t y requiring i n v e s t i g a t i o n , also backwashing with a c i d i c and/or alk a l i n e solutions holds some promises of removing respectively adsorbed metal ions and organic matter from the coal surface. 9. Aerated, expanded-type coal beds are recommended to be used i n future research studies to avoid develop- ment of anaerobic conditions and " f o u l i n g " of the bed due to the increase of the pressure drop along the bed. 10. Experimental p i l o t beds should be one of the early developments for treatment of sewage flows ,231. emanating from small urban areas. These larger size beds would minimize the "scaling-up" e f f e c t which i s hazardous i n forecasting the design parameters such as that envisioned f o r 70 MGD based on data obtained from small columns. 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U.S. Dept. of Inter i o r , Office of Coal Research. 1971. Development of a coal-based sewage treatment process. Report No. 55, Contract No. 1401-0001- 483. U.S. Environmental Protection Agency. 1973. Process design manual for carbon adsorption, October, 1973. Van Dijk, H. 1971. Cation building of humic acids, Geoderma S: 53-67. Van Krevelen, D.W. 1961. Coal, Chapter VII, E l s e v i r , N.Y. Vlasova, N.S., V.C Eva Kushner, A. Ya Barsukova (U.S.S.R.). 1973. E f f e c t of the degree of oxidation of coals on the adsorption of n-a l i p h a t i c alcohols, Koks Khim 6: 3-5 (Russ.), (CA. 79: 81447g, 1973). 241. Ibid. 1973. E f f e c t of the ash content of coals on adsorption of heteropolar reagents during f l o t a t i o n , Ugol ' 2_: 45-49 (Russ.), (C.A. 79_: 94558u, 1973). Walker, P.L. J r . and K.A. K i n i . 1965. Fuel, Lond. 44: 453. Walker, P.L. J r . and R.L. Patel. 1970. Surface areas of coals from carbon dioxide adsorptions at 298°K, Fuel, Lond. 4_9(1) : 91. Weber, W.J. J r . and J.C. Morris. 1963. Journal of Sanitary Eng., Div. Proc. A.S.C.E. 89: SA2: 31-59. Weber, W.J. J r . , C P . Hopkins and R. Bloom. 1970. Expanded bed adsorption systems for treatment of sewage eff l u e n t s . Paper presented at 63rd Annual Meeting of Am. Ins. of Chem. Eng., December, 1970. Wood, J . C , S.E. Moschopedis and Den Hertog. 1961. Studies i n Humic Acid Chemistry II. Humic Anhydrides, Fuel Lond. X L ( l l ) : 491-502. Wright, J.R.'and M. Schnitzer. 1960. Oxygen containing functional groups in the organic matter of the AO and Bh horizons of a podzol. In: Cong. S o i l S c i . Trans. 7th (Madison I I ) : 120-127. Wright, J.R. and M. Schnitzer. 1961. Nature, 190-703. 242. APPENDICES 242a LIST OF APPENDICES i . Appendix Page A APPARATUS AND INSTRUMENTS 243 B GENERAL TECHNIQUES 247 B- l E l e c t r o n microprobe a n a l y s i s 248 B-2 I n f r a - r e d Absorption 251 B-3 BET surface area and pore s t r u c t u r e 253 B-4 Adsorption and a n a l y s i s of heavy metals 254 B-5 Exchangeable cations and t o t a l exchange cap a c i t y of coal 256 B-6 Iodine number 258 C DATA RESULTS 262 C-l C h a r a c t e r i s t i c s of the coal 263 C-l-1 Proximate and u l t i m a t e a n a l y s i s 263 C-l-2 Pore s i z e d i s t r i b u t i o n 268 C-2 Sorptive p r o p e r t i e s of the co a l 272 C-2-1 Adsorption of metal ions 272 C-2-2 Regression a n a l y s i s of adsorption isotherm data 292 C-2-3 Comparison of adsorption of metal on coa l and a c t i v a t e d carbon 298 242b i i . C-2-4 Factors i n f l u e n c i n g the adsorption process 299 C-2-4-1 Contact time 299 C-2-4-2 Coal dosage . . . 303 C-2-4-3 S o l u t i o n concentration 308 C-2-4-4 Coal p a r t i c l e s i z e 309 C-2-5 A n a l y s i s of variance f o r data f o r batch t e s t s 311 C-2-6 Data of column adsorption t e s t s 312 C-2-7 Long term adsorption of lead 318 C-2-8 A c t i v i t y i n adsorption of mixed metals. . 320 C-3 Adsorption of d i s s o l v e d organics., 326 C-3-1 Batch t e s t s 326 C-3-2 Column Adsorption t e s t s 327 C-4 Adsorption of phosphates 330 C-4-1 Batch t e s t s 330 C-4-2 Column adsorption t e s t s 336 C-5 Absorbance and s p e c i f i c e x t i n c t i o n c o e f f i c i e n t of assigned i n f r a r e d bands 339 C-6 Molar r a t i o between adsorbed lead and released hydrogen 340 C-7 A c i d i c groups i n c o a l 341 C-7-1 Carboxyl and phenolic hydroxyl groups. . .341 C-7-2 A n a l y s i s of variance of the a c i d i c groups data 342 C-7-3 Released lead ions during a c i d groups a n a l y s i s -348 242c i i i . C-8 B i o l o g i c a l o x i d a t i o n of organics 349 C-9 A p p l i c a t i o n s i n sewage treatment 352 C-9-1 Batch t e s t s 352 C-9-2 Column adsorption t e s t s 354 D DATA RESULTS OF DESIGN APPLICATIONS . . 355 D-l Tentative c a l c u l a t i o n of a c o a l bed f o r Iona Sewage 356 D-2 F i e l d study on Iona Sewage 363 D-3 Treatment of r e f i n e r y e f f l u e n t s 368 D-4 Design of a c o a l bed f o r removal of phenol, cyanide and ammonia 376 A P P E N D I X A APPARATUS AND INSTRUMENTS 244. LIST OF APPARATUS AND INSTRUMENTS 1. "BiCO" Jaw Crusher, c a p a c i t y = 400 l b s / h r , motor power 2 hp, 210 v o l t . 2. "BiCO" p u l v e r i z e r , c a p a c i t y 200 l b s / h r , motor power 1 hp, 210 v o l t , a djustable range of p a r t i c l e s i z e 4 mesh to f i n e . 3. F u l l height U.S. standard screen f i n e mesh s i e v e s , 8" diameter, made of bra s s . A s e r i e s of sieves of mesh s i z e 4, 8, 16, 20, 50,. 60, 100, 140 and 325 were used. i 4. Ro-Tap mechanical sieve shaker, which reproduces c i r c u l a r and tapping motion and accommodates s i x 8" diameter f u l l h e i g h t s i e v e s , w i t h r e c e i v i n g pan. Motor power 1/4 h.p.1750 rpm. APPENDIX A, TABLE 1 U.S. Sieve S e r i e s and T y l e r Equivalents U.S. Number SIEVE OPENINGS Tyl e r Screen Scale Equivalent Mesh M i l l i m e t e r s Inches No. 4 12 14 16 20 50 60 100 140 200 270 32 5 4. 76 1.68 1.41 1. 19 0.84 0 . 297 0 .250 0.149 0 .105 0.074 0.053 0 .044 0 .187 0.0661 0.0555 0.0469 0 . C 3 31 0.0117 0.0098 0.0059 0.0041 0.0029 0.0021 0.0017 4 10 12 14 20 48 60 100 150 200 2 70 32 5 245. 5. D i g i t a l pH/ion Fisher-Accumet pH meter, model 420, with a glass calomel electr o d e combination. 6. Reic h e r t low power l i g h t microscope 4.5 X, model MeF. 7. Scanning E l e c t r o n Microscope, model ETEC Autoscan , l i g h t r e s o l u t i o n 10 nra (100 °A) to 2.5 nm (25 °A). I t s b a s i c components are: lens system, e l e c t r o n gun, e l e c t r o n c o l l e c t o r , v i s u a l and rec o r d i n g cathode ray tubes (CRTS) and the e l e c t r o n i c s a s s o c i a t e d w i t h them. 8. The JEOL Co. E l e c t r o n Microprobe, model JXA-3A. I t s main components are: a) E l e c t r o n o p t i c s to produce a small diameter e l e c t r o n beam; i t has an e l e c t r o n gun plus two e l e c t r o n lenses. b) X-ray spectrometer to measure the wave length and i n t e n s i t y of the c h a r a c t e r i s t i c X-ray r a d i a t i o n produced. c) L i g h t microscope to locate the area i n the specimen to be examined. The probe operates i n vacuum and so a l l elements having atomic numbers > 4 can be detected. 9. Perkin-Elmer double beam g r a t i n g i n f r a - r e d spectrophotometers, model 621 and 521. 10. The M i c r o m e r i t i c Surface Area and Pore Volume Analyzer. This t e s t was conducted by the Fuel Science D i v i s i o n , N.R.C., Edmonton, A l b e r t a . 2 4 6 . 11. J a r r e l Ash atomic absorption spectrophotometer, model MV-500 f o r mercury a n a l y s i s . 12. Perkin-Elmer double beam, s i n g l e channel atomic absorption spectrophotometer, model 306. 13. Technicon I n d u s t r i a l AutoAnalyser I I . 14. High-low ad j u s t a b l e speed Eberbach mechanical shaker, 115 v o l t s , 3.6 amp., 60 cycles A.C. 15. TXT American p r o p o r t i o n i n g pump, adjustable c a p a c i t y , s e r i e s 100. 16. Beckman t o t a l organic carbon a n a l y z e r , model 915, equipped w i t h Beckman i n f r a - r e d analyzer u n i t , model 215A. A P P E N D I X GENERAL TECHNIQUES- 2 4 8 . B - l The E l e c t r o n Microprobe A n a l y s i s B-l-1 P r e p a r a t i o n of coal s e c t i o n s f o r microscopic study Coal specimen were prepared by mounting coal p a r t i c l e s of average p a r t i c l e s i z e of 1 mm in epoxy r e s i n mounts. Each specimen was then prepared by repeated g r i n d i n g on a s e r i e s of coarse and f i n e abrasive papers followed by p o l i s h i n g on diamond abrasive t i l l a f l a t , smooth, s c r a t c h - free surface was obtained. Any ridges or v a l l e y s on the surface cause v a r i a t i o n s i n e l e c t r o n incidence and X-ray " t a k e - o f f " angles. No e t c h i n g was a p p l i e d because i t may a l t e r the topography or surface chemistry of the specimen. The specimens were then coated w i t h carbon to ensure e l e c t r i c a l and thermal c o n d u c t i v i t y . The c o a t i n g m a t e r i a l was a p p l i e d very t h i n l y to y i e l d s t a b l e specimen currents and X-ray flux.Thickness i n the range of 50-500 °A i s recommended. B-l-2 Theory and technique The e l e c t r o n microprobe i s a powerful instrument which permits the c h a r a c t e r i z a t i o n of heterogeneous m a t e r i a l s and surfaces on such a micrometer (Urn) or sub-micrometer s c a l e . The area to be examined i s i r r a d i a t e d with a f i n e l y focussed e l e c t r o n beam which may be s t a t i c or swept i n a r o s t e r across the surface of the specimen. The types of s i g n a l s produced when t h e • e l e c t r o n beam impinges on a specimen include 249. secondary e l e c t r o n s , back-scattered e l e c t r o n s , c h a r a c t e r i s t i c X-rays, auger e l e c t r o n s and various energy values are used to measure many c h a r a c t e r i s t i c s of the sample, e.g. composition, surface topography, c r y s t a l l o g r a p h y e t c . a) Elemental i d e n t i f i c a t i o n Most SEM's and EMP's are equipped with detector systems, an energy d i s p e r s i v e spectrometer (EDS) or c r y s t a l spectrometer. The EDS system i s capable of i d e n t i f y i n g elements with an atomic number Z > 11 i n a few minutes. With adjacent elements i n the range 4 < Z< 11, overlapping of the peaks may occur. For elements present i n trace amounts, longer counting times are necessary but instrument i n s t a b i l i t y l i m i t s counting time to 10 to 15 minutes i n p r a c t i c e . A 30 k i l o v o l t a c c e l e r a - t i n g p o t e n t i a l i s s u f f i c i e n t f o r non-ambiguous i d e n t i f i c a t i o n of a l l the elements. b) Elemental d i s t r i b u t i o n The a m p l i f i e d s i g n a l f o r the detector system i s made to modulate the brig h t n e s s of a cathode ray tube (CRT) scanned i n synchronism w i t h the e l e c t r o n probe. Thus, on the CRT a p i c t u r e i s obtained by the v a r i a t i o n of X-ray emission from the s u r f a c e . An X-ray area scan can show tones ranging from black to white, depending on the experimental c o n d i t i o n s . In places of high c o n c e n t r a t i o n of the element i n the scanned area, the p i c t u r e w i l l be nearly p h o t o g r a p h i c a l l y w hite, i t w i l l be gray where the element concentration i s lower and black where the element i s absent. Care must be taken to ensure that no * Scanning Electron Mici"cscope ** Electron Microprobe 250 other peak i n t e r f e r e s w i t h the s i g n a l of the d e s i r e d element. The d e s i r e d peak should be c a r e f u l l y i s o l a t e d by means of a s i n g l e channel analyzer from which the a m p l i f i e d output i s d i s p l a c e d on a CRT and so provide the elemental d i s t r i b u t i o n d e s i r e d . c) Absorption e l e c t r o n image (AEI) E l e c t r o n images are obtained f o r the d i f f e r e n t coal p a r t i c l e s . The AEI i s the exact converse of the back- s c a t t e r e d image. In t h i s case, the specimen current ( i . e . the e l e c t r o n s remaining i n the specimen and producing X-rays) was used to c o n t r o l the spot i n t e n s i t y of the cathode ray tube (CRT). A set of e l e c t r o n images are a l s o produced on the CRT showing the elemental d i s t r i b u t i o n across c e r t a i n areas of the specimen. Each image gives the c o n c e n t r a t i o n of a p a r t i c u l a r element i n the given area. d) D i s p l a y c i r c u i t s This gives a time trace across the given area which shows the l e v e l s of c o n c e n t r a t i o n of p a r t i c u l a r elements across that s e c t i o n . This l i n e shows the v a r i a t i o n in X-ray i n t e n s i t y which' i s c a l l e d the Y-axis d i s p l a y . M a g n i f i c a t i o n up to 2500 X i s p o s s i b l e by the microprobe without exceeding the r e s o l u t i o n of the instrument. 251. B-2 Infra-red Absorption B-2-1 Grinding The size of the coal sample was f i r s t reduced to approximately 325 mesh to obtain r e l i a b l e spectra. Size reduction i s accomplished by both grinding in an agate mortar and pestle for about 10 minutes for each sample, followed by a Spex 3" x 2" vibratory mixer m i l l for 30 minutes, the freshly prepared samples are then used in the preparation of the KBr p e l l e t s . B-2-2 Preparation of the KBr p e l l e t s (Laury, 1963) The KBr p e l l e t s were prepared by adding 1 mg from the coal (0.5 mg from activated carbon) to 300 mgs of dry KBr. The mixture was then ground using a mortar and pestle for 5 minutes. The ground mixture was then placed in a Perkin Elmer p e l l e t press, the press was evacuated for one minute and then loaded to 18,000 lbs for one minute to y i e l d a 13 mm diameter KBr p e l l e t . The p e l l e t s were then stored in glass v i a l s in a dessicator u n t i l required. B-2-3 Calculation of the s p e c i f i c extinction c o e f f i c i e n t K For each main absorption band, K is calculated using the following r e l a t i o n s h i p : K m/A =. D ^ 3 2 o where K = the s p e c i f i c e x t i n c t i o n c o e f f i c i e n t (cm /mg) m = the weight of the coal i n the d i s c i n m i l l i g r a m s A = the area of the d i s c ( d i s c diameter - 13 mm) D = o p t i c a l d e n s i t y (absorbance) A l i n e a r r e l a t i o n s h i p was e s t a b l i s h e d between the absorbance and the c o a l d e n s i t y (m/A), the gradient of t h i s 2 l i n e i s equal to K i n cm /mg. The absorption i n t e n s i t i e s were c a l c u l a t e d by the base l i n e method according to the method of R.A. F r i e d e l as o u t l i n e d i n a paper by F u j i i et a l . , 1970. The K values f o r the main absorption bands f o r each type of c o a l as w e l l as a c t i v a t e d carbon, before and a f t e r adsorption of heavy metals, were c a l c u l a t e d and compared. B-2-4 Base l i n e technique (Ewing, 1960) Po Since the absorbance A = l o g p— at c e r t a i n wave length X where Po = the t r a n s m i t t e d power from empty curvette c a l l e d the background and P = the t r a n s m i t t e d power through the sample i f a base l i n e drawn across the dip i n the curve and designated Pg the power l e v e l i s where t h i s l i n e i n t e r s e c t s the X wave- length l i n e . Therefore, the base l i n e absorbance can be defined as : PB A B = l 0 g P~ I t i s e x a c t l y so i f the absorption curves of the other sub- stances present are assumed to be l i n e a r over t h i s short range. 253 B-3 BET Surface Area and Pore S t r u c t u r e of the Coal The BET equation (Brunauer, et a l . 19 38) P 1 ^ C-l p /Dr> vTPo-^P) = 7 T C + — C ' P / P o  J m m where P = p a r t i a l pressure of ^ i n the gas mixture Po = s a t u r a t i o n pressure of at the temperature of the l i q u i d coolant v = volume of adsorbed on the sample at STP v = volume of adsorbed N„ due to monolayer coverage m 2 . J C = constant. ^ f t e n v ( p 0 p) i - s p l o t t e d as a f u n c t i o n of P/Po and the slope and i n t e r c e p t of the best s t r a i g h t l i n e were evaluated by the method of l e a s t squares. can be evaluated as the r e c i p r o c a l of the sum of the slope and i n t e r c e p t , and converted to the sample surface area by m u l t i p l y i n g by F where 6.0,2 X 1 0 2 3 X 16.2 X 1 0 " 2 0 X 10~ 6 h 2 2.414 2 3 and 6.02 X 10 = Avogado's No. (molecules/mole) - 2 0 2 16.2 X 10 - area covered by a molecule (m /molecule) 10" 6 = l i t e r s / v l i t e r 22,414 = Molar volume of N 2 at STP ( l i t e r / m o l e ) APPENDIX B-4 : ADSORPTION OF HEAVY METALS. 2 5 4 . B-4-1 Metal 1, 2. 3̂ 4, 5 , 6. Lead Cadmium Mercury Copper Zinc Chromium SYNTHETIC WASTEWATERS CONTAINING HEAVY METALS Reagent used* P b ( N 0 3 ) 2 c r y s t a l s , A.R., F.W. 331.23 Cd(N0 3) 2 4H 20 c r y s t a l s , A.R., F.W. 308.47 Hg(N0 3) 2 granular, A.R., F.W. 324.60 Cu(N0 3) 2 3H 20 c r y s t a l s , A.R., F.W. 241.60 Zn(N0 3 ) 2 X H 20 f l a k e s , A.R. C r ( N 0 3 ) 2 9H 0 c r y s t a l s , A.R., F.W. 400.15 The above reagents were s u p p l i e d by M a l l i n c h r o d t Inc., St. L o u i s , M i s s o u r i , 63147, U.S.A. B-4-2 Sieve No, PARTICLE SIZE OF COAL USED IN THE ADSORPTION TESTS Size of Opening mm Mean Size of P a r t i c l e Finenes: Modulus 0.533 mm 0.29 6 5 mm 0.1117 mm 0.0 3414 mm 3 6.680 3.87 60 0.246 150 0.104 Pan ( f i n e s ) B-4-3 C e r t i f i e d atomic absorption standards, reference s o l u t i o n of 100 ppm for cadmium, mercury, copper, z i n c , and chromium were supplied by F i s h e r S c i e n t i f i c Company, Fa i r l a w n , New Jers e y , 0 7410, U.S.A. B-4-4 STANDARDIZED INSTRUMENT PARAMETERS FOR DIFFERENT METALS Metal Lamp Current Fuel Support Flame Starchiometry Wave Working DETECTION LIMIT Length nm Range Absorption Concentration Scale Scale (Expanded) Copper 3 mA Acetylene Air Oxidizing 324.7 218.2 < 20 mg/l 10-100 mg/l 0.1 mg/l 0.03 mg/l Lead 6 mA it .... 217.0 283.3 < 20 mg/l 10-100 mg/l 0.2 mg/l 0.1 mg/l Zinc 5 mA ti tt ii 213.9 307.6 < 20 mg/l 10-100 mg/l 0.01 mg/l - Mercury 3 mA Flameless or cold vapor method 253.7 253.7 5-100 mg/l < 5 mg/l 0.5 yg/1 i n a 100 mis sample Chromium 3 mA Acetylene Air Oxidizing 357.9 425.4 < 20 mg/l 10-100 mg/l - 0.015 mg/l Cadmium 3_mA it " Reducing 228.8 326.1 < 20 mg/l 10-100 mg/l - 0.01 mg/l 2 5 6 . B-5 EXCHANGEABLE CATIONS AND TOTAL EXCHANGE CAPACITY (Black, 196 5) (by Ammonium acetate method (pH 7.0) Reagents : A. 1. IN NH 40 AC-.dissolve 77.0 8 gms of NH40 AC/1 of d i s t i l l e d water. Adjust pH at 7 with NH^OH or HOAC. 2. ISO propanol 3. IN K C l : d i s s o l v e 74.6 gms of KC1/1 of d i s t i l l e d water. Procedure A. For exchangeable cations Weigh out a c c u r a t e l y 10 grams of c o a l , add 40 ml of IN NH^O AC, stopper the tube and shake f o r 5 minutes. Shake to ri n s e down c o a l adhering to s i d e s , l e t stand overnight, shake tube again f o r 15 min. Prepare Buchnter funnels w i t h Whatman No. 42 f i l t e r paper and place above 500 ml f i l t e r i n g f l a s k s . Transfer contents to funnel w i t h s u c t i o n a p p l i e d . Rinse the tube and sopper with. IN NH^O AC from the wash b o t t l e . Wash the coal w i t h four 30 ml po r t i o n s of IN NH^O AC, l e t each p o r t i o n d r a i n com- p l e t e l y before adding the next but do not allow coal to become dry. Transfer the lcachate to a 250 ml volumetric f l a s k . Rinse the f i l t e r i n g f l a s k and make up to volume wi t h IN NH^O AC. Mix w e l l and save a p o r t i o n of the e x t r a c t ( i n 60 ml p l a s t i c b o t t l e s ) of Na, Ca, Mg and K by A.A B. For t o t a l exchange ca p a c i t y (CEC) Replace the funnels c o n t a i n i n g the ammonia saturated co a l onto f i l t e r i n g f l a s k s . Wash with three 40 ml porti o n s of 150 propanol, again l e t t i n g each p o r t i o n d r a i n completely before 2 5 7 . adding the next. D i s c a r d the washings and r i n s e out f l a s k s w e l l w i t h tap water and f i n a l l y w ith D..W. Replace the funnels and f l a s k s and leach c o a l w i t h four 50 ml p o r t i o n s of IN KC1, again l e t t i n g each p o r t i o n d r a i n completely before adding the next. Transfer the leachate to a 250 ml v o l u m e t r i c f l a s k . Rinse the f i l t e r i n g f l a s k and make up to volume wi t h D.W. C a l c u l a t i o n s A. For exchangeable cations Sample x Blank = b m.eq = r r M T - n I M ( m g M ,250 mis, 100 gm 1 1 J l1000 ml's J J 1 10 gm J ( J Q Q Q m r ) (100 gms) ( d i l u t i o n f a c t o r f o r AA*) B. For t o t a l exchange c a p a c i t y (CEC) CEC = [(mis KC1 - mis Blank). N K C 1 ^ f ^ J [ 2 5° m l x T o V x 2iria} [ 1 0° ^ AA* Atomic Absorption Spectrophotometer, B.6 Iodine Number ? 5 8 . The Iodine Number is defined as the milligrams of iodine adsorbed by one gram of carbon when the iodine concentration of the residual filtrate is 0.02 normal. B.6.1 Reagents and Equipment Hydrochloric Acid , 5 percent weight-To 550 ml of distilled water add 70 ml of reagent-grade concentrated hydrochloric acid (HC1). Sodium Thiosulfate, 0.1 normal-Dissolve 25 grams of reagent-grade sodium thiosulfate (Na2S2C>3 5 ^ 0 ) in one (1) liter of freshly boiled distilled water. Add a few drops of chloroform to minimize bacterial decomposition of the thiosulfate solution. Standarize the thiosulfate solution against 0.100 normal potassium biniodate_.(KH (IO3) 2)- Prepare the 0.1000 normal K H (IO3) 2 using primary standard quality K H (IO3) 2 which has been dried overnight at 105 degrees C and cooled in a desiccator. Weigh 3.249 grams K H (IO3) 2 a n d make-up to exactly one liter in a volumetric flask with distilled water. Store in a glass-stoppered bottle. To 80 ml of distilled water add, with constant stirring, one ml of concentrated sulfuric acid (H2SO4), 10 ml of 0.1000 K H (IO3) 2 solution and approximately one gram of potassium iodide (KI). Titrate the mixture immediately with the thiosulfate solution adding 2-3 drops of starch solution when the iodine fades to a light yellow color. Continue the titration by adding the thiosulfate dropwise until a drop produces a colorless solution. Record the volume of titrate used. 1.000 Normality of sodium thiosulfate - ——r——— ml oi Na2S2C>3 consumed Iodine Solution—Dissolve 12.7 grams of reagent-grade iodine (I2) and 19.1 grams of potassium iodide in a small quantity, approximately 20 ml, of distilled water. (If excess water is used, materials will not go into solution.) Dilute to one (1) liter in a volumetric flask with distilled water. Store in a glass-stoppered bottle in a dark place or use in a dark bottle. To standarize the iodine solution, pipette 25.0 ml into a 250 ml Erlenmeyer flask and immediately titrate with the 0.1 normal thiosulfate solution. Add 2-3 drops of starch solution near the endpoint and continue titrating until solution is colorless. Record the volume of titrar.t used. - . ,. , . ml of Na-)S';0-5 used x normality NaoSoOo Normality of iodine solution = ~—-2 ^ =̂_=—=L Starch Solution—To 2.5 grams of starch (potato, arrowroot, or soluble), add a little cold water and grind in a mortar to a thin paste. Pour into one (1) liter of boiled distilled water, stir, and allow to settle. Use the clear supernatant. Preserve with 1.25 grams of salicylic acid per one (1) liter of starch solution. 259. Filter Paper-Whatman Folded No. 2V, 10.5 cm. Spex-Mixer M i l l - N o . 8000 Spex-Mixer Mil l and No. 8001 Grinding Vials, Spex Industries, Inc., 3800 Park Avenue, Metuchen, New Jersey. B.6.2 Procedure Grind a representative sample of carbon in a Spex-Mixer Mi l l (usually 70 seconds) until 90+ 5 percent will pass a 325 mesh sieve (by wet sieve analysis). Load the Spex-Mixer Mil l with a 5.5 ± 0.5 gram sample and use 64 one-fourth inch diameter smooth steel balls. An adequate sample of the pulverized carbon should then be dried at 140 degrees C for one (1) hour, or 110 degrees C for three (3) hours. A moisture balance can also be used. Weigh 1.000 gram of the dried pulverized carbon (see Note I) and transfer the weighed sample into a dry, glass-stoppered, 250 ml Erlenmeyer flask. To the flask add 10 ml of 5 percent wt. HC1 acid and swirl until the carbon is wetted. Place the flask on hot plate, bring contents to boil and allow to boil for only 30 seconds. After allowing the flask and contents to cool to room temperature, add 100 ml of standarized 0.1 normal iodine solution to the flask. Immediately stopper flask and shake contents vigorously for 30 seconds. Filter by gravity immediately after the 30-second shaking period through Whatman No. 2V filter paper. Discard the first 20 or 30 ml of filtrate and collect the remainder in a clean beaker. Do not wash the residue on the filter paper. Mix the filtrate in the beaker with a stirring rod and pipette. 50 ml of the filtrate into a 250 ml Erlenmeyer flask. Titrate the 50 ml sample with standarized 0.1 normal sodium thiosulfate until the yellow color has almost disappeared. Add about 1 ml of starch solution and continue titration until the blue indicator color just disappears. Record the volume of sodium thiosulfate solution used. Notes on Procedure 1. The capacity of a carbon for any adsorbate is dependent on the concentration of the adsorbate in the medium contacting the carbon. Thus, the concentration of the residual filtrate must be specified, or known, so that appropriate factors may be applied to correct the concentration to agree with the definition. The amount of sample to be used in the determination is governed by the activity of the carbon. If the residual filtrate normality (C) is not within the range 0.008N to 0.035N given in the Iodine Correction Table, the procedure should be repeated using a different weight of sample. 2 6 0 . 2. It is important to the test that the potassium iodide to iodine weight ratio is 1.5 to 1 in the standard iodiix-. solution. Calculation Iodine Number = — D X. = A — (2.2B x ml of thiosulfate solution used) m Weight of sample (grams) c N 2 x ml of thiosulfate solution used 50 X / m = mg iodine adsorbed per gram of carbon N l = Normality of iodine solution N 2 .= Normality of sodium thiosulfate solution A = N j x 12693.0 B = N 2 x 126.93 C = Residual filtrate normality D = Correction factor (obtained from Table B- l ) T A B L E B-6 IODINE C O R R E C T I O N F A C T O R (D) 261 Residual Filtrate Normality (C) .0000 .0001 .0002 .0003 .0004 .0005 .0006 .0007 .0008 .0009 1.1625 1.1438 1.1250 1.1100 1.0950 1.0800 1.0675 1.0538 1.0413 1.0300 1.0200 1.0100 1.0013 0.9938 0.9863 0.9788 0.9725 0.9650 0.9600 0.9538 0.9488 0.9425 0.9375 0.9333 0.9300 0.9263 1.1613 1.1425 1.1238 1.1088 1.0938 1.0788 1.0663 1.0525 1.0400 1.0288 1.0188 1.0088 1.0000 0.9925 0.9850 0.9775 0.9708 0.9650 0.9588 0.9525 0.9475 0.9425 0.9375 0.f-333 0.9294 0.9263 1.1600 1.1400 1.1225 1.1075 1.0925 1.0775 1.0650 1.0513 1.0388 1.0275 1.0175 1.0075 1.0000 0.9925 0.98.50 0.9775 0.9700 0.9638 0.9588 0.9525 0.9475 0.9425 0.9375 0.9325 0.9288 0.9257 1.1575 1.1375 1.1213 1.1063 1.0900 1.0763 1.0625 1.0500 1.0375 1.0263 1.0163 1.0075 0.9988 0.9913 0.9838 0.9763 0.9700 0.9638 0.9575 0.9519 0.9463 0.9413 0.9363 0.9325 0.9288 0.9250 1.1550 1.1363 1.1200 1.1038 1.0888 1.0750 1.0613 1.0488 1.0375 1.0250 1.0150 1.0063 0.9975 0.9900 0.9825 0.9763 0.9688 0.9625 0.9575 0.9513 0.9463 0.9413 0.9363 0.9325 0.9280 0.9250 1.1538 1.1350 1.1175 1.1025 1.0875 1.0738 1.0600 1.0475 1.0363 1.0245 1.0144 1.0050 0.9975 0.9900 0.9825 0.9750 0.9688 0.9625 0.9563 0.9513 0.9463 0.9400 0.9363 0.9319 0.9275 1.1513 1.1325 1.1163 1.1000 1.0863 1.0725 1.0588 1.0463 1.0350 1.0238 1.0138 1.0050 0.9963 0.9888 0.9813 0.9750 0.9675 0.9613 0.9563 0.9506 0.9450 0.9400 0.9363 0.9313 0.9275 1.1500 1.1300 1.1150 1.0988 1.0850 1.0713 1.0575 1.0450 1.0333 1.0225 1.0125 1.0038 0.9950 0.9875 0.9813 0.9738 0.9675 0.9613 0.9550 0.9500 0.9450 0.9394 0.9350 0.9313 0.9275 1.1475 1.1288 1.1138 1.0975 1.0838 1.0700 1.0563 1.0438 1.0325 1.0208 1.0125 1.0025 0.9950 0.9875 0.9800 0.9738 0.9663 0.9606 0.9550 0.9500 0.9438 0.9388 0.9350 0.9300 0.9270 1.1463 1.1275 1.1113 1.0963 1.0825 1.0688 . 1.0550 1.0425 1.0313 1.0200 1.0113 1.0025 0.9938 0.9863 0.9788 0.9725 0.9663 0.9600 0.9538 0.9488 0.9438 0.9388 0.9346 0.9300 0.9270 A P P E N D I X C DATA RESULTS APPENDIX C-l C-l-1 TABLE 1. CHARACTRISITICS OF HAT CREEK COALS. PROXIMATE AND ULTIMATE ANALYSIS 0 » T F : 2 7 J U N 7 5 H A T C R E E K C O A L P R O J E C T - S T A T I S T I C A L A N A L Y S I S O F P R O X I M A T E T E S T D A T A D I A M O N D D R I L L H O L E 7 4 - 0 3 9 P A C E I o | | | S A M P L E D A T A I M O I S T U R E S I O R Y B A S I S I E S T I M A T E D [ N - S I T U M O I S T U R E O F 2 0 . 0 0 1 I L I B 1031.1 « » « « « • « • » « » « « « » « » • » « » » • « I » ' • - « » • » » » » • « I » « « « * « « « » • « • « « « » « • « * » « • « « * » « « • » • • « « « • « » • • | « * » v » » » » « » « « « » « « » « * » » « » » » » « « » « « » « « « » » « » » » I i i i F O O T A G E j I I I I I I G R O S T I 1 I I I" T" " T G R D S S l I I I t / O l H O L l I / O I » * » » » » » » » * « « « « * * * * * « l X I A S I X l X I X I B T U 1 X 1 1 1 X 1 * 1 X 1 * 1 B T U 1 * 1 * 1 * I I a I d I F R O M I T O I L E N G T H l E Q U I L l R E C V O I A S H I V . M . I F . C . I / L B . I S U L F R I S O O A l P O T A S l A S H I V . H . I F . C . I / L B . I S U L F R I S O O A I P O T A S | . « « | » . o I » » e | » « » • « . | « » » « « . | » « « • » » ! » » « » • | * « « « « ! » • « • « | » » « « " « ! » « • * • ! « » « » » I » * * • * I * * » * * | * * • * » ! * • * * » ! I < • • « ' * » I * » » » * l « , » * * I • • * * • I I I I I I 3 0 - 3 0 1 1 2 . 0 3 3 . 0 3 1 . 0 1 1 0 . 0 0 1 91.19 ; I I I I C T 3 " - 0 0 1 I 3 3 . 0 5 3 . 0 I I I C T 3 9 - 0 0 2 1 5 3 . 0 7 3 . 0 - I I I f . T 3 ° - 0 0 3 l 7 3 . 0 9 3 . 0 _j ! I 3 9 - 3 0 2 1 9 3 . 0 9 8 . 0 I I I C T 3 9 - 0 0 * 1 9 8 . 0 1 1 3 . 0 I I I C T 3 9 - 0 0 5 1 1 1 8 . P 1 3 8 . 0 I I 2 0 . 0 1 2 6 . 7 5 1 6 1 . 7 1 2 3 . 3 6 1 4 . 9 4 2 8 0 0 0 . 3 1 I 2 1 . 5 3 1 5 2 . 8 7 2 6 . 4 9 2 0 . 6 3 4 3 4 2 0 . 3 7 I 1 7 . 6 4 1 5 4 . 6 1 2 6 . 7 1 1 8 . 6 7 4 3 0 5 1 . 0 3 — 1 r 5 . 01 1 0 . 0 0 1 9 9 . 9 9 I I , ' _ 2 0 . 0 1 1 1 . 8 5 1 4 1 . 4 1 3 4 . 6 8 2 3 . 7 1 " 6 2 1 3 2 . 0 9 I I 2 D . 0 1 1 8 . 3 8 1 6 . 7 1 1 3 0 . 2 8 3 4 . 0 9 3 5 . 6 3 8 5 3 8 0 . 6 2 I 2 0 . 0 I I 2 0 . 01 U 9 . 3 7 13 . 6 9 1 1 . 9 5 2 2 4 0 0 . 2 5 I | 4 2 . 3 0 2 1 . 2 0 1 6 . 5 1 3 4 7 3 0 . 3 0 . I 1 4 3 . 6 9 2 1 . 3 7 1 4 . 9 4 3 4 4 4 C . 3 3 . 1 2 4 I I I C T 3 9 - 0 C 6 I 1 3 8 . 0 1 5 8 . 0 I I I C T 3 9 - 0 0 7 1 1 5 8 . 6 1 7 8 . 0 I I I C T 3 0 - 0 0 ° ! 1 7 5 . 0 - 1 9 8 . 0 I T I C T 3 ' - 0 C 9 l 1 9 8 . 0 2 1 8 . 0 I I I C T 3 0 - O I O ! 2 1 8 . 0 - 2 3 8 . 0 I I I C T 3 ° - 0 U I 2 3 8 . 0 2 5 8 . 0 i • i 2 0 . 0 1 1 8 . 4 1 1 2 4 . 6 8 3 6 . 8 7 3 8 . 4 5 9 3 6 0 0 . 5 4 I I _ 2 0 . 0 1 2 0 . 9 4 2 0 . 4 0 1 3 4 . 3 1 3 2 . 0 9 3 3 . 6 1 7 7 4 0 0 . 2 3 . 1 6 1 I I 2 0 . 0 1 2 2 . 8 4 1 2 0 . 5 5 3 6 . 3 1 4 3 . 1 3 3 7 2 1 0 . 1 6 T I I 1 3 3 . 1 3 2 7 . 9 1 1 8 . 9 7 4 9 7 1 1 . 6 7 I . 1 4 8 1 2 4 . 2 2 2 7 . 2 7 2 6 . 5 1 6 8 3 0 0 . 5 0 . 0 9 9 I I 2 0 . 0 1 ; 2 0 . o i I 2 0 . 0 1 1 2 1 . 4 7 1 2 3 . 8 0 3 4 . 5 3 4 1 . 6 7 9 1 1 2 0 . 1 9 I _ 2 3 . 1 1 1 2 6 . 7 8 3 4 . 9 1 3 8 . 3 1 6 7 6 4 0 . 2 2 I 2 0 . 4 7 1 2 3 . 6 1 3 7 . 6 8 3 8 . 7 0 9 0 4 7 0 . 2 3 U . 9 . 7 5 2 9 . 4 9 3 0 . 7 6 7 4 8 8 C . 4 3 . 0 9 9 1 2 7 . 4 5 2 5 . 6 7 2 6 . 8 8 6 1 9 2 0 . 1 8 I 1 1 6 . 4 4 2 9 . 0 5 3 4 . 5 0 7 7 7 7 _ 0.J 2 _ 1 1 9 . 0 4 2 7 . 6 3 J 3 . 3 3 7 2 9 0 0 . 1 5 I 1 2 1 . 4 2 2 7 . 9 3 3 0 . 6 5 7 0 1 2 0 . 1 8 I 1 1 8 . 8 9 3 0 . 1 5 3 0 . 9 6 7 2 3 8 O . H ! . 1 2 9 . o e o I I I C T 3 9 - 0 1 2 1 2 5 8 . 0 2 7 8 . 0 2 0 . 0 1 I I I I C T 3 9 - 0 1 3 1 2 7 8 . 0 2 9 8 . 0 2 0 . 01 I I I I f .T 3 9 - O U I 2 9 8 . 0 3 1 8 . 0 2 0 . 0 ! N I 1 1 I I C T 3 0 - 0 1 5 1 3 1 8 . 0 3 3 8 . 0 5 ! I ' I I C T 3 9 - 0 1 5 1 3 3 8 . 0 3 5 8 . 0 1 I I C T . J O - 0 1 T I 3 5 8 . 0 3 7 8 . 0 T I 2 2 . 2 4 1 1 6 . 0 8 3 7 . 7 6 4 6 . 1 7 1 0 2 3 1 0 , 3 0 I 2 2 . 2 5 115 . 3 2 3 8 . 0 1 "45 . 6 7 1 0 5 2 9 0 . 3 2 I 2 3 . 7 3 1 2 0 . 6 1 3 6 . 1 6 4 3 . 2 3 9 8 8 5 0 . 2 8 I • 8 5 0 . 2 4 1 1 2 . 8 6 3 0 . 2 1 3 6 . 9 3 I . 1 1 3 . 0 6 3 0 . 4 1 3 6 . 5 4 6 4 2 3 0 . 2 6 I 1 1 6 . 4 9 2 8 . 9 3 3 4 . 5 8 7 9 0 8 0 . 2 2 2 0 . 0 1 2 1 . 6 6 1 1 4 . 0 2 3 6 . 9 2 4 9 . 0 7 1 0 7 3 9 0 . 4 0 I I 2 0 . 0 1 2 3 . 5 8 1 1 5 . 2 6 3 6 . 5 9 4 8 . 1 5 1 0 7 6 0 0 . 2 7 I I 2 0 . 0 1 2 4 . 8 1 2 2 . 4 9 1 1 8 . 1 7 3 6 . 9 1 4 4 . 9 2 1 0 0 6 1 0 . 2 8 I 1 1 1 . 2 1 2 9 . 5 3 3 9 . 2 5 I 8 5 9 1 8 6 0 8 0 . 3 2 0 . 2 2  I l l - T 3 9 - 0 1 6 1 3 7 8 . C 3 9 8 . 0 I I I C T 3 9 - 0 1 9 1 3 9 3 . 0 4 1 8 . 0 I I I C T 3 9 - 0 2 0 1 4 1 5 . 0 < . 3 8 . P "I "1 I I I 3 9 - 3 0 3 1 4 3 8 . C 1 4 4 1 . ; ; 1 0 0 3 . 0 1 1 0 . 0 0 l o 9 . 9 9 I I 2 0 . 0 1 2 4 . 5 8 2 2 . 3 3 1 2 1 . 2 0 3 4 . 5 4 4 4 . 2 5 9 7 6 6 0 . 3 0 I I 2 0 . 0 1 2 3 . 1 0 1 1 6 . 9 4 3 7 . 1 9 4 5 . e 6 " 1 C 5 6 2 0 . 2 9 I I 2 0 . 0 1 1 9 . 5 6 1 2 7 . 4 9 3 3 . 4 2 3 9 . 1 0 6 8 9 7 0 . 3 9 1 1 1 2 . 21 2 9 . 2 7 3 8 . 5 2 I • • 2e<? . 0 4 9 1 1 4 . 5 3 2 9 . 5 3 3 5 . 9 4 8 0 4 9 0 . 2 3 . 2 3 1 . 0 3 9 "I . 3 1 6 . 0 3 6 1 1 6 . 9 6 2 7 . 6 3 3 5 . 4 0 7 8 1 3 0 . 2 4 I 1 1 3 . 5 6 2 9 . 7 5 3 6 . 6 9 8 4 4 9 0 . 2 3 I I 2 1 . 9 9 2 6 . 7 3 3 1 . 2 8 7 1 1 8 0 . 3 1 I . 2 5 3 . 0 2 9 O N \>1 CUTE: 3 JUL 75 HAT CREEK COAL PROJECT - STATISTICAL ANALYSIS OF PROXIMATE TEST DATA DIAMOND D R I L L HOLE 74-039 PAGE 1 T O T A L > li»PlE..TY.g£_ LENGTH C Q i a i S E R I E S 1-199 : 4 c e . o 2 0 S E R I E S 2 C 1 - 2 9 9 : 0 . 0 0 S E R I E S 3 0 1 - 3 9 9 : 1 0 3 9 .0 3 S T D A c O Q T A S H T E S T S : 4 I M O I S T U R E S I D R Y B A S I S I E S T I M A T E D - N - S I T U M O I S T U R E O F 2 0 . 0 0 S I I I ? I I I I G R O S S I j I I | I I G R O S S I I I | I % I A S I % I J I ? I 8 T U I % t % I S I * I « | % | 6 T U I ? I X I S I I E Q U I L I R E C V 0 I A S H I V . M . I F . C . I / L B . I S U L F R I S C C A I P C T A S I A S H I V ,H . | F .C . I / L B . I S U . F R I S C 0 A | P O I A S | | « * * » * | * * « « * | * « # « « | « * « « * | « * « * » | « * * * ^ | 4 « 4 ' 4 4 | 4 « 4 4 4 | 4 4 4 4 4 | 4 » » ' i ' « | « » » » * | 9 4 ' C « ° | « * * * a | 9 » » « e | c * « * o [ 9 e « c i o | M A X IMJM 1 26 .75 161 .71 38.CI 49. 07 10760 2. 09 0.316 C.148149.37 30.41 39. 25 86 08 I .57 0 .253 MI M M.U« 1 11 . 8 5 1 1 4 .02 23.36 14.94 2800 0. 16 0. 124 0.C36I11.21 18.69 11.95 2 240 C.12 0 .099 R A N G E 1 | 14.90147. 69 i 14. 65 34.13 7960 . 1.93 0.192 0.112138.16 1 11.72 27.30 6368 1.55 0.154 W E I G H T E Q M E A N 20 1 t 21.11128.03 34. 27 37. 69 6568 C.44 1 122.43 27 .42 30.16 6655 C.35 (EXCLUOING S E R I E S 301-3991 1 l 1 • A S ] T H V E T I C M E A N | 20 1 1 21 .11 128.04 34.27 37.69 8569 0.44 0.223 i 0.083 122.42 27.41 30. 15 6855 0. 35 0.178 ( S E R I E S 1-199) 1 1 1 S T A N D A R D D E V I A T I O N 1 3.16 114.05 4.13 10.27 2336 0. 43 0. CS4 C. C51 1 11. 24 3.30 6.22 1669 0.35 0 .075 COEFP. O F V I ' I A T I O N i I 14.951 50. 10 12. 04 ,27.24 27.26 98.19 1 50.11 12.05 27.25 27.26 0.00 I I 0.1191 0 .0291 0.090 I I I REGRESSION EQUATIONS !DRY BASIS): 80.16 - O.OC607X 13195.12 -164.60Y WHERE Y X PERCENTAGE OF ASH, - GRCSS BTU PER POUND. LINEAR CORRELATION COEFFICIENT * -0.9956 .<><> NOTE: IN DERIVING THE ABOVE REGRESSION EQUATIONS FROM T!'E 1-199 SERIES SAMPLES, ONLY THE 19 SAMPLES CONTAINING ASH VALUES < 55.00% HAVE BEEN USED. ( 55.COS OR Y 4SH = 44.00* ASH AT 20.00? HCISTUPE ) ?65. C. l . l TABLE 2 COMPOSITE DRILL HOLE SAMPLE LOCATION: D.P.I1. No. 74-39 SAMPLE NO. 39-401 FOOTACE: 33' - 93' WIDTH: 60' Analysis report no. 67 -9115' P R O X I M A T E ANALYS I S As received Dry basis U L T I M A T E A N A L Y S I S % Moisture 22. 22 X X X X X Moisture % A s h 15. 23 19.58 Carbon % Volatile 30. 22 38. 85 Hydrogen % Fixed Carbon 32. 33 41.57 Nitrogen 100.00 100.00 Chlor ine Sulfur Btu 7607 9780 Ash % Sulfur 0. 24 0.31 Oxygen (diff) % Alk. as N a : 0 0. 27 0.35 S U L F U R F O R M S 0.03 • M I N E R A L A N A L Y S I S % Pyn'tic Sulfur Phos. pentoxids, P , 0 , " % Sulfate Sulfur 0.01 S i l ica; S i O , % Organic Sulfur (c l i f f . ). 0.27 \ Ferr ic cr.ide, F e , 0 , % Total Sulfur • 0.31 . . Alumina, A l , 0 , Titania. T i O , W A T E R E O L U E L E A L K A L I E S L ima, C a O % Na,0 - ND Magnes ia, M g O % K - 0 - Sulfur trioxide, S O , Potass ium oxide, K , 0 Sod ium oxide, N a , 0 FUS ION T E M P E R A T U R E O F A S H Reducing Oxidiz ing Undetermined Initial Deformation 2f>60'F 27004;F H l> Ctm n..P:.t Softening (H - W) 2675'F 2700+'F vi „ Cor,, w.dm Softening (11 « VJ W) 2685"F 2700+F SILICA V A L U E - Fluid 27G0* F 2700+1" V250 - % EQUILIBRIUM C.'OISTURE - S8 E S T I M A T E D V I SCOS ITY M A R D G R O V E GRINDA3IL ITY INDEX - at Crit ical V iscos i ty Ternporaturo of F H E E SWELL ING INDEX - ND Respectfully submitted, % Weight A s received Dry basis 22. 22 44.82 3.41 0. 84 0.03 0. 24 15. 23 13. 21 TTJ07DTJ X X X X K 57.62 4.39 1.08 0. 04 0.31 19.58 16.98 TOTUJO" 100.00 ND % wt. Ignited Basis 0.11 57.15 6. 50 26. .36 0. 87 4.40 0. 31 2. 27 0. 30 1.59 0. 14 'IF — ND-Not determined C O M M E R C I A I L ^ E S T I N G ^ ENG INE ER ING CO. Poises District Manager mUi\ k • CMARlfStOW. WV • CURHSBUBC, WV • C U V E U N 0 . OH • K O S f O l K . VA « UUi KAUIE. IN • M i N O U S O N , RY • 0 ( N « « . CC • BIRMiNGKAM, At. . K I 0 D U S B 0 R 0 , KV. <-l <•" I- C . l . l . TABLE 3 COMPOSITE DRILL HOLE SAMPLE LOCATION: D.D.H. No. 74-39 SAMPLE NO. 402 FOOTAGE: 178* - 438' WIDTH: 260' ND-Not determined Analys i : report no. P R O X I M A T E ANALYS I S As received Dry basis % Moisture . 1 9 . 0 4 xxxxx % Ash 3 4 . 8 7 4 3 . 0 7 ' % Volatile 2 3 . 5 8 2 9 . 1 2 % Fixed Carbon 2 2 . 5 1 2 7 . 8 1 I 1 0 0 . 0 0 1 0 0 . 0 0 E iu 4 9 6 5 6 1 3 3 % Sulfur 0 . 6 3 0 . 7 8 % Alk. as Na -0 0 . 4 2 0 . 3 2 S U L F U R F O R M S 0 . 4 9 • % Pyritic Sulfur " % Sulfate Sulfur 0 . 0 7 % Organic S u l f u r ( d i f f . ) 0 . 2 2 1 % Total Sulfur * 0 . 7 8 . W A T E R S O L U B L E A L K A L I E S % . N a , 0 - % K :0 - ND FUS ION T E M P E R A T U R E O F A S H Reduc ing Oxid iz ing Initial Deformation 2 5 0 0 'F 2 6 2 0 ~ 7 F ii . i c o n . H t , 8 M Softening [H W) 2 5 3 0 -F 2 6 5 0 *F w is co«. worn Softening (H ™ V J W) 2 5 4 0 *F 2 6 7 0 "F Fluid 2 6 0 0 * F 2 7 0 0 *F % EQUILIBRIUM MO ISTURE ~ ND H A R D G R O V E GR1NDABILITY INDEX » 5 4 • ai Cr it ical F R E E SWELL ING INDEX - ND 6 7 - 9 1 1 4 U L T I M A T E A N A L Y S I S % Weight A M received Dry basis Moisture 1 9 . 0 4 Carbon 3 0 . 4 7 Hydrogen 2 . 3 0 Nitrogen 1 . 0 1 Chlor ine 0 . 0 3 Sulfur 0 . 6 3 Ash 34. 8 7 Oxygen (diff) 1 1 . 6 5 100.00 % wt. MINERAL A N A L Y S I S Igr.itod'Basis Phos. pentoxide, P J O J 0 . 2 5 Si l ica; S i O , 4 9 . 9 3 Ferric oxide, F e , 0 , 1 2 . 3 1 Alumina, A l , 0 , 2 6 . 8 4 Ti lania, T i O , 0 . 8 9 Lime, C a O 2 . 5 7 Magnesia, M g O 2 . 0 1 Sulfur trioxide, S O i 3 . 4 8 Potass ium oxide, K , 0 0 . 7 6 Sodium o> ide, N u , 0 0 . 7 1 Undetermined 0 . 2 5 1 0 0 . 0 0 xxxxx 3 7 . 6 4 2 . 8 4 1 . 2 5 0 . 0 3 0 . 7 8 4 3 . 0 7 1 4 ^ 3 9 . 0 0 . 0 0 SILICA V A L U E - T2SD - E S T I M A T E D V I SCOS ITY Viscos i ty Temperature of HD •F •F- Pois*»s Respectfully submitted, C O M M E R C I A L ^ S T I N G a, E N G I N E E R I N G CO. a.^.-f louscr." District Manager CHItAtO, R o C H M U S T O N . WV . CLARKSBURG, KV . C U V f l A N D , Oil « M R f O U , VA • HMt f . HAUl t . IH . HENDERSON, KY « 0 £ N V £ » , CO • BIHMI•tCHAM. A l . HIOOltSBODO, RT. ?67. C . l . l . TABLE 4 OXIDIZED SURFACE COAL COMPOSITE OF SAMPLES S.S.I and S.S.2 Analysis report no. 64-11737 % Weight PROXIMATE ANALYS I S As received Dry basis ULT IMATE ANALYS I S As received Dry basis % Moisture 14.38 xxxxx Moisture 14.38 X X X X X % Ash 22. 51 26. 29 Carbon 41.92 48. 96 % Volatile 32. 19 37.60 f iydrogen 2.59 3.03 % Fixed Carbon 30. 92 36.11 Nitrogen 0.68 0. 80 100.00 100.00 Chlor ine 0.07 0.08 Sulfur 0.38 0.44 Btu 6607 7717 Ash 22.51 26. 29 % Sulfur 0.38 0.44 Oxygen (diff) 17.47 ?0.40 % A\k. as Na :0 0. 08 0.09 100.00 J 00700" SULFUR FORMS % Pyritic Sulfur % Sulfate Sulfur % Organic Sulfur % To la l Sulfur W A T E R S O L U B L E ALKAL IES % Na ,0 -% K,0 - FUSION T E M P E R A T U R E O F A S H Initial Deformation M i i Con. H»gM Softening (H = W) W i l Con. W>dm ND ND Reducing •F ND Softening (H V4W) Fluid % EQUILIBRIUM MO ISTURE - ND H A R D G R O V E GRINDAGILITY INDEX » ND F R E E SWELL ING INDEX ND ND - Not Determined % M o i s t u r e i s Lab Bat is MINERAL A N A L Y S I S Ph03. pontoxido, P , 0 » Si l ica; S i O , Fsrric oxide, F e , 0 , Alumina, A l , 0 , Titania, T i O , Lime. C a O Magnesia. M g O Sulfur Irioxide, S O , Potassium oxide, K ,0 Sodium oxide, Na.O Undetermined SILICA V A L U E - T250 - E ST IMATED V ISCOS ITY at Critical Viscoait/ Temperature of % Wt. Ignited Sas is "bTbT 85. 22 0.81 8.27 0.31 2.68 0.48 1.62 0.08 0. 28 0. 21 100 0 *F ND •F- Poiaes Respectfully submitted, COMMERCIAL^Tt ; ! jT ING p E N G I N E E R I N G CO. District Manager CWCAM, II • CHMIISTON. WY . CLADK̂ BURG. WV • ClEYCUnO. OH • «0«F0U. VA • T£H« HAUTf, IN . HCNOfRSON. M . OCNVER. CO • BUMINWAM, Al • MIDOLtSBORO. KT. 2 6 8 . C-l-2 TABLE 1. PORE SIZE DISTRIBUTION OF COALS AND ACTIVATED CARBON „ t,. . Sample of Sample of . . . . , „ , Pore Diameter n 1 n , c r n -, Activated Carbon . Core Coal Surface Coal 0 (d) % Pore* A_vV i n3 % Pore* AVy 1 n 3 % Pore* rAVy 3 Volume (V) Ad i U Volume (V) 'Ad" i U Volume (V) Ad 27.6 - - - - - - 37.2 2.6 0.7 0.7 0.19 5.9 1.59 44.2 3.9 0.88 1.2 0.27 9.2 2.08 53.4 4.7 0.88 1.7 0.32 12.4 2.32 66.2 5.4 0.82 3.6 0.54 16.3 2.46 85.4 11.0 1.29 5.7 0.67 19.1 2.24 117.4 20.0 1.70 11.2 0.95 23.5 2.00 181.0 34.4 1.88 14.8 0.82 31.8 1.76 228.0 42.3 1.86 26.2 1.15 37.0 1.62 372.0 63.2 1.70 74.7 2.01 67.1 1.80 * I pore volume associated with pores of diameter <_ given in column 1 269 SURFACE AREA CALCULATIONS C.1.2 TABLE 2 Core Coal (-60 + 100 mesh) SAMPLE IDENTIFICATION NUMBER » 1 Wi» 25.3271 HI" 512.100 X 1» 131.700 P3« 751.000 W2« 20.8713 H2" 144,380 X2" 529,000 ALPHA* 0 . 6 6 E - 0 4 e 4.4558 IS* 77.000 VD» 27,220 S» 16,2 B« 0,01820 C> 0.1100E-05 VS» 15.91368 ITERATION WHICH X A PI P2 V X Y 1 1 0.04169 149.9900 60.3700 2.6340 0.0804 0.0332 2 0 0.00714 174.7700 84.6600 2.8316 0.1127 0.0449 3 0 0.00714 201.8600 109.8800 3.0242 0.1463 0,056; 4 0 0.00714 236.7400 137.3200 3.2274 0, 1828 0.0693 5 0 H,00714 273.0500 166,9900 3,4350 0,2224 0,0832 6 0 0.00714 312.5000 198,3900 3.6658 0.2642 3.0975 7 1 0.04169 370.4200 303.2200 4,5022 0,4038" 0. 1504 8 1 0,04169 442.5000 385.6000 5.3131 0.5134 0,1986 9 1 0.04169 518.93*90 461.6000 6.2484 0,6146 0.2553 10 1 0,04169 613.1000 540.8000 7.7343 0.7201 0.3326 11 I 0.04169 703.2000 607.8000 10.4080 0.8093 0,4078 12 1 0.04169 759.8000 652.6000 14.0002 0.8690 0.4737 13 I 0.04169 793,5000 678.4002 18.5003 0,9033 0,505i 1 0.04169 870.5000 710.1000 24.5627 0.9455 0,7068 IS 1 0,04169 9?5.7000 717.2000 32.2816 0 O9550 0,6573 SW» 11« 065 p l i n i t i a l pressure, ton P2 - equilibrium nressure, ton V 8 v o l . of N 2 absorbed, ml/g coal X St P1/P2 (rel a t i v e vapour pressure) Y a X v(i - xr n surface area, m2/g 2 7 0 . C.1.2 TABLE 3 Surface Coal ( - 60 + 100 mesh ) SAMPLE IDENTIFICATION NUMBER a 2 diB 24,9419 HI" 307.600 AI20 20.2280 H2" 140,g80 '•o 4 07139 ISs 77,000 Bo 0,01756 Xlo 131.700 X2a 529,S0« 27,220 Co 0,1064E<=05 VSe 16,27952 PSo 751,000 A L P H A B 0,66E"04 So 16,2 ITERATION WHICH X A P i 1 1 0,03941 149,6600 2 0 0.00675 174,9700 3 0 0,00675 206.2400 4 S 0,00675 249, 1330 5 0 0,03675 299,9900 6 1 0,03941 360,0700 7 1 0,03941 430,3000 8 1 0,03941 501 ,3300 0 10 1 0603941 605,9000 1 0,03941 682,5000 u J 0 e S 3 9 4 i 754,4000 12 1 0O03S41 827,0000 13 1 907.9000 JHs 3-,t32 P2 V X Y 90,0400 0.7676 0.1199 0.1775 111.5700 0.8128 0.1486 0,2147 135,3000 0.8687 0.1802 0,2530 164,6200 0.9149 0.2192 0,3069 199,2400 0.9735 0.2653 , 0,3709 305.7600 1.1859 8 a4071 ' 0.5791 387,2000 1.3942 0,5156 0.7634 459,7000 .1 .6951 0.6121 0.9310 549,1000 2.2676 0.7312 1.1594 620,7000 3.3566 0.8265 1.4192 668,5000 5,8369 0,8901 1 .3882 695,7000 10,4943 0.9264 1 ,1988 709,2000 18.0680 0,9443 0.9390 271 . .1.2 TABLE 4 Activated Carbon - Calrron ( -60 * 100 mesh) SAMPLE IDENTIFICATION NUMBER a 3 Wl"> 21.7717 H1 0 505,300 X I " 131 .700 PSs 751 ,000 W 2B 21.5526 H2° 128,410 X2° 529.000 A L P H A B 0.66E-04 8 .0.2191 13" 77.303 VD® 27,220 Se 16,2 Bo 0,42647 . Cs 0 o2609E-04 VSo 18,56200 ITERATION WHICH X A P i P2 V X Y 1 i 0,84791 150.0100 7,3720 117,7991 0,0098 0.0001 2 i 0,84791 175,2603 91,6000 152.5973 0.1220 0,0039 3 0 0,14523 206.1 100 112.3200 157,4452 0.1492 0,001 1 4 0 rfo.4S23 242, 1400 136,0100 162,4724 0.1811 0,0014 5 0 H,14523 287,4300 164,5600 167,9130 0.2191 0,0017 6 0 0,14523 300.6200 190,2400 172.7542 0,2533- 0.0020 7 1 0„84791 356,8400 286,2700 190.4437 0,3812 0,0032 e 1 (J, 84791 416,4000 360,2700 205.2300 0,4797 0,0045 9 1 0,84791 494 O7000 435.0000 222.4298 0,5792 0,0062 IS 1 0„84791 585.9000 §14,5000 247,0969 0.685-1 0,0038 n 1 0.84791 654,2000 579,7000 280.5992 0,7719 0.0121 12 i 0004791 726, 1000 640,4000 325,4463 0,8527 0.0178 13 I 0,84791 809,9000 669,0000 405,5468 0.9174 B,02/4 14 1 S 084791 901.8000 712.60B0 555,0443 0,9489 0.0334 CALQON ACTIVE CARBON Hie calgon active carbon did not exhibit a Type II isothem; i t more closely resembled that of a Type I isotherm. Therefore, the class i c a l BET interpretation for surface area could not be used. The specific surface area for this sample was determined using the isotherm plot (see Figure 1). - 705.9 mZ/g, APPENDIX C-2, C-2-1 SORPTIVE PROPERTIES OF COAL ADSORPTION OF METAL IONS. BATCH TESTS . TABLE 1. CONTACT PROCESS LEAD. TIME: 8 Hrs., % COAL: 1% „/„ C o ^ g ^ i o n ° g 5 ^ " ™ i ^ f f i * - ° g T - T C o a l ^ Q . i i ? ^ ° - G 5 < 0-°6 >0.008* >40-100 <0.06 >0.008* >40-100 <0.06 >0.008* >40-100 Ccai <0.04 >0.Gai2--'->6Q-I0O 0-1 <0.Q5 >0.023* >70-100 <0.06 >0.028* >70-100 <0.06 >0.028* >70-100 <0.04 °' 2 < 0 ' 0 6 > 0 - 0 6 8 * > 8 5 - 1 0 0 < 0 - 0 6 > o - o g 8 * >8s-ioo o . i o o i ~7o 7TZ 77~. - x J.uj. su < 0 . 0 4 >0.572*>90-100 0.5 < 0.0 6 >0.188* >94-100 <0.06 > 0. 1 8 8* >94-100 <0.06 >0.188* >94-100 <0.05 >0.18S* >9K-100 °- 1 9 8 °- 2 0.U8 96 0.3 0.47 94 <0.06 >1.988- >99.4-i; 5 0 1'° '4-2 9 8 -. 89 97.8 !. 3 4.87 9 7 . „ 4.97 10 0 2 3 7.2 72 2.2 9 . 78 97 .3 250 • 130 1 2 . 0 48 6.2 18. 8 97.5 5 0 0 2 2 3 54.4 180 32.0 64 130 37.0 74 79.0 42.1 84.2 Blank: < 0.06 The above fig-.res are calculated on the basis that since a blank i s 0.06 then ,-v, the e f f l u e n t concentration w i l l be = 0.03 mg/1 as an average value. ^ C.2.1 TABLE 2 CONTACT PROCESS LEAD Time: 8 h r s . Coal: 5% w/w S o l u t i o n Concentration mg/1 Hean p a r t i c l e s i z e _0_LS3^on^-n^ E f f l u e n t J mg Pb removed cone. per mg/1- gm c o a l J C-2-1 TABLE 3 > CONTACT PROCESS MERCURY. TIME: 8 HRS. COAL: U w/M Cn,;/1) 0.1 •J. 5 50 I C O 253 S O U - C o a l size 0.2905 mm av. Cool s i r n n n 7 -,™ Lffl^e l T t r ^ T - * S 1 2 c 1 1 7 *v. • • i ^ / l per pm Coal r  3 o l u t i ° " . C o i l size 0 . 5 33 mm J v . Concentration Lt-iu-jnt my _ -P'"" C o n c - Removed Removal " L T " ' d .. „ °" E f l l J i T u jrs Removal srj — 1 Coal ^ _ V ms'l per rir. ~ L O a l , — . COrli Co-nl s i z e 0.034 14 ^- a v . t*t 1 luent 0. CP 0.000 00 0.013 0.0087 87 0.018 0.0082 82 0.003 0.0002 0.C3 57 Q.0UG4 9 2 . 9 0 - 0 2 2 8 0 _ 0 L ) 7 7 Q ^ ^ 0.035 0.0465 93 0.2 2 0.4 70 •3 5.6 0 . 157 . 0.484 96 . 05 0.66 0.434 8G . 0 .28 0.472 G.2 't. 38 87 . 6 3 .36 '1.664 9 3 - 2 8 1-217 4.878 97.57 1 . 9 1 3 4 . S09 l.G 0. 84 03.4 1. 3 3 9. 807 98.67 3.072 9.093 96.93 0.4G7 2 8 - 0 5 2 2 - H 80.42 10.17 23 . 98 95.93 5.7 24.43 97 . 72 24 . 6 "9.53 32 . 041 04 . 00 21. 33 47 . 87 95.73 42.67 45.73 9 1 . 4 7 g 49.2 92 94.4 9C.17 9. 953 99 . 52 98.U 93.u < S e n s i t i v i t y 0.002 mg/l J C-2-1 TABLE 4:-. CONTACT PROCESS MERCURY." TIME: 8 HRS. COAL: 5% w/w Sol;i t io: Concentration LiTiuent Coal size 0.533 mm av. Coal size 0 . 29C5 ram av. Onr/l) L'l'iluent mg Coal size 0.117 mm av. Ef f l u e n t mg Coal size 0.03414 ,-r.- av. u t l l l u c r v t m g i ' Cone. Removed Removal Ccnc. Removed Removal Cone. Removed Removal Cone. Removed Removal ;ng/i per' cm mg/1 per gm mg/1 per gm mg/1 Coal Coal Coal Coal a. i 0 . 0032 0 .00193 30 . 8 0 .0095 0 . 00101 90 .5 0 . 028 0 .0014 4 72 0 . 002 0 .00105 33 0.5 0. . 11C 0 . 007G8 76 . 8 0 .0143 0 . 00971 97 .14 0 . 5G 0 .0012 -12 0 .0045 0 . 0033 93 . 1 5 0. .03U3 0. .0083 98, . 3 0 . 0434 •o. . 09913 99, .13 0 .075 0 .0385 98 , .5 0 , .0375 0 , . 00025 09 .25 50 0. . 307 0. ,00027 99. .27 1. . 224 0 , 9755 97 . 55 0. ,378 0. . 9924 99. , 24 1. .06 0 . . 0608 06 , .03 100 0. C33 1. 9373 09. ,37 0. 331 1. .99 22 99 . 51 0 . ,267 1. ,9947 99. 73 0 . 90 1. ,0808 90. , 04 ? 50 1. 0 3 : 4 . 97 83 90. 57 0 . 8 4 . 984 99. GO 12. 45 4 . 751 95. 02 2 . 4 4 . 052 00*. 04 500 8. 57 G29 98 . 20 2. 933 9. 9413 99. 41 2 . 94 9 . 9412 99 . 41 1 . 57 9 . 9G8G 99. 60 < S e n s i t i v i t y 0.002 mg/1 C-2-1 TABLE S . CONTACT PROCESS MERCURY. TIME: 8 HRS. COAL: l o t w/w Solution _Co.il sir.n 0. 5 33 ram av. 0.1 0 . 5 100 253 500 1 size 0 • 2_9G_S__mm av. Ef f l u e n t mg : ^ . Coal P 6£ o af - S / l • per B n Coal <0.002 >0.00')98 >08 <0.C02 >0 . 00038 >98 < n . 0 0 4 6 >0.00095 >9.5.4 0.0'J 13 0.00 4 08 81. 74 <0.001C >0.0039G .-98.4 0.01714 0.00482 96.57 0.005 100 0-015 Q.04985 99.7' 0.0435 0.04956 99.13 0.05 0.0495 99 0 . 2 52 U.'ilVS 0.0375 0. 0'i902 99 . 25 99.5 0.56 0.4944 98, 0.694 0.4931 98.61 0.73 0.4927 02.54 °-'-22 °- 5 9"8 99.43 0.705 0 . 992' 09.24 0.264 0.9974 0 9 ' 7 1 4 0.33 0.09C7 90 . 67 2. 2 J 2.477 39.08 1.265 2.4074 99.49 5.38 3.0 4 . 37 99 . 4 2 - 4 " G 97.65 0.643 2.4930 93.74 2.44 ' 4 - 9 7 S C 99.51 1. 143 4.90SC g g _ 7 7 1-8M 4.3CI5 90.63 < S e n s i t i v i t y 0.002 mg/l —J < C-2-1 TABLE 6.; CONTACT PROCESS COPPER. TIME: 8 HRS. COAL: 1% w/w Solution Coal size 0. 533 .to i av. Coal s i i s 0.296S eot av. Coal, s i z e 0.117 cm AV. Coal s i z e 0.03414 i m av. Concentration <oe/i) Litluent Cone. ag/1 ntg Removed per ga Coal % Heaoval E f f l u e n t Cone. Eg/1 ag Removed per gm Coal % . Removal E f f l u e n t Cone. .ag/1 Removed per gat Coal Renoval L'f: luent Cone. ES/1 I3g Removed per ga Coal \ Reooval 0.5 0.04? 0.0458 91.6 0.032 0.04S8 93.6 0.009 0.0491 93.2 0.010 0.040 98 5.0 0.467 0,4533 90.6 0.334 0.4GG6 S3.3 0.210 0.479 95. 6 0.145 0.4855 97.1 so 8.332 *.1608 83.2 5.349 4.4051 88.1 5.147 4.4853 89.7 tt.998 4.5002 90 100 33.753 6.62.47 ' G5.2 28.34$ 7.1655 71.7 14.545 8.5455 85.5 11.935 8.8065 e s . i 253 160.997 8.9003 35.5 141.830 10,817 43.3 101.591 14.8419 59.4 95.831 15.4169 61.7 500 355 . 493 14.3S07 28.7 335.410 16.459 32.9 316.243 18.3757 36.8 314.327 18.5673 37.1 Blank: < 0.003 ag/1 C-2-1 TA3LE f. CONTACT PROCESS COPPER. TINE: 8 h r s . COAL: S\ w/w So)ut ion Coal 3> ze 0.533 n.n i av. Coal s i z e 0.29GS sura av. Coal s i r e 0.177 ru3 av. Coal s i z e 0 . 0341H as av. Concentration ppai Cone. »£/! Kg Rcxoved per go Coal 4 Removal t.t; luent Cone, mg/l mg Removed per go Coal ..... ..^ . . Renoval- E f f l u e n t Cone. ttg/1 Removed per g»a Coal \ Removal i-i : luent Cone. mg/l » 2 P.esoved per gm Coal Resoval O.S 0.021 0^00953 95.8 0.030 0.0094 "94 - 0.013 0.Q0S7 97.4 0.011 0.00958 9S.8 5.0 0.340 0,0 S-3 2 93.2 0.184 0.0963 96.3 0.83 0.0983 98.3 0.092 0.098 98.16 50 5.520 0.S89S 88.96 4.513 0.9097 9Q.97 1.846 0.9631 96.31 1.566 0.9S87 96.87 100 8.392 1.832 91.61 8.013 1.84 91.93 4.476 1.9105 95.52 4.848 1.903 95.15 250 30.61 4.268 ' 65. 36 21.8S *.56 3 91.26 15.525 4.6895 93.79 14.753 4.7C48 94 .10 500 166.747 6.665 £6, ,65 93.915 8.1217 'SI.22 59.607 8.6079 86.08 50.982 8.9804 83 .80 Blank: < 0.003 ag/1 C-2-1 TABLE 8. CONTACT PROCESS COPPER. TIME: 8 HRS. COAL: 10% w / „ _Coa.l size 0.29SS mm av. KfTIuent _Coal s i z e 0.117 nn av. .- - . - , C o j l 0. S33 BUS av. Concentrate-, ^ I ^ T ^ 5 ^ 5 r m ^ r t ^ i F ^ ^ r ^ « av. r ^ , . ^ ^ ^ ^ „ entration Cone. Removed Removal Cone. ReaoVd R J L , = I L r t l u e n t s s 5 K r i i u e n t 55 - t •-r n = " S ^ l Per s*m ' c a Kesioval Cone. Removed Removal f r , - ^ b S t»f,/l> Coal ^ ^ £ a "g/i Per 7 a * e"°*al Cone. Removed Reooval U o a l Coal 100 260 500 '"' >•»» »•» ,.„1H S6.,6 ,.„s 2_i2s? Blank: < 0.003 ag/l 95.78 —J C-2-1 TABLE 9;- CONTACT PROCESS ZlilC. TIME: 8 HRS. COAL: 1% w/w Solut ion Coal size 0.533 mm av. Coal sir.e 0 . 2965 mm av. Coal size 0.117 mm av. Coal size 0.03414 mm av. Concentration i.:iiuent ~;\ " 1. E f l i u c n t mg » E f f l u e n t m g % ETliuent mg i ppm Ccr.c. Removed Rcnovel Cone. Removed Removal ' Cone. Removed Removal Cone. Removed Removal (rr.g/i) mg/l per gm mg/l per gm mg/l per gm mg/l per gm Coal Coal Coal 0.5 0, .027 0. . 0473 94 , .6 0 , . 025 0. . 0475 95, .0 0, . 022 0 .0478 95, .6 0, .095 0. .0405 81 5 . 0 0, . 151 a. .4809 90 . 18 0. . 119 0, ,4 881 97 , .02 0 , .115 0, .4885 97 . 7 0, . 125 0 , .487 5 97 , . 5 50 12, .630 3 % ,73 64 74 . 73 10. .306 3 . 9094 79, .39 7 , .463 4 . 2537 85 . 07 7, ,600 4 . ,234 84. .68 125 60, .512 0 , .44 83 51. . 59 54 . 727 7. .0273 50. ,22 44'. ,049 8 . 0951 . 64. , 76 42 . 209 • 8. 27 31 66. , 19 2 50 10 5. .072 8, ,432 33. , 97 146. ,385 10. , 3015 41. , 4 4 110. .225 11. , 0225 44 . 09 121. ,023 12. , 898 51. ,59 500 327. .739 17. .2261 34. ,45 319. , 84 18. .0158 36. ,03 323 . ,79 17, .6209 35. ,24 307 . ,996 19. , 2004 38. ,40 Blank : < 0.01 C-2-1 TABLE 10-. CONTACT PROCESS ZINC. TIME: 8 HRS. COAL: 5% w/w Solution i c c n t r a i ppm real size 0.533 mm av. Coal size 0__29 6 5' mm_av_ Coal size 0 • 117 mm av. "me Coal s i z e -0.03414 mmay. Concentration EiUuent ^ m g ^ " ̂ E f f l u e n t ^ g ^ E f f l u e n t ^ g m ^ ^ l u e n t ^ g ^ R e ^ v a l •- -- per gm 0.! 5.0 50 125 250 500 mg/l per gm Coal mg/l mr./l Coal per gm Coal mg/l per gin Coal 0.024 0.00052. 95.2 0.018 0.009G4 90 . 4- 0 .015 0 . 0097. ' 97 . 0 0 .023 0.00054 95.4 0.117 0 . 0976G 97.GG 0.119 0.4881 97.G2 0 . 115 0 . 4885 97.7 0.05G 0.00883 93.83 3.909 0.9218 92.18 2.725 0.9455 94.55 1.777 0.9645 96.45 1.777 0.904! 5 3.338 3.923 78.46 53.838 3.923 78.46 38.205 4.235 84.69 35.150 4.297 173.74 6 . 525 9G .45 13.954 2.1209 84.84 13.615 2.2277 89.11 7.475 2.3505 ' 94.02 7.875 2.3425 93.7 85.94 65.25 157.947 6.8410 68.41132.675 7.346 73.46 123.727 7.4255 74.25 Blank: < 0.01 C-2-1 TABLE 11, CONTACT PROCESS ZINC. TIKE: 8 hrs., % COAL: 10'w/w Solution Concentration ppm <mg/I) Coal s i z e 0.533 nm av. Coal size 0.2969 mm av. Coal s i z e 0.117 ram av. Coal size 0.03414 p~i av Effl u e n t mg % cone. removed Removal mg/1 per gm coal E f f l u e n t mg % cone. removed Removal mg/1 per gm coal . E f f l u e n t mg % cone. removed Removal mg/1 per gm coal E f f l u e n t mg i cone, removed Re.T.oval rag/1 per gn coa l 0.5 0.021 0.00479 95.8 0.087 0.00413 82.6 0.022 0.00478 95.6 0.016 0.30484 96.8 • 5.0 0.078 0.04922 98.44 0.115 0.04885 97.7 0.064 0.04936 98.72 0.047 0.04953 99.05 5C 2.290 0.4771 95.42 1.461 0.4854 97.08 1.050 0.4895 97.9 1.003 0.48997 97.99 125 11.475 1.1352 90.82 9.522 1.1548 92.38 4.538 1.2046 96.37 5.028 1.1997 95.98 250 33.815 2.1618 86.47 34. 705 2. 152 86 .-12 27.141 2.2286 89.14 13.704 2.353 94.52 500 103.193 3.9101 78.36 88.450 4.1155 62.31 65.548 4.3445 86.89 52.912 4.471 89.42 Blank: < 0.01 C-2-1 TABLE 12. CONTACT PROCESS CADMIUM Coal: 1% w/w. Time: 8 hours Size 'coal'sra 0.533 =a ^ 0.2955 tun 0.117 mm 0.03414 era iJUTTTtTofr Li fluent ttg C-J 5 E f f l u e n t rag""c3 ? E f f l u e n t ng^Cd" * If f l u e n t sg CJ S Concentration Cone. Removed "eooval Cone. Removed _ Removal Cone. Rersoved Removal Cone. Keaovea Kersoval ^Z1^ isg/i per gm ng/'l per go ' OR/1 per gn eg/1 per gc Coal Coal Coal Coal 0-1 0. 007 0. 0093 93 - 0.007 C.0033 93 0.006 0.0034 94 <0.003 >0.C0955*>98.5-1 CO 0.2 0.01 0.019 95 0.01 0.019 95 <0.003 >0.0198e>99.2-100 0.004 0,0196 93 0. 5 0.023 0. 0477 95.4 0.01 0.043 98 0.01 0. 049 98 0 .007 0.0195 08.D 0.043 0.4957 99.14 0.018 0.4982 99.64 0.004 0.4390 90.92 0.013 0.49C7 99.7* 0.305 4.9135 98.27 0.830 4.917 98.34 0.425 4.9574 99.15 0.140 4.900 99.92 i"0 70.417 2.3583 29.583 54.533 4.5467 4S.47 47.651 5.2349 52.35 41.297 5.87C3 58.70 2 " 133.363 11.6032 46.653 123. 957 12.6043 $0.42 120. 391 12. 311 51.64 109 .100 14. 0 33 50.33 500 405.057 3.^54 18.985 311.627 13.837 37.574 400.969 9.903 19.8 322.395 16.701 33.S * Calculated on average of e f f l u e n t b a s i s . C-2-1 TABLE 13. CONTACT PROCESS CADMIUM Coal 5% w/w. Time: S hours .'tear. P a r t i c l e ~ ~ " " — — — • ^ i ^ l L « ° - " 3 0.29S5 w, 0.117 nm 0 C^'U ,v.u-.iOi. U f l u e n t mj>- Co 5 t..Jf. u » n T m^~cT' { F7f— ; , .. * per &rn rac/A p e r ^ i l ' h 0, 1 0 . 2 10 3 Coal > Coal Coo-] C o l 0.003 0.00104 97 <0.003 >C.00I97*>93.5-100 C.004 0.00192 96 0.005 G.0G19 9 5 0.003 0.00334 93.5 0.004 0.00392 96 0.024 0.0017G S3 <0.0C3 >C.O«397* »S3.?-:03 22.7C0 1. 54468 77.23 14.507 1.702S5 (15.43 3.789 1 - 32422 S.1.21 5.718 1.ESS6 04.28 00 C-2-1 TA3LX,'1.4,. CONTACT PROCESS CADMIUM Coal 10% w/v. Tlae: 8 hours Mean P a r t i c l e Q S 3 3 ^ 0.2365 an 0.117 an 0.03414 tr.a Si?.'.- of '.'vai :— e v i c t i o n L l f l u e n t rag Co 5 Af f luen t r.g Cu 5 E f f l u e n t rag Cd ri ETfluen t mg CU Concentration Cone. Rcaoved Removal Cone. Removed Removal Cone. Removed Removal Cone. Removed Re.-oval ar./l ng/1 per gm Eg/1 per gn mg/l per gm ag/1 per grr. Coal Coal . Coal Cc a l 0.1 O.0C0 0.00001 01 <0.003 >0.00037 >37 0.005 0.0009S OS <0.033 >0.00038->S3.5-1C0 0.2 0.000 0.00194 97 0.003 0.00137 98. 5 <0. 003 >0.0019S'>99.2-100 <0.003 >-3.00198 >93'. 2-100 0.5 0.005 0.00435 99 <0.003 >0.004SS*>93.7-100 0.006 0.00434 38.8 0.010 0.0043 9E 5 0. 011 0. 04380 99, ,78 0. ,004 0. .04996 99 .92 <0. .003 >0 . 04993* >99 , 97 <0. .003 >3. . 04 9 9 6 - > 3 3 . .57 11 3. .125 0. ,4987 99. .75 0, .076 0. .49924 99 .85 0. .0,51 0 .49048 99, .898 0. .038 0. .49352 99, .9^ 100 10. .801 0. , E320 89. . 130 6. .030 0. ,93964 93 .964 4, .024 0 .55976 95, . 976 2 .047 0, .9735 97 , . 353 250 14. .613 2. , 353P 94, ,153 12. .481 2. , 375 95 .00 9. .223 2 .408 96. . 31 5. ,0 79 2. .443 57 , . 73 500 85. . 303 4 . 1469 32, .938- 65, .550 4, .345 86 .89 49, .14 4 .509 90, ,172 22, . 651 4, ,773 95. .4678 * Calculated on average of e f f l u e n t basis C-2-1 TABLE 15.. CONTACT PROCESS CADMIUM Time: 4 hrs. Coal 1%. Size: 0.2965 nun (Medium) So l u t i o n cone. mg/1 E f f l u e n t cone. mg/1 ' mg Cd removed per gm coa l % Removal 0,1 0.007 0.0093 93 .0.5 o.om 0.0486 97.2 5 0.085 0.4915 98.3 50 9.645 4.0355 80.71. 100 33.395 S.660S 65.805 250 15S.948 9.4052 37.621 500 356.169 14.383 28.77 :-2-i TABLE 16. CONTACT PROCESS CADMIUM EFFECT OF PARTICLE SIZE Time: U hrs. Coal 5% Corse, of Cd = 500 ppm P a r t i c l e Size 0.03414 0.117 0.29S5 Solution cone, rag/1 500 S00 500 E f f l u e n t cone. sig/1 88.972 124.093 173.479- mg Cd removed per gja coal 8.221 7.518 6.5304 Removal 82.21 75.18 65.30 0.533 5Q0 231.205 5.376 53.75 C-2-1' TABLE 17. CONTACT PROCESS CHROMIUM. TIME 8 HRS. COAL: 1% w/w Solution Coal size 0.533 nun av. Coal size 0 . 2065 mm av. Coal s i z e 0.117 ram.'av. Coal size 0.03414 ran av. Con-ontration E f f l u e n t mg 1 Affluent Hg ' E 7 Fluent rag 1 E i : luent mg r, ppm Cor.c. Removed Removal Cone. Removed Removal Cone. Removed Removal Cone. Removed Removal (mg/l) mg/1 per gm mg/1 per gm mg/1 per gm mg/1 per gm Coal Coal " Coal ' Coal 0.1 <0.025 >0.0075 >75 <0.019 >0.0081 >31 <0.010 >0.0081 >31 <0.017 >0.0033 >83 0 . 5 <0 . . 0 5 >0 . 0 4 5 >90 < 0 . 0 5 >0, . 0 4 5 >90 <n . 0 5 >0. . 0 4 5 >90 < 0 . 0 5 >0 . 04 5 >90 5 0 . . 3 0 . 4 2 84 0 . 4 0 . . 4 6 0 2 0 , .6 0 , . 4 4 83 0 . 4 0 , . 4 6 02 50 1 6 . , 3 3 . 3 7 67 . 4 1 1 . 8 3 . , 82 7 6 . 4 8 . . 0 5 4 . , 1 3 5 3 3 . . 9 9 . 1 4 . , 09 8 1 . 8 1 0 0 80 2 . . 0 20 7 5 2 . , 5 25 70 3 . .0 30 73 2 . , 7 27 2 5 0 2 1 4 3 . . 6 14 . 4 2 1 2 3 . 8 1 5 . 2 2 0 6 4 . .4 1 7 . . 6 2 1 4 3 . , 6 14 . 4 5 0 0 4 9 3 0 . ,7 1 . 4 4 8 0 2 . 0 4 4 6 8 3 . , 2 6 . , 4 4 6 5 3 . , 5 7 Blank: C-2-1 TABLE 18. CONTACT PROCESS CHROMIUM. TIME: 8 HRS. COAL: 5% w/w Solu L ion Co.li S ize 3 . 5 3 3 mm ,iv. Coal size 0 . 2 9 6 5 mm av. Coal size 0 . 1 1 7 mm av. Coal size CO 3 " 1 4 mm av. Conor;. 1 rat ion' L: i ;:i.:nt n i g 'i It 1luent mg •i E f f l u e n t "P. 0 Lt1luent mg i Dt).Tl Cone. Removed Removal Cone. Removed Removal Cone. kemoved Removal Cone. Removed Removal (mg/i) "I/-./1 :r gm mg/l per gm mg/l per gm mg/l per gm Co.ii Coal Coal Coal 3 . 1 < 0 . 0 2 5 >C . 0 0 1 5 >75 < 0 . 0 2 1 > 0 . 0 0 1 G >7 9 < 0 . 0 0 5 > 0 . 0 0 1 3 >9S < 0 . 0 1 5 > 0 . 0 0 1 7 >3S U . 5 < o . o r u >Q. 0 0 0 5 >95 . 2 < 0 . 0 5 > 0 . 0 0 9 >90 < 0 . 0 5 >0 . 0 0 9 >90 < 0 . 0 0 5 >0 . 0 0 9 9 . >99 0 . 0 3 2 0 2 . 0 0 . 3 0 . 0 9 4 94 0 . 2 0 . 0 9 6 96 0 . 17 0 . 0 ' J o C ' 9 6 . 6 8 - 5 0 . 8 3 8 3 . 0 ' C . 8 0 . 8 6 4 8 6 . 4 3 . 0 - 0 . 0 2 4 9 2 . 4 3 . C 0 . 9 2 8 9 2 . 6 1 0 0 1 1 . 3 i.77i; 80.7 10 1 . 8 90 10 1 . 8 90 9 . 5 1 . 81 9 0 . 5 2 5 0 1 3 7 7 . 3 0 47 . 2 1 2 5 2 . 5 50 1 3 5 2 . 3 46 1 3 3 2 . 34 5 0 0 4 7 5 0 . 5 5 4 0 2 0 . 7 6 7 . 0 4 5 0 1 . 0 10 4 4 5 1 . 1 1 1 C-2-1 TA3LE 19. CONTACT PROCESS CHROMIUM. TIME 8 HRS. COAL 10% w/w. Lolutiun C e i l ^i=G 0. 533 i?.ra av. Concj.-Urution L.r f k^n t (.TW1) 0. 0.5 53 10 0 500 cc;:c. ni,;/I _ Coal size 0.20G5 mm av. Coal s i z e 0.117 mm av. Effluent Coal s i z 0 . 0 3 1.14 n.r.-, u \ "T. • - ,-nr' 1 Ef f lup-it ~« ^ - n X ^ S R C m O V a l ITn ?™r» ? ~ « - v e d Removal HcoveC ^ o v a l <0.011 >C.0003 >80 0 . 3 G8 36 5 <0.05 >0.0005 >50. <0.01 >0.0000 >9C <0.028 >0.00'J7 >72 <0.05 >:1.00«5 >30 <0.033 >0.004G >93.4 <0.045 >0.0045 >01 0.047 04 . 0 0 . 5 0.04! 90 0.2 0.048 0.4 5! 01.0 5.2 0.448 80.6 3.2 ' J- i 0.301 90.0 10.8 1 32 1.3! 0 . 896 09.6 12.6 72.0 84 1. CO 66.4 95 27 330 1.7 34 405 0.374 1. 5S 0.95 <0.C5 -0.0045 >00 06 0.09 0.468 03.6 2.9 87.4 6.2 62 61 19 - 400 0.04 91 'Jo . 2 0.471 04.; 0.933 03.3 1. Q'J 1.0 7 5. C 20 Blank < 0.05 f\3 O C-2-1 TABLE 20. CONTACT PROCESS CHROMIUM Contact time: 4 hrs Coal size : 0.2965 mm Coal 1% w/w Coal 51 w/w 1 r. ; 1 j-?;; t So I v. t ion Cone. m*/ 1 L:;;ucnt Cone. mg/1 mg Removed per gm Co a 1 Removal i n f l u e n t S o l u t i o n Cone. mr /I L i l lsicnt Cone. mg/1 mg Removed per gm Con 1 Remova1 0.1 0.04 0.005 60 0.1 <0 . 05 >0.001 >50 0 . 5 0.07 0.043 36 0.5 <0.05 >0.000 >v0 0.7 0.43 80 5 1.0 0.08 80 50 17. 5 3.25 65 ' 50 7.1 0.853 85.8 10 0 C4 . 6 3.54 3 5.4 100 13 . 5 1.73 80 . 5 250 220 3.00 12 250 130 2.4 48 500 4 70 3. 00 5 500 445 1.1 11.0 Blank < 0.0 5 r 2 9 2 . C-2-2 REGRESSION ANALYSIS OF ADSORPTION ISOTHERM DATA (1) LEAD ADSORPTION DESCRIPTION OF THE ISOTHERM. . LINEAR REGRESSION ANALYSES % Coal Particle Size mm (Contact time) (x/m) Ci k n 2 r 1% 0.533 (8 hrs) 36.071 1.5587 1.9782 0.94493 1% 0.2965 (4 hrs) 40.0 6.93179 3.5405 0.97263 n 0.0 3414 (8 hrs) 110.0 7.3757 2.365 0.98764 X m 293. (2) CADMIUM ADSORPTION DESCRIPTION OF THE ISOTHERM LINEAR REGRESSION ANALYSES % Coal Particle Size mm (Contact time) (x/m) Ci k n 2 r 1% 0.533 (8 hrs) 20.51262 0.59105 1.75212 0 .8113 n 0.2965 (8 hrs) 30.749 0.96444 1.79595 0 .81083 i % 0.117 (8 hrs) 23.656 0.90342 1.90329 0 .85189 i % 0.03414 (8 hrs) 18.744 3.2777 3.56397 0 .79474 5% 0.533 (8 hrs) 18.89 0.36551 1.57520. 0 .89090 5% 0.2965 (8 hrs) 21.22 0.614036 1.75403 0 .87872 5% 0.117 (8 hrs) 29.95 0.37969 1.42276 0, .98669 5% 0.03414 (8 hrs) 16.92 1.4356 2.51907 0. .93665 10% 0.533 (8 hrs) 14.55 0.401846 1.73146 0, .86261 10% 0.2965 (8 hrs) 9.34 0.74568 2.45856 0. .93274 10% 0.117 (8 hrs) 11.42 0.84994 2.39212 0. .92601 10% 0.03414 (8 hrs) 17.15 1.04146 2.21855 0. .91953 1% 0.2965 (4 hrs) 27.67 0.62748. 1.64136 0, .92654 294. (3) COPPER ADSORPTION DESCRIPTION OF THE ISOTHERM LINEAR REGRESSION ANALYSES % Coal Particle Size mm (Contact time) (x/m) Ci k n 2 r 1% 0.533 (8 hrs) 25.78 0.55460 1.61871 0.95036 1% 0.2965 -(8 hrs) 31.91 0.694715 1.62379 0.94888 1% 0.117 (8 hrs) 41.534 1.10285 1.71267 0.96761 Vo 0.03414 (8 hrs) 69.77 0.66324 1.33478 0.89472 5% 0.533 (8 hrs) 25.2 0.21845 1.30870 0.98186 51 0.2965 (8 hrs) 49.2 0.26656 1.19054 0.98243 51 0.117 . (8 hrs) 72.05 0.34290 1.16212 0.94609 5% 0.03414 (8 hrs) 75.87 0.51385 1.24421 0.98967 10% 0.533 (8 hrs) 13.91 0.08470 1.21831 = 1.00 10% 0.2965 (8 hrs) 58.8 0.19509 1.08860 0.99709 10% 0.117 (8 hrs) 54.25 0.311675 1.20453 0.91311 10% 0.03414 (8 hrs) 108.83 0.419063 1.11782 0.98867 295. (4) ZINC ADSORPTION "' DESCRIPTION OF THE ISOTHERM LINEAR Rl AGRESSION ANALYSES % Coal Particle Size mm (Contact time) (x/m) Ci k n 2 r 1% 0.533 (8 hrs) 22.01 0.65223 1.76598 0.96179 1% ' 0.2965 (8 hrs) 25.56 0.77173 1.77555 0.95237 1% 0.117 (8 hrs) 30.44 0.86905 1.74754 0.95154 i % 0.03414 (8 hrs) 36.14 0.65825 1.55154 0.88909 5% 0.533 (8 hrs) 19.33 0.24748 1.42607 0.96825 5% 0.2965 (8 hrs) 22.1 0.28698 1.43012 0.96955 5% 0.117 (8 hrs) 31.8 0.35961 1.38631 0.96302 5% 0.03414 (8 hrs) 31.69 0.37888 1.40395 0.93452 10% 0.533 (8 hrs) 16.83 0.17202 1.35587 0.96286 10% 0.2965 (8 hrs) 26.27 0.13423 1.1778 0.88812 10% 0.117 (8 hrs) 30.82 0.24067 1.28071 0.93774 10% 0.03414 (8 hrs) 40.76 0.29564 1.26147 0.95417 1% 0.2965 (4 hrs)' 21.07 0.60051 1.74666 0.89521 296. (5) CHROMIUM ADSORPTION DESCRIPTION OF THE ISOTHERM LINEAR REGRESSION ANALYSES % Coal Particle Size mm (Contact time) (x/m) Ci k n 2 r 1% 0.533 (8 hrs) 4.13 0.18031 1.98438 0.74904 1% 0.2965 (8 hrs) 6.69 0.23962 1.86705 0.81934 1% 0.117 (8 hrs) 9.28 0.25614 1.7311 0.85201 i % 0.03414 (8 hrs) 8.45 0.26405 1.79329 0.84776 5% 0.533 (8 hrs) 3.92 0.08182 1.60609 0.76578 5% 0.2965 (8 hrs) . 5.29 0.08638 1.51048 0.79665 51 0.117 (8 hrs) 5.44 0.11900 1.62508 0.83628 51 0.03414 (8 hrs) 6.08 0.11001 1.54897 0.80208 10% 0.533 (8 hrs) 7.14 0.06176 1.30813 0.90841 10% 0.2965 (8 hrs) 8.53 0.04280 1.17363 0.89515 10% 0.117 (8 hrs) 4.70 0.06264 1.43892 0.87755 10% 0.03414 (8 hrs) 6.36 0.06827 1.37048 0.78332 1% 0.2965 (4 hrs) 8.34 0.170825 1.5985 0.84300 1% 0.296 (4 hrs) 6.47 0.05713 1.31396 . 0.81913 2 9 7 . (6) MERCURY ADSORPTION 0, 0 Coal Particle Size mm- (Contact time) (x/m) Ci k n 2 r 1% 0.533 (8 hrs) 258.72 1.49243 1.20547 0.77304 1% 0.2965 (8 hrs) 1007.19 1.17190 0.91609 0.95645 1% 0.117 (8 hrs) 2116.51 1.60065 0.86469 0.94287 1% 0.03414 (8 hrs) 6123.00 2.9508 0.81367 0.980608 5% 0.533 (8 hrs) 3061.60 1.50744 0.81596 0.84065 5% 0.2965 (8 hrs) 1037.95 1.931190 0.72352 0.87219 5% 0.117 (8 hrs) 1160.47 0.72156 0.84175 0.56056 5% 0.03414 (8 hrs) 1361.06 1.93099 0.94764 0.94849 10% 0.533 (8 hrs) 1120.11 1.11197 0.89871 0.81218 10% 0.2965 (8 hrs) 2951.26 1.45626 0.81620 0.98332 10% 0.117 (8 hrs) 2047.03 1.31187 0.84521 0.87939 10% 0.03414 (8 hrs) 3618.69 2.26493 0.84251 0.960397 1% 0.2965 (4 hrs) 1373.41 2.43744 0.98113 0.767318 5% 0.2965 (4 hrs) 1299.76 3.47967 0.59028 0.95303 Appendix C-2-3. Comparison of a d s o r p t i o n of metal ions by c o a l and a c t i v a t e d carbon. I n i t i a l Cone. = 50 p.p.m. Pb-K- Contact time = 8 hours Solution = 100 c.c. Pa r t i c l e size of materials = 48/100 Mesh Tyler. Coal/Carbon Dosage Oxidized Surface Coal C e x/m % efficiency mg/l mg/gm cos C.-C i o x 100 Unoxidized Core Coal C e x/m Z e f f i c i e n c y mg/l nig/gm coal C -C i o x 100 Calgon Activated Carbon _£e x/m % efficiency. mg/l mg/gni coal C.-C i o x 100 0 50 217* 50 125* 50 19.3* 0.025 26 96 48.0 35 60 30 46 16 8 0.05 15 70 70.0 14 72 72 42 16 16 0.1 3 47 94.0 6 44 88 36 14 28 0.2 2.330 24.79 99.1 0.286 24.86 99.4 18 16 64 0.5 0.285 9.94 99.4 0.286 9.940 99.4 2 9.6 96 1 0.286 4.97 99.4 0.143 4.990 99.7 0.286 4.97 99.4 2 0.143 .. 2.49 _ 99.7 0.143 2.490 99.7 0.286 2.49 99.4 5 0.143 0.997 99.7 0.143 0.997 99.7 0.143 0.997 99.7 Obtained by extrapolation of the isotherm l i n e to the i n i t i a l concentration 50 p.p.m. and this value, rapresents the maximum adsorptive capacity. ?\5 CO 2 9 9 . Appendix C-2 - 4 . FACTORS INFLUENCING THE ADSORPTION PROCESS. C-2-4-1 Table 1. E f f e c t of contact time Type of Coal: Oxidized Hat Creek coal I n i t i a l Cone. = 50 mg/1 Pb P a r t i c l e s i z e of coal = 0.533 mm av. Coal weight = 1%' W/W Contact Time (hours) Equilibrium Concentration (mg/1) 0 50.00 1 9.00 2 • 4.85 3 2.63 4 0.4 8 0.03 16 0.03 24 0.03 C.2.4.1 TABLE 2 EFFECT OF TIME ON THE EFFICIENCY OF REMOVAL OF LEAD IN COHTACT WITH COAL. Coal % w/w: _1%. Mean particle size: 0.2965 Solution concentration 0.1 rng/1. Contact time hrs. Solution cone. mg/1 Effluent cone. Kig/1 mg Pb removed per gm coal % Removal 1 < 0.1 .. 0.7 0.003 30 2 0.1 0.07 C.003 30 3 0.1 < o.os 70-100 «• 0.1 < 0.06 > 0.007* 70-100 8 0.1 < 0.06 > 0.007- 70-100 Blank : < O.OS * Calculated *u K • 0-06 on the basis — ^ — = 0.03 as an average value C.2.4.1 TABLE 3 EFFECT OF CONTACT TIME ON ABSORPTION OF LEAD BY CONTACT PROCESS. Solution cone. 500 ppm. Coal 5% w/w Contact time h r s . 4 HOURS 8 HOURS Mean P a r t i c l e S i z e iron E f f l u e n t mg Pb removed % cone. per Removal mg/l c o a l . E f f l u e n t mg Pb removed % cone. per Removal mg/l gm c o a l s 1 0.03414 | 1.5 9.97 99.7 1.0 9.98 99.8 : " 0 .117 • 2,1 9.96 99.6 3.3 9.93 99.3 — 1— • j 0.2965 .J 10 9.8 98.0 j 8.2 9.84 98.4 \ — — — * • ~ " 0.533 j 26 9-48 94.8 j 16 9.68 96.8 S 3 ' . • C.2.4.1 TABLE 4. CONTACT PROCESS LEAD. TIME: 24 h r s , MEAN PARTICLE SIZE 0.533 ram* - S o l u t i o n Concentration .rag/1 C o a l 1% w/w C o a l 5% w/w C o a l 10-3 w/w — ! J. J.UCJ1 I Cone. mg/1 mg Pb Removed p e r gm C o a l % D e t e c t a b l e Removed E r i r l u e n t Cone. mg/1 mg Pb Removed p e r gm C o a l a. — o D e c t e c t a b l e Removed E f f l u e n t Cone. mg/1 mg Pb Removed p e r gm C o a l D e c t e c t a b l e Removed 0.05 <0. 03 >0.0035 >70-100 <0.03 >0.007 >70-100 <0.03 >0 . 00035 >70-100 0.1 <0. 03 >0.0085 >85-100 • <0.03 >0.0017 >85-100 <0.03 >0.00085 >85-100 0.2 <0.03 >0.0185 >92.5-100 <0.03 >0.0037 >92.5-100 ^0.03 >0.00185 >92.5-100 B l a n k : < 0 .03 * The above f i g u r e s are c a l c u l a t e d : on the basis that since a blank i s 0 .03 then the e f f l u e n t concentration w i l l . 0.03 be 2 = 0.015 mg/1 as ; an average value O APPENDIX" C-2-4-2 EFFECT OF COAL DOSAGE TABLE 1 CONTACT PROCESS MERCURY COAL S I Z E : 0.295S mm a v . T I K E : 8 HRS. I n f l u e n t Cone. mg/ l F f f 1 1, c. •-, +• C o a l 1% w/w ' jr—• — C o a l 5% w/w C o a l 10% w/v Cone. mg/l mg Hg Removed per- gm C o a l : Removal • E f f l u e n t Cone. mg/l mg Hj p e r g Removed gm C o a l a Removal E f f l u e n t Cone. mg/l mg Hg Removed p e r gm C o a l Removal 0.1 0.013 0.0087 87 0.0095 0, . 00181 90.5 <0.002 >0 .00098 >98 0.5 0.0228 0.0477 95.4 0.01431 0' . 00971 97.14 0.01714 0.00482 96 . 57 5 0.157 0.484 96.86 0.0434 0. 09913 99.13 0.0435 0 .04945 93.13 50 . 3.36 4.664 93 .28 1.224 0. 97 55 97.55 0.56 0.4944 93. 88 100 1.33 9. 867 98.67 0.391 1. 9922 99.61 0.765 0.9924 99.24 250 10.17 23.98 95.93 • 0.8 4. 984 99.68 1.265 2.4874 99.49 500 21.33 47. 87 95.73 2.933 9 . 9413 99.41 2.44 4.9756 99 . 51 o V J 4 2-' CONTACT PROCESS CADMIUM. TIME 8 h r s . MEAN PARTICLE S I Z E : 0.2965 S o l u t i o n C o a l 1% w/w C o a l 5% w/w C o a l 10% w/w C o n c e n t r a t i o n mg/1 E f f l u e n t Cone. mg/1' mg Cd Removed p e r gm C o a l Removal E f f l u e n t Cone. mg/1 mg Cd Removed p e r gm C o a l Removal E f f l u e n t Cone. mg/1 mg Cd Removed D e r gm C o a l . Removal 0.1 0. 007 0.0093 93 <0.003 >0.00197* >93.5-100 <0.003 >0.00093* >9S.5-100 0.2 0.010 0.019 95 0.004 0.00392 98 0.003 0.00197 98.5 0.5 0. 010 0.049 .98 0.003 0.00994 9 9.4 <0.003 >0 . 00493* >39.7-lC0 5 0.018 0.4982 99.64 0.007 0.09986 99.86 0.004 0.04996 3 9.92 50 0.83 4.917 98.34 0.118 0.99754 99.76 0 ,075 0.49924 99 . 85 100 54.533 4.5467 45.467 14.507 1.70986 85.49 6 .036 0.93954 93.954 250 123.957 12.6043 50.42 30.95 4. 381 87.62 12.481 2.375 95.00 500 400.969 9.903 19. 8 110.915 7.782 77. 32 65.550 4. 345 86. 39 C a l c u l a t e d on a v e r a g e o f e f f l u e n t b a s i s VJ-J O C-2-4-2 TABLE 3. CONTACT PROCESS COPPER., TIME: 8 HRS. MEAN PARTICLE S I Z E 0. S o l u t i o n C o n c e n t r a t i o n C o a l •&r f l u e n t 1% ""7 /w C o a l 5% w/w C o a l 10% w/w mg/1 Cone. mg/1 mg CU Removed p e r gm C o a l Removal E f f l u e n t Cone. mg/1 mg cu Removed p e r gm C o a l Removal E f f l u e n t Cone. mg/1 mg c u Removed p e r gm C o a l c Removel 0.5 0.032 . 0468 93 . 6 0.030 0.0094 94 0.021 0.0048 95 . 8 5. 0 0.334 0 .4665 93.3 0.184 0.0963 96.3 0.172 0.0483 96.5 SO 5.949 4 . 4051 8 8..1 4.513 0.9097 90. 97 2. 816 0.4718 94.4 100 23.345 7 . 16S5 71.7 8.019 1.84 91.98 5.221 0.948 94.8 250 141.33 10 .817 43.3 21.85 4. 563 91.26 14.18 2.358 94.3 500 335.41 16. . 46 32.9 93.915 8.1217 81.22 • 35.65 4.643 92.9 o U 1 C-2-4-2 TABLE 4. CONTACT PROCESS ZINC. TIME 8 HRS. MEAN PARTICLE SIZE .2965 S o l u t i o n C o n c e n t r a t i o n ag/1 C o a l 1% w/w C o a l 5% w/w C o a l . 10% w/w E f f l u e Cone. mg/l n t mg Zn Removed p e r gm C o a l Removal E f f l u e Cone, mg/l n t mg Zn Removed p e r gm C o a l i Removal E f f l u e n t Cone. mg/l mg Zn Removed p e r gm C o a l R e m o v a l . 5 0.025 0.0475 95.0 0.018 .0.00964 96.4 0.087 0.00413 82. 6 5.0 0.119 0.4881 7.62 0.119 0.4881 97.62 0.115 0.04885 97.7 50 10.306 3.9594 79.39 2.725 0.9455 94.55 1.461 0 . 4854 9 7. 08* 125 54.727 7.0273 6 .22 13.615 2.2277 89.11 9.522 1.1543 92.38 250 146.385 10.3615 41. 44 53.838 3.923 78.46 34.705 2.152 86. 12 500 319.84 18.0158 36.03 157.947 6.8410 68.41 88.450 4.1155 82. 31 V>4 O CTv C-2-4-2 TABLE 5. CONTACT PROCESS CHROMIUM MEAN PARTICLE S I Z E : 0.2965 ram. TIME: 8 HRS. ErFECT Or PERCENTAGE COAL I n f l u e n t S o l u t i o n Cone. 0.1 0.5 E f f l u e n t Cone. mg/1 C o a l 1% w/w <0.05 mg % Removed Removal p e r gm C o a l <0.019 >0.0081 >81 C o a l 5% w/w E f f l u e n t mg % Cone. Removed Removal mg/1 p e r gm . C o a l =0.021 >0.0016 >79 >0.045 >90 <0.05 >0.009 >90 C o a l 10% w/w E f f l u e n t mg % Cone. Removed Removal mg/1 p e r gm C o a l <0.05 >0.0005 >50 <0.033 >0.0046 >93.4 0.4 0.46 92 0.3 0.094 94.0 0.5 0.45 90 50 11.8 3.82 76.4 6 . 8 0.864 86.4 5.2 0.448 89.6 100 75 2.5 25 10 90 10.8 0 . 896 89.6 250 212 3. 15.2 125 2.5 50 84 1.66 65.4 500 430 2.0 4.0 462 0.76 7.6 330 1.7 34 O -3 PPENDIX C-2-4-3 EFFECT OF SOLUTION CONCENTRATION 3 0 8 . C-2-4-3 TABLE 1.CONTACT PROCESS ZINC EFFECT OF CONCENTRATION AT 4 HRS. CONTACT MEAN COAL SIZE 0.2965 mm. COAL 1% w/w S o l u t i o n cone, mg/1 E f f l u e n t cone, mg/1 mg Zn removed per gm Coal % Removal 0 5 50 100 250 500 0.069 0.130 12.117 37.736 159.329 373.166 0.0431 0.487 3.7883 6.2264 9.0671 12.6834 86.2 97.4 75.77 62.26 36.27 25.37 C" 2" 4 - 3 T A B L E 2- CONTACT PROCESS COPPER EFFECT OF CONCENTRATION AT 4 HRS. CONTACT MEAN COAL SIZE 0.2 96 5 mm COAL 1% w/w 500 °' 5 0.017 5.0 50 S o l u t i o n E f f l n p n i - o- cone, mg/1 cone Z>1 ° U r e r n o y e d % a uonc. mg,i p e r g m c o a l 359.155 14.0845 Removal 0.0483 96.6 0.775 0.4225 7.218 4.2782 84.5 85.56 1 0 0 30.63, 6 . 9 3 3 6 6 9 _ 3 7 „ " 7 - 8 8 7 • W.2113 ,0.85 28.17 APPENDIX C-2-4-4 EFFECT OF COAL PARTICLE .SIZE 309. C-2-4-4 TABLE 1. CONTACT PROCESS MERCURY EFFECT OF TIME OF CONTACT MEAN COAL SIZE 0.29 6 5 mm. COAL 5% w/w P a r t i c l e S i z e mm I n f l u e n t Cone, mg/l a f f l u e n t Cone, mg/l mg Hg Removed per gm Coal % Removal 0.03414 50 0. 36 0.9928 99.28 0.117 50 0.63 0.9874 98.74 0.2965 50 0.77 0.9846 98.46 0.533 50 0.9 0.982 98.2 C-2-4-4 TABLE 2. CONTACT PROCESS CHROMIUM TIME 4 HRS 5% w/w COAL P a r t i c l e S i z e mm I n f l u e n t S o l u t i o n Cone. mg/l E f f l u e n t Cone, mg/l mg Removed per gm Coal % Removal 0.03414 50 4'. 3 0.914 91.4 0. 117 50 5.6 0.888 88.8 0.2965 50 7.1 0.858 85 . 8 0.533 50 7.6 0.848- 84. 8 3 1 0 . C-2-4-4 TABLE 3. CONTACT PROCESS ZINC COAL PARTICLE SIZE EFFECT AT 4 HRS. CONTACT WITH 5% COAL w/w Solution P a r t i c l e E f f l u e n t mg Zn removed % cone, mg/l siz e mm cone, mg/l per gm Coal Removal 100 0.533 (> \ in) 16.897 1.662 83.1 100 0.2965(> 60 ) 11.8 1.764 88.2 100 0.117 (> 150 ) 9.644 1.807 90.4 100 0.Q3414 (< 150) 7.044 1.859 93.0 C-2-4-4 TABLE 4- CONTACT PROCESS COPPER COAL PARTICLE SIZE EFFECT AT 4 HRS CONTACT WITH 5% COAL w/w Solution P a r t i c l e Cone, mg/l siz e E f f l u e n t cone, mg/l mg. Cu removed % per gm coal Removal 500 500 500 500 1/4" mesh (0.533 mm) > 60 mesh (0.2965 mm) > 150 mesh (0.117 mm) < 150 mesh (0.03414 mm) 207.746 142.606 70.423 63.204 5.845 7.1478 8.5915 8.7359 58.45 71.48 85.92 87.36 311 . Appendix C-2-5. A n a l y s i s of Variance f o r data from the batch t e s t s w i t h heavy metal. Square Degree Sum Mean of of Variation Freedom Square Square F-Value Coal Dosage (C) 2 P a r t i c l e size (P) 3 Solution Cone (N) 8 Type of Metal Ion (E) 5 C x P 6 C x N • 16 P x N 24 C x E 10 P x E 15 N x E . 40 2104.9 16.727 7914.7 531.26 28.544 3601.6 70.369 538.46 57.696 1744.0 1052.5 5.5757 989.34 106.25 4.7573 225.10 2.9320 53.846 3.8464 43.599 341.14** 1.8072(N.S.) 320.67** 34.439** 1.5420(N.S.) 72.961** 0.95034(N.S.) 17.453** 1.2467(N.S.) 14.132** C x P x N C x P x E C x N x E P x N x E 48 30 80 120 117.71 103.46 1474.2 385iOS 2.4522 3.4435 18.428 3.2087 0.79482(N.S.) 1.1178(N.S.) 5.9729** 1.0400(N.S.) Error Total 240 647 740.46 19429.0 3.0852 ** highly s i g n i f i c a n t at the 1% l e v e l . N.S. Non s i g n i f i c a n t APPENDIX C-2-6 DATA OF COLUMN ADSORPTION TESTS. C-2-6 TABLE 1 . COLUMN ADSORPTION PROCESS - LEAD Volume o f S o l u t i o n = 500 m l . R a t e o f F l o w - O.&zpm/ft2 Depth o f Column = J^_'(20cm.) = 600 gms c o a l , contact time = 30 min. „ , . l ! e a n P a r t i c l e S i z e Mean P a r t i c l e S i z e Mean P a r t i c l e S i z e Mean P a n i c l e Siz<=- S o l u t i o n _ Q.£„3 mm 0-2965 mm 0.117 mm 0 ?414 ^ C o n c e n t r a t i o n E f f l u e n t mg Pb % E f f l u e n t Sg"T5 % E f f l u e n t S F T b % E f f l u e n t F F ^ b % mg/1 Ccr.c. Removed Removal Cone. Removed Removal Cone. Removed Removal C o n e ' " Removed R e - o v a l m g „ J ^ ^ f n-'t m g / 1 P e r S m „ P e r gm ,, mg/1 p e r gm u corii y i n c o a l X 10 — t c o a l X 10 0. <0. . 018 >0. .76* >91-100 <0. ,018 >0.76* >91 -100 <0 .01 >0 . ,79* >95 -10 0 <0 .01 >0. .7 9* >95-100 0. 2 <0. 018 >1. 59* >95.5-100 ' <0. 018 >1.59* >9-S . 5-100 <0 .031 >1. 5 3* >92 -100 <0 .03 >1. 54* >92.5-100 0. 5 <0. 02 >4. 0 8* >98-100 <0. 02 >4.08* >98--100 <0 .01 >4. 12* >99 -100 <0 .02 >4 . 0 8* >98-100 5 0. 028 41. 43 99.44 <0. 02 >41.6* >99 .8-100 <0 .02 >41. 6* >99 .8-100 0 .034 41. 38 99.32 50 0. 08 416. 0 99.8 <0. 02 >416.6* >99, .98 0 .037 416 . 36 99 .93 <0 .02 >415. 6* >99. 93 500 0. 17 4160. 0 99.97 <0. 02 > 416 6 . 6 * • >99. .998 <0. .01 >4166. 5* >99 .999 0 ..035 4166 . 4 99.39 * C a l c u l a t e d on a v e r a g e o f e f f l u e n t b a s i s . C-2-6 TABLE 2 COLUMN ADSORPTION PROCESS MERCURY VOLUME OF SOLUTION = 500 m l . RATE OF FLOW = 0 3 c W f t 2 DEPTH OF COLUMN = 9" 600 gms OF COAL ^ CONTACT TIME = 30 min. S o l u t i o n C o a l s i z e 0.533 mm av C o n c e n t r a t i o n E f f l u e n t mg ppm 250 500 C o a l s i z e 0 . 2965 mm av. % E f T T u e n t mg C o a l s i z e 0.117 mm a v . E f f l u e n t mg C o a l s i z e 0.0341 S/l- ~ — £}f ~ " KeSved K J v a l R e S v e d C o a l P S C o a f P " f \ , a - "'•S71 C o a l J C o a l 0.0038 2083.3X10"* 99 . 998 0. 011 2083 . 2 X 1 0 ^ 99 . 995 0 . 00455 2083 . 2 X 1 0 ^ 99.99 3 0.004 55 2 8 3 . 2 X 1 0 ^ 0.032 4166.4X10-" 99.993 0.0045 4 1 6 6 . 6 X 1 0 ^ 99.999 0.0023 4 1 5 6 . 6 X 1 0 ^ 9 S . 9 9 9 0 . 0 0 2 3 , l 6 6 . 5 X 1 Q - » < S e n s i t i v i t y 0.002 m g / l C-2-6 TABLE 3 COLUMN ADSORPTION PROCESS ~ COPPER. Volume o f S o l u t i o n = 500 m l . R a t e o f F l o w =0.3 gpm. D e p t h o f Column = 9 i n s . Wt. o f C o a l = 600 gins. contact time = 30 min. S o l u t i o n C o n c e n t r a t i o n ppm (ng/1) C o a l s i z e 0.533 mm av. C o a l s i z e 0.2965 mm av. C o a l s i z e 0.117 mm av. C o a l s i z e 0.03414 ra av. E f f l u e n t m % cone. removed Removal mg/ l p e r gm u c o a l X l O E f f l u e n t mg % cone. removed Removal mg/l p e r gm_, c o a l X l O E f f l u e n t mg % c o n e . removed R e m o v a l mg/l p e r gm_ u c o a l X l O E f f l u e n t mg % c o n e . removed R e m o v c l m g / l p e r gm u c o a l X l O 0.5 0.053 3.725 89.4 0.048 3.766 90.4 0.039 3.841 92.2 0.143 2.975 71.4 5.0 0.C53 41.225 98.94 0.056 41.20 98.88 0.025 41.46 39.5 0.075 410.41 93. 5* 50 0.070 415.083 99.86 0.087 415.94 99.83 0.104 415.8 99.79 0.382 413.48 39.24 100 0,141 832.15 99.86 0.155 832.033 99.84 0.0S2 832.9 99.95 0.069 832.76 S9.93 250 0.141 2082.158 99.94 0.139 2082.18 99.94 0.052 2032.9 99.93 0.087 2082.61 99.97 500 1.426 41S4.783 39.71 3.401 4138.32 99.34 1.701 4152.49 99.66 3.089 4140.92 93.38 C-2-6 TABLE 4 . COLUMN ADSORPTION PROCESS CADMIUM Mean P a r t i c l e S i z e o f C o a l rrjn 0.533 mm E f f l u e n t mg Cd °e!iiov< per i C o a l , 0.2965 mm 0.117 mm 0.03 414 r nun cJSSSSt« " 1 ; = ? " R , * o v , i ES= e n t K " 8 C d H » * , ™s C d 1 « « — t . s cd % X 10" C o a l X 10" 4 C o a l , X 10" C o a l , n 1 0, . 007 0.775 93 <0 .003 >0, . 821* >98 . 5 <0.002 >0.825* >98 -100 <0 .002 >0.325* : >99--100 0. 2 0. .007 1.6 96.5 0 .003 1. .641 98 .5 0.009 1.59 95 . 5 <0. .002 > 1. 5 6 * >99 .5-100 0. 5 0. 007 4.11 98.5 0, .004 4. 133 99, .2 0.006 4.12 98 .8 <0 . ,002 >4.15* >99 . .S-100 5 0. 008 41.6 99 . 84 <0. ,03 >41. 54* >99. ,7-100 <0.002 >41.66* >99. . (.8 0. 005 4.525 99 . 9 50 0. 012 416.033 99.75 <0. 03 >416. 5 4* >99. 97 <0.002 >416.66* >99 . ,98 <C. 002 >416.66* >99 . 98 500 <0. 03 >4166.54* >99.997 <0. 03 >4166. 5 4* >99 . 997 <0.03 >4166.54* >00. 997 <0. 03 >4166.54* >99. 997 vuxixiut; o x iOXUTx.On~ i .UU ( F l o w R a t e 0.3 gpm/ft . * C a l c u l a t e d on a v e r a g e o f e f f l u e n t b a s i s . D e p t h o f Column 9" C20cm.) C o a l 6 00 gms contact time = 30 min. C-2-6 TABLE S COLUMN ADSORPTION PROCESS — ZINC. Volume of S o l u t i o n = 500 ml. Rate of Flow = 0.3 gpm/ft - D e p t h of Column = 9" (20cm.) Wt. of Coal = 600 gms. contact time = 30 min. S o l u t i o n C o n c e n t r a t i o n (mg/1) C o a l s i z e 0.533 mm av. C o a l s i z e 0.2965 mm av. C o a l s i z e 0.117 mm a v . C o a l s i z e 0.03414 mm av. E f f l u e n t mg % co n e . removed Removal mg/1 p e r gm u c o a l X l O E f f l u e n t mg % cone. removed Removal mg/1 p e r gm u c o a l X l O E f f l u e n t mg % c o n e . removed R e m o v a l mg/1 p e r gm u c o a l X l O E f f l u e n t mg % c o n e . removed Removal mg/1 p e r gm u c o a l X l O 0.5 0.044 3.S00 91.2 0.057 3.691 88.6 0.034 3.883 93.2 0.028 3.933 94.4 5.0 0.044 .41.30 99.12 0.067 41.108 98.66 0.043 41.308 99.14 . 0.038 41.35 99.24 50 0.078 416.02 99.84 0.050 416.25 99.9 0.074 H16.05 99.85 0.039 416.34 99.92 100 0.055 832.875 99.95 0.059 832.84 99.94 0.079 832.68 99.92 0.039 833.01 99.96 250 0.066 2082.78 99.97 0.075 2082.71 99.97 0.16 2082.0 99.94 0.039 2083.1 99.98 500 ' 3.194 4140.05 99.36 2.39 4146.75 99.52 1.56 4153.67 99.59 3.03 4141.42 S9.39 C-2-6 TABLE 6 . COLUMN ADSORPTION CHROMIUM volume of s o l u t i o n = 500 ml. , rate o f flow =0.3 gpm/ft 2 depth o f column = 9" C20cm.) , wt. of c o a l = 600 gms. contact time = 30 min. S o l u t i o n C o n c e n t r a t i o n E f f l u e n t C o a l s i z e 0.533 mm av. 5— ppm .(mg/l) Cone. mg/l mg C o a l s i z e 0.2955 mm av. " E f f l u e n t C o a l s i z e 0.117 mm av. C o a l s i z e 0.03414 rrcn av. E f f l u e n t Removed Removal Cone. Removed Removal Cone. Removed Removal Cone. E f r l u e n t mg p e r gm mg/l p e r gm m g / l p e r gm mg/l Removed Removal p e r g r C o a l C o a l C o a l 0 . 1 <0 .03 >0.58X10~ 4 >70 <0, .02 >0.67X10" 4 >80 <0, .03 >0.58X10 _ i + >70 <0 .034 >0.5 5 X 1 0 - 4 >65- 0 .5 <0, .02 >4.0X10 - l + >96 <0, .02 >4.0X10~ 4 >96 <0. .008 >4.0X10" 4 >98 . 4 <0 .052 >3.7X10" 4 >39 . . 6 5 0. , 104 .40X10" 1* 97. 92 <0. 045 > 4 1 X 1 0 " 4 >99 . .1 <0. 115 > 4 0 X 1 0 " 4 >97 . 7 <0 .052 > 1 1 X 1 0 " 4 >3 3 . 96 50 0. 10 4 1 5 X 1 0 " 4 99. 8 0. 08 4 1 6 X 1 0 " 4 99. 84 0. 09 4 1 5 X 1 0 " 4 99 .82 0 .08 4 1 6 X 1 0 " 4 99. 8 100 0. 11 8 3 2 X 1 0 " 4 99. 9 0. 16 8 3 2 X 1 0 " 4 99. 84 0. 08 8 3 2 X 1 0 " 4 99. .92 0 .03 8 3 2 X 1 0 " 4 99 . 9 2 250 0. 4 2082X10" 4 99. 84 0. 08 2082X10"" 4 99 . 96 ' 0. 07 2 0 8 2 X 1 0 " 4 9 9 , .97 C . 18 2081X10"^ 29 . 92 500 0. 98 4 1 S 8 X 1 0 _ 1 + 99. 8 0. 27 4 1 6 4 . 4 X 1 0 " 4 99. 95 0. 09 4155X10" 1 4 99. .98 0. . 26 4164X10"'' 99. 94 APPENDIX C-2-7 LONG TERM ADSORPTION OF LEAD THROUGH A COAL COLUMN C-2-7 TABLE 1 . BREAK-THROUGH DATA DURING 32 DAYS. DAYS OF OPERATION S a m p l i n g P o i n t 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 3 I n f l u e n t 4.97 4. 97 4. 2 4 . 42 4.64 4.835 5.13 2 .29 2. 29 4.45 5.23 5.23 5.72 5.72 5.2 5.33 3.24 3. 24 6" L e v e l 0.03 0. 335 0. 245 0.325 0.27 0.465 0.505 0 .28 0. 55 0.65 0.66 0.605 0.65 C.65 0.728 0.715 0.587 0. 333 1 1 / 2 ' Tt <0. 02 <0. 02 <0. 02 <0.02 <0.02 <0. 02 <0.02 <0 .02 <0. 02 < 0 . 0 2 <0 . 02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0. 02 2 1/2' n <0.02 <0. 02 <0. 02 <0.02 <0.03 3 1/2' IT <0.02 <0. 02 <0. 02 <0.02 4 1/2' I I <0.02 <0 . 02 <0. 02 <0.02 5 1/1' I I <0.02 <0. 02 <0. 02 <0.02 6 1/2* I I <0.02 <0. 02 <0. 02 <0.02 7 E f f l u e n t . <0.02 <0. 02 <0. 02 <0. 02 <0.02 <0.02 <0.02 <0 .02 <0. 02 <0.02 <0.02 <0.02 <0. 04 <0 .02 <0.62 . <0. 02 <0.02 <0. 02 column dimensions : 6 ^'15.24cm.) diam. , 2 m. depth, c o a l p a r t i c l e s i z e = 0.533 mm. DAYS OF OPERATION 19 20 21 22 23 24 25 26 27 28 29 30 31 32 5 .15 5 .76 5. ,76 5. 71 4. 906 4 .906 4, .96 4. 96 5 .077 5. 077 4. , 6 4. 6 4. 5 4. 5 0 .7205 0 .6 0, ,68 0. 55 0. 66 0 .622 0. ,61 0. 544 0 .439 0. 3365 0. , 573 0. 555 0. 441 0. 539 <0 . 02 <0 .02 <0. , 02 <0. 02 0. 047<0 .02 <0. . 02 0. 01 0 .03 0. 005 0. ,02 0. 19 0. 0245 0 . 206 0. 035<0. 02 <0 .02 0. 223 0 .045 0. ,03 0. 107 0. 039 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 0.025 0.03 0.045 0.02 0.047 CO & C-2-7 TABLE 2 .CONTINUOUS ADSORPTION OF LEAD ADSORPTIVE CAPACITY OF COAL • column dimensions 6"(l 5-24cm.) coal p a r t i c l e s i z e = 0.533 ,2 m.depth, mm. B a t c h No. R a t e of F l o w 1/hr I n f l u e n t Cone. mg/1 Pb. T o t a l mg of L e a d A p p l i e d A v e r a g e E f f l u e n t f r o m 5" L e v e l mgs o f L e a d i n E f f l u e n t mgs o f L e a d A d s o r p e d mgs Removed p e r gm C o a l % Removal 1 , 8.21 4.94 1346.67 0.25 67.74 1278.93 0.676 94.97 2 5.55 4.2 948.4 0.26 68.71 889.69 0.470 93 . 81 3 1.70 4.64 1047.8 • 0.34 76.78 971.02 0. 513 92.57 4 6.35 5.13 1042.42 0.49 99 . 57 942.85 0.498 90.45 5 7.78 2.5 700 0.46 128. 8 571.2 0.302 81.6' 5 5.93 4.45 844.16 0.38 7 2.08 772.08 0.408 91.45 7 5.65 ' 5.23 - 1180.99 0.63 142.26 1038.73 0.549 87.95 8 5.36 5.77 1485.2 0.65 167. 3 1317.9 0.696 38.74 g 9.41 S. 20 1174.2 0.73 164.38 1009.82 0.533 86 . 00 10 6.35 5.33 ' 1083.06 0.75 151.99 931.07 0.492 85.97 11 5.91 3.24 804.82 0.67 166.43 638.39 0 .340 79.32 12 6.02 5. 15 930 .1 0.72 130.21 799.89 0.423 86.0 13 7.34 5.76 1690.56 ' 0.64 187.84 1502.72 0.794 88 . 89 I t 8.09 5.71 1108.88 0.60 115.5 992.38 0.524 89 .49 15 6.21 4.91 1218.65 0.65 161.46 1057.19 0.559 86.75 15 4.70 4.96 1119.97 0.61 137.74 982.23 0.519 87.7 17 4.70 5.08 1146.39 0.43 97.32 1049 ,07 0.0570 91.51 13 4.70 4.60 1033. 68 0.61 137.74 9 0 0.94 0.4760 86.74 19 5.51 4.50 1016.10 0.49 110.64 905.46 0.4780 89 .11 20 5.72 4.45 763.66 0.67 115.32 643.34 0.3 42 5 S.66 84.9 APPENDIX C-2-8 SELECTIVITY IN ADSORPTION OF MIXED METALS BY COAL. C-2-3 TABLE 1 . CONTINUOUS ADSORPTION OF MERCURY. column dimensions :6 '[15.24cm.) , 2m. deptli. c o a l p a r t i c l e s i z e 0.533mm. DAYS OF OPERATION S a m p l i n g P o i n t 1 2 3 4 5 6 7 rt O 9 10 I n f l u e n t 6.2 6.79 6.08 7.448 7.448 5.7 6.14 . 6..14 ' 5.75 5.55 6" L e v e l 0.36 1.63 1.26 1.8 1.24 1.5 1.78 1. 75 2.4 2.52 1 1/2''" 0.0215 0.0085 0.0118 0.0104 0.0146 0.02 0.0325 0.02 0.062 0.0S6 2 1/2* " 0.0236 0 0 0.0063 0.0083 0.0035 0.0123 0.00 7 3 0.01 0.016 3 1/2' " 0.005 0.0055 0.003 0.00341 0.0034 0.0031 0.00923 0.0055 0.0071 0.0053 4 1/2' " 0.0075 0.03 45 0.005 0.007 0.00156 0.0021 0.0057 0.005 0.005 0.00S5 5 1/2* " 0.0075 0.002 0.015 0.0031 0.0018 0.0018 0.005 0.0043 C.0037 0.012 3 6 1/2' " 0.0051 0.002 0.011 0.007 0.0021 0.00135 0.C1 0.0028 0.0037 0.0053 7' E f f l u e n t - 0. 003 0.004 0.0021 0. 001 0.0015 0.005 0.0028 0.0025 0.0083 ro 11 12 13 14 15 16 17 18 19 '5.65 5. S 5.8 8.2 8.5 8.6 8.6 •8.6 6.0 1.7 1.43 1.56 1.92 1.8 1.16 1. 35 1. 54 1.73 0.0515 0.025 0.0624 0.045 0.0685 0.076 0.06 0.086 0.08 0.0135 0.0105 0. 016 0.0148 0.018 0.0136 0.0126 • 0.0186 0.023 0. 0063 • 0.0036 0.0083 0.0077 0.0083 0.01 0.0063 0.C05 0.0124 0. 006 0.0058 0.0062 0.0075 0.0077 0.0075 0.0057 0.0067 0.0094 0 .0054 0.0054 0 .006 0.0125 0.0074 0.0057 0.0045 0.0058 0.0068 0.0056 0.0052 0.0063 0.007 0.0078 0.0068 0.005 0.0053 0.0062 0. 0051 0.0052 0.004 0.0074 0.0075 0.003 0.0058 0. 0-066 O 2 1/2' " 3 1/2' " C-2-8 TABLE 2. CONTINUOUS ADSORPTION THROUGH COLUMN 6" DIAM. , 2 M LENGTH, COAL S I Z E : O.S LEAD DAYS OF OPERATION 33 mm 1 1/2* " 0.0195 0.0370 0.0278 0.019 0.0254 0.092 0 .14; 0.181 0.457 0.0115 0.0845 0.0215 0.022 0.0215 0.0215 0.074 0.0179 0.015 4 1/2' " 0.0122 0.023 0.0278 11 12 13 14 15 16 17 18 19 4.64̂  5.87 5 .87 6.37 5.97 5 , .97 5.97 5.65 5.79 6.23 5.05 6.14 B. 09 6.03 6 , .23 6.47 6.29 6.20 0.153 0.116 0;205 0.133 0.278 0, .205 0.159 0.385 0 . 306 0 0.0273 0.0168 0.0107 0 0. .0175 0.0187 0 .0.0234 0 0.00813 0.0124 0.0083 0 0.0526 0 0.0127 0.0274 0 0 0 0 0 , .0187 0.01244 0 0 0 0 0 0.0493 0.0107 0. .00313 0 0 0 0 0 0 0.0107 0.0473 0, . 0062 0 0 0 0 0 0.0151 0.0278 0 0.0378 0 0.0151 C-2-8 TABLE 3 . CONTINUOUS .'ADSORPTIONTHROUGH COLUMN 6" DIAM. , 2 M LENGTH, COAL S I Z E : 0.533 COPPER S a m p l i n g P o i n t I n f l u e n t 5" L e v e l 1 1/2' " 3 1/2* " 4 1/2' " 5 1/2* n 5 1/2' " DAYS OF OPERATION 5.84 6.27 2.0 3.13 5.75 6.187 6.187 S. 89 5.51 5.51 3.62 4.087 0.014 0.064 5.28 0.052 4. 79 0.089 4.98 5.34 0.188 " 0.236 2 1/2' " 0.0596 0.009 0.067 0.039 ° - 0 3 ! 4 0-039 0.018 0.036 0.027 0.035 10 3.75 4.44 3.84 5.12 0.427 1.27 0.075 0.0054 0.024 0.048 0.037 0.035 0.0135 0.033 0.0463 0.04S ° - ° 5 7 ° - 1 1 5 ° - 0 5 7 0-020 0.027 0.068 0.022 0.052 0.0463 0.0392 0.111 0.058 0.05 0.035 0.054 0.045 0.0389 0.0463 0.044 0.0294 0.096 0.251 0.05 0.036 0.018 0.11 0.011 0.0452 0.0426 0.0294 7' E f f l u e n t • 0.0143 0.058 0.07 0.061 0.05 0.054 0.063 0.0393 0.037 0.0392 11 4. 44 4. 35 12 2.14 2.85 0.552 0.497 13 2.14 2.92 0.75 14 5.97 4.99 0.653 15 5. 59 4.85 16 5.59 5.14 17 5.59 5. 32 6.8 6.57 19 5.986 6 .204 0,304 0.836 0.79 1.6! 1. 59 0-0431 0.024 0.087 0.032 0.044 0.0618 0.0718. 0.0235 0.0717 0.0294 0.043" 0.046 0.058 0.0679 0.013 0 0.044 0.04 0.0235 0.0431 0.0353 0.0528 0.0255 0.044 0.048 0.083 0.0294 0.0604 0.0431 0.085 0.056 0.065 ro C-2-8 'TABLE 4 . CONTINUOUS ABSORPTION THROUGH COLUMN 6" DIAM., 2 M LENGTH, COAL S I Z E : 0.533 CADMIUM DAYS OF OPERATION ? c i n "S 1 2 3 4 5 6 7 8 9 10 I n f l u e n t .5.104 5.625 5.21 5.47 5.47 5.76 5.64 5.64 T .67 4.07 6" L e v e l 3.125 5.417 5.16 5.69 6.061 3.065 5.2 5.56 3.88 5.279 1 1/2* rt 0.C4 0,117 0.0042 0.0552 0.173 0.638 1.43 1.6 2.21 4.23 2 1/2' tl 0.0515 0.012 . 0.0094 0.0167 0.0158 0 0.0062 0.037 0.0062 0.0455 3 1/2' M 0.00S8 0.0146 0 0.0203 0 0.0356 0.0014 0 0 0.0105 4 1/2' II 0.018 0.0033 0.0031 0.00682 0 0.035 0.0026 0 0 0 5 1/2' r l 0.0375 0.0396 0,0042 0.0G65 0 0 0.0016 0.0083 0 0 6 1/2' It 0.0104 0.0155 0.0052 0.0072 0 0.079 0.0014 0.0048 0.0079 0 7' E f f l u e n t 0.0033 0.0073 0.0188 0 0 0.0396 0 0.0122 0 0.00406 11 12 13 14 15 16 17 18 19 4. 07 5.0 5,0 5.175 5.3 5 5 .35 5.3 5 S.22 5.48 5.221 4.38 5.71 5.14 5.18 5.45 5.42 5.77 5.73 2.75 3.28 3.95 3.64 3.48 4.52 4.5 5.65 5.42 0.0374 0.0279 0.0638 0.03 0.0269 0.0241 0.0243 0.1057 0.220 0.0013 0.0122 0.0029 0.002 0.002 - 0.035 0.0029 0.0016 0.0181 0.H0 8 5 0.0033 0.0011 0 0.002 0.0055 0.0052 0.0013 0.0031 0.0024 0.0013 0.022 0.014 0.0011 0.0078 0 0.00087 0 0 0.0011 0.0081 0 0.0074 0.0065 0.0011 0 - 0.0098 0 0.002 0.00293 0.0069 0.0145 0.0013 0 ro C-2-8 TABLE 5 . CONTINUOUS ADSORPTION THROUGH COLUMN 6" DIAM. , 2 M LENGTH, COAL S I Z E : 0.533 ZINC DAYS OF OPERATION -3 amp l i n g P c i r . t 1 2 3 4 5 6 7 8 9 10 I n f l u e n t 5.35 5.5 6.6 7 .52 7. 52 7.00 6 . 56 6.56 3.5 5.0 6" L e v e l 4.33 6.138 7.02 7 .05 7.58 8.13 6.64 6. 81 4.3 3 5.38 I 1/2' " 0 . 097 0.145 0.03 0 .169 0.717 1.276 2.29 2.71 3.54 6.379 2 1/2' " 0.077 0.04 0.05 0 . 046 0.048 0.0343 0.052 0. 113 0.035 0.133 3 1/2' " 0.052 0.033 0.017 0 . 068 0.015 0.066 0 . 041 0.033 0.033 0.027 4 1/2' " 0.0395 0.1074 0.082 0, .2 5.4 0. 0135 0.101 0.022 0.038 0.0375 0.01025 5 1/2' " .0363 0.054 0.076 0. .046 0.034 0.025 0.042 0.048 0.035 0.0102 5 1/2' " 0.0395 0.023 0. 081 0 . 076 0.062 • 0.184 0.019 0.04 . 0.053 0.032 7' E f f l u e n t 0.0063 0.0034 0.101 0. 046 0.037 0.074 0. 04 8 0.091 0.0163 0.01311 11 12 13 14 IS 16 17 18 19 •5.0 •4.3 4 4.34 5.39 5.39 5.39 5 . 39 5 .35 5.56 6.58 4.63 6.38 5.6 5.39 5.4 3 5.56 5.97 . 5.97 4.34 4.95 5.64 5.39 5 .19 6.26 6.17 7.41 6.58 0.0803 0.0421 0.2049 0.134 0.1211 0.1088 0.159 0.514 0. 761 0.01025 0.0475 0.031 0.043 0.0298 1.138 0.0434 0.0102 0.033 0.12 2 7 0.0123 0.0556 0.0225 0.0127 0.020S 0,0597 0.0281 0.072 0.0184 0.0184 0.0246 0.0809 0.033 0.0289 0.0679 0.0086 0.0475 0.01148 0.0172 0.0254 0.033 0.0705 0.351 0.0372 0.0413 0.072 No E f f . 0.0495 0.0225 0.0372 0.0664 0.0597 0.1045 .0.0703 0 .129 C-2-8 TABLE 6 . CONTINUOUS ADSORPTION THROUGH COLUMN 6" DIAM. , 2 K LENGTH. COAL: S I Z E : 0.533 mm CHROMIUM S a m o l i n K I n f l u e n t 5.2 5" L e v e l 1.31 6.13 2.16 5.13 5.4 DAYS OF OPERATION 5.4 3.42 4.5 4.5 2.3 2.5 4.08 0.98 0.617 3.4' 2.0 10 1.94 2.75 3.92 1 1/2' " 0.031 0.042 2 1/2' " 0.022 3 1/1' " 0.0155 0.011 0.014 0.013 0.007 0.054 0.026 0.02 0.057 .0.065 0.188 0.109 0.957 0.038 0.003 0.033 0.032 0.037 0.0435 0.021 0.024 0.026 0.026 0.0069 0.0337 4 1/1* " 0.023 0.011 0.012 0.021 0.016 5 1/1' " 0.0088 0.012 0.018 0. 037 0.024 5 1/2* " 0.014 0.0088 0.0095 0.016 0.006 0.157 0.018 0.459 0.0194 0.02 0.0156 0.02 0.029 0.0813 0.017 0.0253 0.0013 0.0106 0.014 0.0197 7' E f f l u e n t 0 0.0083 0.0108 0.013 0.021 0.016 0.015 0.0181 0.0075 0.0314 11 12 13 14 15 16 17 18 19 2.75 4.0 4.0 5.06 5 .89 5.89 5.89 4 .98 6 .04 2.33 1.33 4.23 3.61 3 .42 3.75 4.08 4 . 23 3 .87 0.2732 0.093 0.46 0.237 0 .156 0.282 0.2 0 .479 0 .443 0.0904 0. 03 0.159 0.77 0 .050 0.079 0.077 0 . 084 0 .098 0.0207 0.029 0.082 0.03 9' 0 .039 - 0.067 0 .045 0 .057 0.479 0. 015 0.042 0.033 0 .031 0.052 0.042 0 .045 0 .037 0.01436 0.012 0.05 0.042 0 .017 0.033 0 . 016 0 .034 0 .034 0.021 0. 015 0.043 0.04 0 . 014 0.04 4 0 .04 0 .008 0 .032 - 0.019 0.033 0.024 0 . 031 0 . 033 - 0 .0186 C .0304 APPENDIX C-3 - ADSORPTION OF DISSOLVED ORGANICS C-3-1 - BATCH TESTS C -3-1 TABLE 1 ADSORPTION ISOTHERMS FOR BOD REMOVAL WITH COAL AND ACTIVATED CARBON CONTACT TIME = 4 h r s Carbon Dosage (M) gm P e r L i t r e A c t i v e C a r b o n 4/8 C o l u m b i a H.C. C o a l S i z e 1 5 0 tAesh (0.03414 mm) H.C. 1/4" C o a l S i z e ( O . 5 3 3 mm) C f X= Co-Cf X M C f mg/l X= Co-Cf X M - C f mg/l X= Co-Cf X M 0 3 6 6 1 gram 270 9 6 9 6 258 108 318 48 48 48 2 grams 282 84 42 246 120 60 • 3 0 6 6 0 30 3 grams 168 198 66 2*-'0 126 42 282 84 28 4 grams - - - 228 138 34.5 258 108 27 5 grams 1 7 4 192 38.4 2 3 4 1 3 2 26.4 258 108 21.6 8 grams - - - 228 138 17.3 2 3 4 1 3 2 I 6 . 5 10 grams 2 1 6 1 5 0 1 5 2 3 4 1 3 2 13.2 .j C - 3 - 1 TABLE 2 ADSORPTION ISOTHERMS FOR COD • j ' REMOVAL WITH COAL AND ACTIVATED CARBON • j CONTACT TIME = 4 h r s Ca r b o n Dosage (M) gm P e r | L i t e r 0 1 2 3 4 5 8 10 A c t i v e C a r b o n 4/8 C o l u m b i a C f mg/l 733 480 443 381 335 X= C 0 - C f 2 5 3 290 3 5 2 3 9 8 X M 2 5 3 145 117 . 3 79.6 H.C. C o a l S i z e 1 5 0 Mesh. mg/l 4 6 2 446 440 428 3 3 5 3 2 0 3 0 4 X= Cn-Cl 271 287 2 9 3 3 0 5 398 413 429 X M H.C. C o a l S i z e 1 / 4 " ( 0 . 5 3 3 mm) 271 143.5 97-7 76.2 79.6 51.6 42.9 mg^l 684 554 5 3 2 5 0 2 441 418 382 149 1 7 9 201 2 3 1 2 9 2 3 1 5 3 5 1 X M 149 39-51 67 57.8 58.4 39.4 35.1 3 2 7 . A1THNDIX C-3-2 . COLUMN ADMONITION TliS'IS. C-3-2. TAilLE 1. flJ-DUCTTON OF DUOr ant COO I E L F DCITOCT AEROBIC LFJCHDK: CauXW 20 cm X 7 cm I.D. Particle size 0.5.13 nm Flow •= 5-7 nu/iuin. Iain Biroughixit Service UOD of BCD o f IXC Roroval COO of CCO oi Rmoval Number Voliioe ' Time Influent Efflusnt ItoTtA'ed E f f i c i - Influent Effluent Rcixrvod Eff i c i - Rijnarks Liters (hrs) ing/l im/1 urj/1 ency % rrrr/l mq/1 nrj/1 ency "i 257 10 3.7 522 _ _ This period considered 1 1 3 hrs 267 ' 260 7 2.6 520 512' 8 1.5 s i inocnlation period 252 15 5.6 496 24 4.6 for tiie column "2° 1 - 50 - - 176 The colum vashoi and dried 2 2 6 hrs 276 72 42 204 234 74 85 ™ 22 432' ' 472 68 ' 74 Itaiioval efficiency i n-creases due to bacter.ca action 120 205 63 280 400 59 3 2 C hrs 325 85 77 98 240 248 227 74 76 70 200 680 200 232 480 4S0 448 71 71 C6 Samples withdrawn for analysis every 1 nr. 10 315 97 120 560 82 167 418 72 320 790 71 120 465 80 300 810 73 133 452 77 290 820 74 Sacples vithdravn for 4 2 6 hrs 585 136 449 77 1110 340 770 69 analysis every 1 lir. 46 539 92 •256 854 77 13 572 98 296 C14 73 85 225 73 192 433 69 179 131 42 306 318 51 Sacples are taken for 5 2 6 hrs 310 196 201 114 109 47 35 624 325 202 239 422 48 68 analysis every 1 hr. 106 204 66 306 318 51 Back Hash 2 < 20 < 20 < 20 18.18 149 211 165 298 Backwashing with city tap water did not improve cr regenerate the surface . nrrrr-rTipfi of rhfi revs.- . r-1 CO 184 176 49 388 293 43 6 2.5 6 hrs 360 114 77 246 283 68 79 6E1 356 253 525 423 48 63 135 122 48 277 349 56 7 4 12 hrs 257 84 84 111 173 173 146 67 67 57 626 152 203 264 474 413 362 76 67 58 117 158 58 344 304 47 8 4 12 hrs 275 50 97 225 178 82 65 648 160 224 488 424 75 65 93 204 69 2)6 439 67 9 7 20 hrs 297 71 71 » 226 226 76 76 655 247 223 408 432 62 66 180 238 57 4 SO 232 33 10 2.5 6 hrs 418 141 90 277 328 66 78 712 336 240 376 472 53 66 Washing Tic coal wasixii with warm water then dried V?i>Ti vmi laei FLOW R-VTil 50 inlyniu AVERAGE: 0.5 I 302 1G6 36 539 171 24 The efficiency of rcr.v7va 0.5 I 50 ruin 468 352 116 25 710 548 162 23 drops greatJ.y with fastcj 1 t 352 116 25 COS 102 14 flow rate beoiu'in of in- 0.5 I 359 109 23 608 102 14 sufficient contact tire. 3 2 8 . C-3-2. TABLE 2. REDUCTION OF 1XD5 and COD KEEF EXTRACT AJJOBIC LCTCHUK COLUM 20 an X 7 cm I.D. Particle size 0.2965 ntn F'lcv too 5-7 ml/min. Run Wircuriiput Service IKo'cc "ECO 'of ~ bob Re.oval NUBtoac VOIUCYE Tine Influent Effluent , Liters (hrs) r.-.i/I nrc/1 ceo REJDVAL. viash H 2 ° Back Wish COO OL CCD Gt OX) R ._TOYoi Itatcveft E f f i c i - Influent Effluent Rtcwvou E f f i c i - ___rx;/l enry % rrr/j. itq/l ny,/i encv S Remarks 3 hrs 3J0 326 6 hrs 322 6 hrs 510 300 340 190 10 120 3.2 38.7 640 554 544 384 0G 13.4 bacterial inoculation 96 15 paricd. No appruciai- 255 40 rodustion 68 32 52 44 22 90 0 30 84 66 274 282 304 84 87 93 620 133 185 175 232 322 292 233 _256_ 377 325 33S 72 =100 91 74 80 627 175 150 120 214 159 151 12G 111 74 64 66 1019 76 18 30 10 TBS" 251 451 430 251 79 39 32 444 47C 500 413 468 476 501 516 768 568 539 72 7G 81 'Ins col urn washed anc! dried Appreciable iix i v i s c Ln~ tits reduction eff Acid-/..// due to t-iacterial ncti -*n 06 75 76 80 82 Ssirples withdrawn for analysis every 1 hr. 75 56 53 Sicrples withdrawn for analysis every 1 lir. BacJwashing with city tap water did rot irprcve or regenerate the surface propartiea of the coal 117 243 68 230 451 66 c. 2.5 6 hrs :i60 119 241 67 681 245 436 64 125 235 65 . 204 477 70 125 132 51 237 389 62 6 4 12 hrs 257 145 112 44 626 240 386 62 13.4 143 56 240 386 62 140 117 46 344 282 45 • 180 95 35 384 264 il 7 4 12 hrs 275 177 98 35 648 336 312 48 190 85 31 344 304 47 129 168 57 333 322 49 8 7 20 hrs 297 148 149 50 655 327 328 50 147 150 51 325 330 50 177 241 SO 488 224 32 9 2.5 6 hrs 418 191 227 54 712 392 320 45 190 228 55 376 336 47 •Ashing HG.'S WITH aiQi FLOW ROT: 50 ml/rain AVF2V&E 125 343 73 280 430 CI 2.5 50 min 46B 204 264 56 710 339 371 52 150 319 68 302 328 46 C-3-2. TABLE 3. OI-^JLSiiVE EEEtCTION OF EQD & CCD LSOxQOG CF ESEF EEffiSCT TSKOOGH EAT CHEEK CCAL 9" ESD S a r v i c s Coal S i z e 0.533 TJH C o a l Size 0.2965 Vol'T>=S ceo CCD L i t e r s I c t a l 2QD Applied Tota l SCO * Esmoved ReEoval T o t a l CCD T o t a l CCD A o o l i e d Rsrovsd 0. RssDval T o t a l SCO Total BOD & RasDval T o t a l CCD T o t a l CCD teaovsd % Jbznovai cxa 9 3 % % qni % an era % 2 0.552 0.438 79 1.280 0.904 71 0.652 0.573 83 1.240 0.942 .76 *a 1.202 0.932 73 2.640 1.851 70 1.236 1.109 86 2.494 1.832 76 6 2.372 1.397 80 4.860 3.470 71 2.316 1.843 80 4.532 3.245 72 8 2.992 2.210 74 6.108 4.186 69 3.216 2.442 • 76 6.235 ' 4.382 70 10.5 3.S32 2.798 72 7.811 5.058 65 4.244 2.946 ' 69 8.739 5.825 67 14.5 4.920 3.412 69 10.315 6.661 65 5.344 • 3.317 62 11.331 6.998 62 18.5 6.020 4.16C 69 12.907 8.232 64 7.423 4.407 59 15.916 9.285 58 25.5 8.099 5.691 70 17.492 11.266 64 8.463 4.387 59 17.696 10.018 57 28 9.144 6.394 70 19.272 12.166 63 9.638 5 . 7 5 a ' 60 13.471 10.959 56 30.5 10.314 6.711 65. 21.047 12.502 59 VO APPENDIX C-4 ADSORPTION OF PHOSPHATES C-4-1. BATCH TESTS' . TABLE 1. CONTACT PROCESS PHOSPHATE RS-30VAL Time = 1 hr. Coal. = 1% w/w S o . l u t J . c n Cone. Coal size 0.533 rrrn av. Coal size 0.29G5 mm av. Coal size 0.117 mm av. Coal size 0.03414 mm av. cor?, (mg/l) Effluent ccnc. ' r r c / 1 rig Removed % per Removal cm coal Effluent cone. mg/l mg Removed per gm coal Removal Effluent cone. r r g / 1 mg Removed per c-Xi coal % Removal Effluent cone, mg/l rng Removed per gm coal % Removal 2 . 2.14 - 2.21 - - 2.42 - - 1.32 0.C58 24 5 4.S5 0.004 . 0.3 5.1 - - 4.9 .0.01 2.0 2.42 0.253 51.6 10 10.08 - 9.77 0.023 2.3 9.65 0.035 3.5 6.28 0.372 37.2 50 50.02 - 49.34 C.066 1.32 49.5 ' 0.05 1 41.37 0.853 17.26 100 35 0.5 5 250 - 239.1-3 1.097 4.4 500 478 2.2 4.4 O C-4-1 TABLE 2 .. CONTACT PROCESS" R E M O V A L O F PKQSPHRB3 Contact time: 3 h r s . Coal : 1% w/w S o l u t i o n Ccr.c. Coal s i z e 0.533 irm av. Coal s i z e 0.2965 ma av. Coal s i z e 0.117 in? i av. Coal s i z e 0.03414 IT?, av. mg/l E f f i u e n ITtVl t :ng Removed per cm coal c u Removal E f f l u e n cone, mg/l t mg Removed qm c o a l Removal E f f l u e n t cone, mg/l mg Removed per qm c o a l % Removal E f f l u e n t cone. mg Removed per om c o a l % Removal 2 2.42 - - 2.14 - .- 1.93 0.007 3.5 1.20 0.CS1 40.5 5 4.75 0.025 5.0 4.63 0.037 7.4 4.41 0.059 11.8 2.51 0.249 49.8 10 9.59 .0.041 4.1 9.1 0.09 9 9.81 0.019 1.9 5.64 0.436 43.6 50 49.34 0.066 .1.32 44.74 0.525 10.52 45.35 0.465 9.3 38.92 1.108 . 22.2 100 63.74 3.625 36.26 250 196.13 5.387 21.55 SCO 410.65 8.935 17.8 C-4-1 TABLE 5., CONTACT PROCESS REM3VAL OF PHOSPHATE Contact time: 6 hrs. Coal : 1% w/w S o l u t i o n Cone. nig/1 Coal : s i z e 0.5331 ism av. Coal s i z e 0.2965 ram av. Coal s i z e 0.117 rm av. Coal s i z e 0.03414 rm av. ccr.c. mg Re-roved per cm coal % Removal E f f l u e n t cone. ng/1 mg Removed per gm c o a l % Removal E f f l u e n t cone. rrg/1 trg Removed per qm c o a l % Removal t-tri u e n t cone. ira/1 per err. c o a l % Rerroval 2 ilk-;/ X 1.99 0.001 0.5 2.05 - - 1.84 0.016 8 0.853 0.1142 57.1 5 5.15 - - 4.9 0.01 2.0 4.2 0.08 16 1.56 0.344 65.S * 10 9.55 0.044 4.4 9.6 0.04 4 9.07 0.093 9.3 3.46 0.654 65.4 50 47.5 0.25 5 43.5 0.05 1 49.11 0.189 3.78 33 1.2 24 C-4-1 . TABLE 4 . . CXWIACT PROCESS t CF PHOSPHATE Time = 3 hours Coal s i z e = 0.03414 ntn Influer.t S o l u t i o n C f 1 % 0. w/w .5 % w/w 1% w/w 5% w/w Cor.c. r r c / l cone. • n c / l irg Removed per qrr.' c o a l Renoval E q u i l i b r i u m cone. ' mq/1 mg Removed per qm c o a l % Removal E q u i l i b r i u m mg. R e e v e d cor.c. • per mq/1 qm c o a l % Removal 2 1.41 0.12 29.5- I - 2 0.081 40.5 0.613 0.0278 69.5 5 3.25 0.35 35. 2.51 0:.249.. 49.8: 0.73 0.0854 85.4 10 7.33 0.524 26.2 . 5.6.4 0,.43:& 43.6. 0...858; 0'.1823. 91.42 * 50 41.37 1.726 17.26. 38.9'2 1.10S 22.2 a. 99. 0.8232 82.02 100" 73.55 5.29 26.5 63.74 3.626. 36.26. 18,. 99 1.6202 81.01 250 199.19- 10.16 20.32 196.13 5.383' 21.55 9S.58: 3.023. 60.57 500 367.74 25-45. 26.45 410J.65 Si. 935 11.8.7 30,6.45 3.8,71 33.7 C-4-1 . T A B L E 5 . COOTACT PROCESS EFFECT OF CCOTACT TIME PHOSPHATE PEMOVAL Coa l S ize = 0.03414 rrm Coal = 1% w/w I n f l uen t Contact ~ : " ' S o l u t i on Tims Krs 1 m - 3 HR. Cone. E f f l u e n t mg Rerroved I E f f l u e n t mg Removed % E f f l u e n t mg Removed % ^ / l cone. per Removal cone. per Removal cone. per Removal rrg/1 gm coa l mg/l gm c o a l mg/l 6 HR. 2 1.32 0.068 34 1.2 0.081 40.5 0.853 0.1142 57.1 5 2.42 0.258 52 2.51 0.249 49.8 1.56 0.344 68.8 10 6.23 0.372 37 5.64 0.436 43.6 • 3.45 0.654 65.4 50 41.37 0.863 17 38.92 1.108 22.2 38 1.2 24 100 95 0.5 C -J 63.74 3.62b' 36.26 250 239.03 1.07 4.4 195.13 5.387 21.55 500 473 2.2 4.4 410.65 8.935 17.87 C " 4 " 1 • TABLE 6. • EFFECT OF PERCENTAGE COAL ON THE REMOVAL CAPACITY FOR PiKJSPHATE Time: 6 hrs Coal s i z e : 0. 03414 mm a v . cLl S S / 1 * 2 5 ^ n 1 0 ^Z'1 5 0 "9/1 Added E f f l u e n t mg Removed % E f f l u e n t mg Removed % E f f l u e n t mg Removed % E f f l u e n t mg Removed % ccr.c. per Removal cone.' per Renoval cone. per Removal cone. per Removal mg/1 gm coal mg/1 gm c o a l mg/1 gm c o a l mg/1 cm c o a l 0.5 0.92 ' 0.216 54 2.94 0.412 41.2 6.25 0.75 37.5 39.53 2.094 20.94- 0.853 0.1142 57.1 1.56 0.344 68.8 3.46 0.654 65.4 38 1.2 5 0.46 0.0308 77 0.43 0.0914 91.4 0.64 0.1872 93.6 . 13.45 0.731 73.1 APPENDIX C-4-2 . COLUMN ABSORPTION TESTS C 4 2 T A B L E ^ 1. COLUMN ADSORPTION PROCESS PHOSPHATE REMOVAL Wt. of c o a l = 600 gms; b e d d e p t h = 20 cm; i n f l u e n t c o n e . = 10 m g / l V o l u - e n * , ^ J i a t l v e ^ 1 1 " % C u m u l a t i v e E q u i l i - % o ^ H * ^ v o i u ^ . e FOA J orium Rerroval Removal b r i u m R p r m , r a i r > ~ ~ , . „ , ~ . ^ . u i a ^ v . S o l n . E f f i c i e n c y mgs. SoLn. Cone. Cone. JH/1 mg/l Cone. Cone. 10 mg/l V 2 5 2 ' 1 4 7 8 - 6 3.93 0.46 95.4 4.77 0.306 97 1 1/2 15 2 20 6.45 35.5 9.255 - 3 1/2 35 - - - € . 2 4 40 - _ 38 23.37 4.35 1 - 5 8 5 9.02 0.37 96 ' 9.67 3 - 5 55 12.27 1.26 87 13.17 2-1 79 17.12 2 1 / 2 2 5 8 - ° 2 0 1 0 - 2 5 5 3.34 65.6 " 13.93 2.1 79 -21.07 3 3 0 8 - 1 19 11.205 4.93 50.7 21.47 2.4 7b 24.87 3-46 65 29.73 337 C-4-2. .TABLE 2. COLUMN ADSORPTION PROCESS PHOSPHATE REMOVAL Coal s i z e l e s s than 150 mesh (0. 03414) I n f l u e n t Cone. = 247 mg/1 PO~ 3 Max. flow r a t e = 7-9 ml/min. Throughput Cumulative E q u i l i b r i u m Phosphate % • Cumulative Volume A p p l i e d S o l u t i o n Removed E f f i c i e n c y Removal^ L i t e r s Phosphate Cone. mg/1 of of PO. mgs. mg/1 Removal mgs. 0.2 49.4 0.735 245.96 99.7 49.2 0.42 103.7 0.46 246.23 99.8 103.4 0.59 145.7 <0.306 246.38 99.9 145.2 1.39 343.3 18.7 228.3 92.4 327.9 1.64 405.1 52.1 194.59 78.9 376.5 2.14 528.6 70.5 176.5 71.4 464.8 2.34 578.0 127.2 119.8 48.5 488.7 2.54 627.4 213.3 33.7 13.6 495.5 Very poor p e r m e a b i l i t y -av. 3 ml/mi 3 3 8 . C-4-2. TABLE 3. COLUMN ADSORPTION PROCESS PHOSPHATE REMOVAL Using Abbotsford sandy loam Sand s i z e l e s s than 150 mesh (0.03414) I n f l u e n t Cone. = 247 mg/1 Max. flow r a t e = 7-9 ml/min. Throughput Cumulative E q u i l i b r i u m Phosphate % Cumulati 1 Volume Ap p l i e d S o l u t i o n Removed E f f i c i e n c y Removal L i t e r s PO - 3 Cone. mg/1 of of P0 4' mg s . mg/1 Removal mgs. 1 247 <0 .306 > 2 4 6 . 4 >99.9 246 .4 2 494 <0.306 >246.4 >99 .9 492.8 3 . 741 <0.306 >246.4 >99.9 739 .2 6.5 1606 0.644 246.05 99.7 1600.4 7 1729 <0.306 >24 6 . 4 >99.9 1723 .6 7.5. 1853 2.298 244.7 99.1 1846 8.0 1976 25.190 221. 8 89.8 1956.9 8.5 2100 73.860 173.14 70 .1 2043.5 N.B. Detectable l i m i t f o r PO.**3 i s 0 .306 mg/1. 3 3 9 . Appendix c-5. Absorbance and S p e c i f i c E x t i n c t i o n C o e f f i c i e n t of assigned i n f r a red bands. n t A: Absorbance, K S p e c i f i c e x t i n c t i o n c o e f f i c i e n t i n cm 2 /mg. Type o f Treatment 1000 cm-1 A K Band Assignment 1600 cm-1 1720 cm-1 A K A K 3000 cm-1 A K Wahsed sample 0.31 Tr e a t e d w i t h l e a d 0.19 T r e a t e d w i t h barium0.12 A c i d a n l y d r i d e 0.33 1 Water Washed S u r f a c 0.42 0.32 0.43 0.24 0 .31 0.25 0.49 0.65 0.08 0 .11 0.17 0.62 0.82 0.05 0 .07 0.44 0.37 0.49 0.33 0 44 Washed sample 0.53 T r e a t e d w i t h l e a d 0.23 Tr e a t e d w i t h barium0.23 A c i d a n l y d r i d e * 0.54 A£i<LWashed S u r f a c e C o a l 0.70 0 .37 0.50 0.31 0.41 0.30 0 34 0.45 0.25 0.33 0.30 0 41 0.54 0 0 0.72 0. 36 0.48 0.36 0.48 Two s h o u l d e r s appeared a t 1775 and 1765 which a r e a s s i g n e d f o r a c i d a n l y d r i d e f o r m a t i o n . 3 _ Water Washed Core Coal Washed sample 0.61 0. 81 0.45 0.60 T r e a t e d w i t h l e a d 0.57 0. 76 0.18 0.23 0.10 0.13 A c i d a n l y d r i d e 0.52 0. 69 0.26 0.34 0.2 0.26 4 M A c i d _ W a s h e d C ° r e C o a l Washed sample 0.57 0. 76 0.38 0.51 0.19 0.25 T r e a t e d w i t h l e a d 0.54 0. 72 0.24 0.32 0.10 0.13 T r e a t e d w i t h barium0.45 0. 60 0.42 0.55 Acid A n l y d r i d e 0.63 0. 84 0.20 0.27 0.15 0.20 0.47 0.63 0.19 0.25 0.2 0.27 A p p e n d i x C-6. C - 6 - 1 . Molar r a t i o between adsorbed lead and released hydrogen. Adsorption of lead ions and the pH drop. No. o f H+ r „ a l c , E f f l u e n t % m g g removed PH PH drop d i s p l a c e d No.Pb++ i o n s ' ft C o a l Samples Cone. E f f i c i e n c y per f r o m p e r absorbed/ ™ ± i * l mg/1 o f removal gram c c a l Measure O r i g i n a l gram c o a l A g r a i H ' c o a l B H + ( A i A- S u r f a c e C o a l Water-washed 1 2 Mean Std.dev. % e r r o r i n i t i a l 530 86 83 87 +1 1.15% 83.8 83.4 44.3 44.4 44.2 44.3 4.235 70 70 70 1.535 1.9.0x10 -4 2.14x10 -4 1:0.89 (1:1) Acid-washed 1 120 77.4 2 125 76.4 Mean 122.5 76.9 Std.dev. +2.5 % e r r o r 2.04% 41.0 40.5 40.75 2.42 2.43 2.425 1.810 3.66x10 1.97x10 -4 1.07:2.0 (1:2) B- C o r e Coal Water-washed 1 122 2 120 Mean 121 Std.dev. +1 % e r r o r 0.83% 77.0 77.4 77.2 40.8 41.0 40.9 3.70 3.66 3.68 0.555 0.11x10 -4 2x10 1:0.055 Acid-washed 1 367 2 364 Mean 365.5 Std.dev. +1,5 % e r r o r 0.41% 30.8 31.3 31.0 ( ) approximate v a l u e s . 16.3 16.6 16.45 2.71 2.70 2.705 1.530 2x10 -4 0.795x10 see sample c a l c u l a t i o n Appendix C-6-2. 0.8:2.0 (1:2) 340a. C-6-2 . Sample c a l c u l a t i o n of the ion r a t i o — + + + i l pH of the o r i g i n a l s olution. = 4.235 pH = - l o g (II +) (H +) =0.0001 per l i t e r s i n c e the volume of the s o l u t i o n = 0.2 l i t e r (H +)/100 c e . (1 gm coal) = 0.0001 x 0.1 = 0.1xlO~ 4 pH a f t e r a b s o r p t i o n of lead = 2.7 = 0.002 i o n s / l i t e r OO a f t e r reaction/100 c.c. •(.!-gm coal)= 0.002 x 0.1 == 2>:10"4 H + r e l e a s e d = 2 x I 0 ~ 4 - 0 . 1 x l 0 ~ 4 '= 1.9 x l 0 ~ 4 JL. H'. ions /gram c o a l ++ . ^ ^ mgs Pb removed/gm c o a l 44.3 Pb i n t e r a c t = — — - ^ » 207TT03— = 2.14 x 10" 4 '> Molar r a t i o of Pb'H"/H+ = — - l x l ° 1 - 4 0 P Q 2x10 U , L-' Appendix C-7. C-7-1. A c i d i c Groups i n Coal. Carboxyl and hydroxyl groups In Coal. Coal/Carbon T o t a l A c i d i t y (A) Ca r b o x y l groups (E) P h e n o l i c s (A-B) % C a r b o x y l % P h e n o l i c s m.equi/gm m.equiv/ BET s u r f a c e area m.equi/gra ni. e q u i v / BET s u r f a c e a r e a m.equiv/gm m.equiv/ BET s u r f a c e a r e a S.W. 7.895 2.547 2.288 0.738 5.607 1.809 28.1 7.895 2.54 7 2.156 0.696 5.739 1.851 71.9 S.W.Pb 8.9471 2.886 2.104 0.679 6.843 2.207 23.3 76.7 8.6840 2.801 1.999 0.645 6.685 2.156 S.A. 8.684 2.801 2.630 0.848 - 6.054 1.953 30.7 69.3 8.684 2.801 2.709 0,874 5.975 1.927 S.A.Pb 7.895 2.547 2.209 0.713 5.686 1.834 72.9 8.421 2.716 2.209 0.713 6.212 2.003 27.1 C.W. 5.263 0.446 0.934 0.0792 4.329 0.367 17.0 83.0 4.370 0.370~ 0.708 0.0600 3.662 0.310 C.W.Pfa 4.265 0.361 1.092 0.0925 3.173 0.269 76.4 4.265 0.361 0.923 0.0782 3.342 0.283 23.6 CA. 4.737 0.401 1.275 0.1081 3.462 0.293 71.5 4.2104 0.357 1.275 0.1081 2.935 0.249 28.5 C.A.Pb 5.526 0.468 1.086 0.0920 4.440 0.376 19.8 80.2 5.526 0.468 1.105 0.0936 -4.421 0.374 Ac.W 0.47 0.0007 0.09 0.0001 0.38 0.0006 80.8 0.47 0.0007 0.09 0.0001 0.38 0.0006 9.5 Ac.A 1.47 0.0021 0.11 0.0002 1.36 0.0019 90.5 1.05 0.0015 0.13 0.0002 0.92 0.0013 9.5 S.W. = water-washed surface coal S.W.Pb= " " " "Treated with S.A. = acid-washed surface -:oal S.A.Pb= " " " "Treated with Lead C C Lead! C C.W. = water-washed c o r e c o a l JAc.W .W.Pb= " " " "Tr e a t e d w i t h Lead'Ac.A A . = acid-washed c o r e c o a l I A.Pb= " " " " T r s a t e d w i t h Lead I I water-washed a c t i v a t e d carbon acid-washed a c t i v a t e d carbon 34 2. A p p e n d i x C-7-2. A n a l y s i s o f v a r i a n c e of t h e a c i d i c groups. T a b l e 1(a) C a r b o x y l groups o f v a r i o u s c o a l samples (m.eq./ u n i t s u r f a c e a r e a ) , e f f e c t o f washing § t r e a t m e n t w i t h Type of Treatment Su r f a c e Coal Core Coal Wash With Lead R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e "(1) R e p l i c a t e (2 Water Untreated 0.738 0.696 0.0792 0.060 Washing Treat e d 0.679 0.645 0.0925 0.0782 A c i d U n t r e a t e d 0.848 0.874 0.1081 0.1081 Washing Treat e d 0.713 0.713 0.0920 0.0936 T a b l e 1(b) A n a l y s i s o f v a r i a n c e f o r d a t a i n t a b l e 1(a) Source o f Degree of „ V a r i a t i o n Freedom S u m S o f s c l u a r e s Mean squares F Washing (A) 1 0.0145 0.0145 55.7** Coal type (B) 1 1.6863 1.6863 6467.6** Treatment (C) 1 0.0103 0.0103 39.3** A x B 1 0.0056 0.0056 21.3** B x C 1 0.0103 0.0103 39.7** A x C 1 0.0038 0.0038 14.8** A x B x C 1 3.7(N.S.) E r r o r . 8 0.0021 0.0003 T o t a l : 15 1.7339 ** S i g n i f i c a n t a t 1% l e v e l . N.S. Not s i g n i f i c a n t . 343. Table 2(a). Carboxyl groups of coals and activated carbon (m.eq/unit surface are'} , effect of acid washing. Type o f S u r f a c e C o a l Core C o a l A c t i v a t e d Carbon Washing R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e (1) R e p l i c a t e ( 2 ) R e p l i c a t e ( l ) R e p l i c a t e ( 2 Water Washing 0.738 0.696 0.0792 0.060 0.0001 0.0001 A c i d Washing 0.848 0.874 0.1081 0.1081 0.0002 0.0002 Table 2(b). Analysis of variance of data in Table 2(a) Source o f V a r i a t i o n Degree o f Freedom Washing (A) Type o f c o a l / c a r b o n (B) A x B E r r o r T o t a l : 1 2 2 6 11 S i g n i f i c a n t a t 1% l e v e l . Sums o f squares Mean squares 0.0111 1.4938 0.0111 0.0014 1.5174 0.0111 0.7469 0.0056 0.0002 47.5** 3191.2** 23.7** T a b l e 3 ( a ) P h e n o l i c OH g r o u p s (m. c q / u n i t s u r f a c e a n d t r e a t m e n t w i t h o f v a r i o u s c o ; a r e a ) . E f f e c t l e a d . 1 s a m p l e ; ; o f - w a shing Type o f Washing Water Washing A c i d Washing Treatment w i t h Lead U n t r e a t e d T r e a t e d U n t r e a t e d T r e a t e d S u r f a c e c o a l R e p l i c a t e ( i ) R e p l i c a t e (2) 1.809 2.207 1.953 1.834 1.851 2.156 1.927 2.003 Core C o a l R e p l i c a t e (1) R e p l i c a t e (2 0.367 0.269 0.293 0.376 0.310 0.283 0.249 0.374 hie 3 ( b ) . Analysis of Variance of data in T a b l e 3(a). Source.-of V a r i a t i o n Degrees o f Suas o f s q u a r e s Kaan squares F Washing (A) 1 0.0037 0.0037 1.5 CK.S.) C o a l fcyps (3) 1 10.5214 10.5214 4482.1** Treatment (C) 1 0.034.5 0.0345 14.2** A i: B 1 0.00S5 ' 0.0025 3.5 (K.S.) E x C 1 0.0107 0.0107 4.4 (t;.s.) A x C 1 0.0208 0.020S 8.5* A x B x C 1 0,0723 0.0723 En/or S 0.0195 0.0024 T o t a l : 15 11.OS18 ** s i g n i f i c a n t r.t tha IS l e v e l * s i g n i f i c a n t a t the 5% l e v e l M.S. n o t s i g n i f i c a n t . 3 4 5 . Table 4 ( a ) . P h e n o l i c OH groups of co a l s and a c t i v a t e d carbon (m.eq/unit surface a r e a ) . E f f e c t of acid-washing. Type o f S u r f a c e c o a l Core c o a l A c t i v a t e d c o a l Washing R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e (1) R e p l i c a t e (2) Water Washing A c i d Washing 1.809 1.953 1.851 1.927 0.367 0.293 0.310 0.249 0.0006 0.0019 0.0006 0.0013 Table 4 ( b ) . A n a l y s i s of v a r i a n c e of data i n Table 4(a) Source p f V a r i a t i o n Degrees o f Freedom Sums o f squares Mean squares Washing (A) 1 Type o f Coal/Carbon(B) 2 A x B 2 E r r o r 6 0.0006 8.1846 0.0160 0.0038 0.-006 4.0923 0.0080 0.0006 1.0 (N.S.) 6440.0** 12.6** T o t a l : 11 8.2051 s i g n i f i c a n t a t 1% l e v e l N.S. n o t s i g n i f i c a n t . 346. T a b l e 5 ( a ) . T o t a l a c i d i t y o f v a r i o u s c o a l s a m p l e s (m.eq/gm) E f f e c t o f w a s h i n g a n d / t r e a t m e n t w i t h l e a d . Type of Treatment S u r f a c e c o a l Core Coal Washing w i t h Lead R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e (1) R e p l i c a t e (2) Water U n t r e a t e d 7.895 7.895 5.263 4.370 Washing T r e a t e d 8.947 8.684 4.265 4.265 A c i d U n t r e a t e d 8.684 8.684 5.263 4.210 Washing T r e a t e d 7.895 8.721 5.526 5.526 T a b l e 5 ( b ) . A n a l y s i s o f v a r i a n c e o f d a t a i n T a b l e 5 ( a ) • Source o f Degrees o f V a r i a t i o n Freedom Sums o f squares Mean squares F Washing (A) 1 0,5346" 0.5346 3.2(N.S.) C o a l type (B) 1 51.5380 51,5380 310.3** Treatment (C) i_ 0.1529 0.1529 0.9 (N.S.) A x B 1 0.2025 0.2025 1.2 (N.S.) B x C 1 0.0005 0.0005 0.0 (N.S.) A x C 1 0.0235 0.0235 0.1 (N.S.) A s B x C 1 1.7394 1.7394 10.5* E r r o r 8 1.3287 - 0.1661 T o t a l s 15 55.5200 s i g n i f i c a n t a t the 12 l e v e l it s i g n i f i c a n t a t the 5% l e v e l N.S. not s i g n i f i c a n t 347. Table 6(a). T o t a l a c i d i t y of co a l s and a c t i v a t e d carbon (m.eq/gm). E f f e c t of a c i d washing. Type o f S u r f a c e c o a l Core c o a l A c t i v a t e d carbon Washing R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e (1) R e p l i c a t e (2) R e p l i c a t e (1) R e p l i c a t e (2) Water Washing 7 - 8 9 5 7 ' 8 9 5 5 ' 2 6 3 4 ' 3 7 0 ° ' 4 7 ° - 4 7 Aci A Washing 8 , 6 8 4 8 - 6 8 4 5 - 2 6 3 4 - 2 1 0 - 1 - 4 7 1 - 0 5 Table 6(b). A n a l y s i s of vari a n c e of data i n Table 6(a). Source o f Degrees o f V a r i a t i o n Freedom Sums o f squares Mean squares F Washing (A) 1 0.7517 0.7517 4.3 (N.S.) Type, o f c o a l / arbon (B) 2 110.3159 55.1580 317. .9** A x B 2 0.5052 0.2526 1.5 (N.S.) E r r o r 6 1.0403 0.1735 T c t a i r 11 112.6137 s i g n i f i c a n t a t 1% l e v e l N.S. not s i g n i f i c a n t Appendix C-7-3. Released lead ions during the total acidity and carboxy group measurements. C o a l Samples T o t a l A c i d i t y U s ing S a ( 0 H ) o Lead Released 3g/l TEg/gm c o a l C a r b o x y l Groups U s i n g Barium A c e t a t e U s i n g C a l c i u m A c e t a t e Lead Released Lead Released mg/1 mg/gm c o a l mg/1 mg/gm c o a l B l a n k (no c o a l added) N.D. 3.5 N.D. 0.5 N.D. 1 Water-washed c o a l O r i g i n a l T r e a t e d w i t h Lead 1 25 N.D. 3.07 6.93 3.5 30 N.D. 7.76 0.5 17.52 12 3.05 6.89 2 Acid-washed c o a l O r i g i n a l T r e a t e d w i t h Lead 0.5 29 N.D. 3.54 8.69 N.D. 36.0 N.D. 9.59 23.53 N.D. 1.32 3.24 A „ . . c i • i j l e a d r e l e a s e d (mg/gm c o a l ) * Tne percentage o f l e a a r e l e a s e d = : — : : —, . ° - r-^— x 100 l e a d absorbed (mg/gm c o a l ) CO APPENDIX C-8 .BIOLOGICAL OXIDATION OF DISSOLVED ORGANICS BY COAL. C-8. TABLE 1. CUMULATIVE REMOVAL OF DISSOLVED ORGANICS USING INOCULATED COAL BED Mean Flow P a r t i c l e Rate = 5 0 ml/min Size of Coal = 0.2 9 65 mm Run Number Volume Throughput l i t e r s Applied TOC (mgs Removed ) % Removal Applied BOD5 (mgs) Removed % Removal Applied COD (mgs) Removed % Removal 1 20 1640 940 57.3 3140 1540 52.2 4420 2360 53.5 2 20 1640 740 45.1 3140 2000 63.7 4420 2120 48.0 TOTAL 40 3280 16 80 51.2 6280 3640 58.0 8840 4480 51.0 NOTE: Three (3) grab samples were obtained during running of the f i r s t 20 l i t e r s and found to have about the same a n a l y s i s . Therefore, the average of these three r e s u l t s were considered as the average a n a l y s i s of the whole batch. ^ C-8. TABLE 2(a) BACKWASHING WITH NaOH SOLUTION pH = 11 350. TOC mg/1 T o t a l TOC Washed mgs BOD Removed mg/1 BOD5 Washed mgs COD mg/1 COD Washed mgs . Wash 1 (5 1) 93 465 13 5 675 2 34 .3 1171.5 Wash 2 (5 1) . 37 185 42 210 70.7 35 3 .5 Wash 3 (5 1) 33 165 30 150 60.0 300 . 0 l Wash '4 (5 1) 40 200 1015 36 180 1215 66 .0 330 .0 2155.0 C-8. TABLE 2(b) CONTROL EXPERIMENTS USING H 20 and LEACHED THROUGH FRESH NaOH SOLUTION COAL TC mg/1 TIC mg/1 TOC mg/1 H ?0 8-10 4 1-6 NaOH T o t a l mgs Wash 1/a 60 8 52 52 Wash l/£ 50 7 4 3 43 Wash l/£ 15 7 8 8 10 3 mgs TABLE 3. CUMULATIVE REDUCTION OF TOC, COD, AND BOD5 BY LEACHING OF OXO BEEF SOLUTION THROUGH HAT CREEK COAL 9" BED INOCULATED COLUMN Average Particle Size of Coal = • 0 .533 mm Service TOC COD BOLV D Volume Liters Total TOC Applied mgs Total TOC Removed mgs % Removal Total COD ' Applied mgs Total COD Removed mgs % Removal Total BOD Applied mgs Total BOD Removed mgs % Removal I 148 51 34 580 392 68 350 . 180 50 2 296 102 34 1160 708 61 720 318 44 3 444 148 33 1740 972 56 1080 456 . 42 u 592 189 32 2320 1288 56 1440 588" 41 5 740 235 32 2900 1664 57 1800 732 41 6 888 297 33 3480 2056 59 2160 906 45 7 1036 348 34 4060 2436 60 2520 1062 42 8 1184 399 34 4640 2800 60 2880 1236 43 9 1332 461 35 5220 3160 61 3240 1446 45 APPENDIX C-9 . APPLICATIONS IN SEWAGE TREATMENT C-9-1. TABLE !• CONTACT PPOCESS REMOVAL OF POLLUTANTS FROM ICNA SC.-AGE. Coal s i z e = 0.2^65 mm EODg COD TOTAL NITROGEN TOTAL FiiOSPlIORUS LEAD Coal Contact E f f l . mg ad- E f f l . mg ad- E f f l . mg ad- % E f f l . irg ad- % E f f l . mg ad- a % % T i r e Cone. sorbed Removal Cone. sorbed Removal Cone. sorbed Rerrcval Cone. sorbed Removal Cone. sorbed Removal Detectable Added Hrs. mg/l per gm mg/l per gm mg/l per gm mg/l per gm ng/1 per gm Removal c o a l c o a l c o a l c o a l c o a l O ( o r i g . Iona)96 i - l l l 213.5 18.4 2.9 0.05 1 11 9.3 >89 36 17.75 83 14.3 0.41 22 1.85 0.105 38 0.03 0.002 60 80 4 11 9.3 >S9 41.8 17.17 80 12.3 0.61 33 1.8 0.110 . 34 <0.02 >0.003 >80 100 1% 16 11 9.3 >89 45.6 16.79 79 10.6 0.78 42 1.9 0.099 34 <0.02 >0.003 >80 100 24 6 9.8 >94 40.8 17.27 81 10.3 0.81 44 0.03 0.002 >80 ' 100 80 6 9.8 = 94 20 19.40 91 9.7 0.87 47 1.9 0.099 34 <0.02 >0.003 >30 100 ( o r i g . Iona)96 -111 213.5 IB .4 2.9 0.05 1 11 1.86 >89 42 3.43 80 9.15 0.185 50 1.99 0.0182 30 <0.02 >0.0006 >80 100 4 11 1.86 >89 35.9 3.55 83 8.25 0.203 55 1.7 0-024 41 <0.02 >U.0C06 >«0 100 5% 16 11 1.86 >S9 49.6 3.28 77 7.00 .'.0.228 62 1.53 0.0274 47 <0.02 >0.C006 >80 100 24 5 1.93 >95 35.2 3.57 84 7.68 0.214 58 1.22 0.0336 58 <0.02 >C0006 >30 100 80 « 5 >1.98 >95 17.2 3.93 92 9.75 0.173 47 0.G4 0.0452 78 Tne s r n s i t i ' - i t y of instrument used i n the lead a n a l y s i s i s < 0.02 BOD, C-9-1. T A B L E .2. COrTTACT PROCESS R E T W A L OF POLLUTANTS FROM IONA SE7WAGE ' C c a l s i z e = Fines l e s s than 0.03414 wr> ODD T O T A L NITROGEN TOTAL PHOSPHORUS C o a l Contact E f f l . a) ad- % E f f l . mg ad- % Tine Cone sexbed Removal Cone, scrbed Added Ji r s . mg.l per gm mg/1 per gir. c c a l c o a l TRO % E f f l . mg ad- % E f f l . mg ad- I '. Removal Cone, scrbed Removal Cone, sorbed Removal mg/1 per gm mg/1 per gm co a l c o a l L E A D E f f l . ng ad- . % % Cone, sorbed R e n o v i l Detectable mg/1 per gm Removal c o a l 1% 5% O ( o r i g . Icna) 96 -111 213. ,5 18, .4 2. .9 0.05 1 12 9.2 >89 35. .9 17, .8 83 11 .9 0. ,65 35 1. .06 0.184 63 0.03 0.002 60 80 4 12 9.2 >89 35. .9 17. .8 83 • 11 .8 0. .66 36 0. .7 0.22 76 <0.02 >0.003 >80 100 • 16 11 9.3 >S9 47. ,6 16. .6 78 8 .12 1. .028 56 - - <0.02 >0.003 >80 100 24 6 9.8 >94 22 19. .2 90 10 .8 0. .76 41 0. .59 0.231 80 <0.02 >0.003 >80 100 80 < 5 >9.9 >95 7. .2 20. .6 97 6 .55 1, .185 64 0. .4 0.25 86 <0.02 >0.003 >80 100 O ( o r i g . Iona) 96 -111 213. .5 18 .4 0.05 1 12 1.84 ~ >S9 39. .8 3. .474 81 7 .8 0. .212 58 1. .45 0.029 50 <0.02 >0.0006 >80 100 4 15 1.73 >36 55. .2 3. .166 74 8 .54 0. .197 54 1. .45 0.029 50 <0.02 >0.0006 >80 100 16 6 1.96 >94 24. .4 3. .782 89 12 0. .128 35 0. .71 0.044 76 <0.02 >0.0006 >S0 100 24 5 1.98 >95 7. .2 4, .126 97 6 .76 0. .233 63 0, .59 0.0462 78 0.03 0.0004 60 80 80 < 5 >1.93 >95 C. .8 4, .134 97 8 .04 0. .207 56 1, .0 0.038 66 <0.02 >0.0006 >80 100 C-9-2. TABLE 1. COLUMN ADSORPTION TESTS REJ-30VAL OF POLLUTANTS FROM IONA SEV.AGE Bf. COAL Flow r a t e = 1 0 - 1 2 ml/min BOD. C u m u l a t i v e T h r o u g h p u t V o l umes L i t e r s E f f l u e n t c o n e . mg/1 O r i g i n a l I o n a 111 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 • 4.5 5.0 -5.5 6.0 8.0 111 78. 75 62 54 28 27 30 30 28 •31 24 24 R e m o v a l o f BOD. mg/I 0 33 36 49 57 83 84 81 81 83 80 87 87 Removal 0 30 32 44 51 75 76 73 73 75 72 78 78 C u m u l a t i v e Removal mgs COD E f f l u e n t c o n e . mg/1 Removal o f COD mg/1 TOTAL NITROGEN Removal C u m u l a t i v e R emoval mgs E f f l u e n t c o n e . mg/1 Rem o v a l o f T-N ' mg/1 % Removal C u m u l a t i v R e m o v a l mgs 213.5 18.4 0 213 = 0 0 0 6.05 12.35 67 6.175 16.5 154.8 53.7 28 29.35 4.55 13.85 75 13.1 34.5 126.8 86.7 . 41 72.70 3.80 14 .6 79 20.4 59.0 119.6 93.9 44 119.65 3.80 14.6 79 27.7 87.5 96.8 116.7 55 178.0 3.83 14 .57 79 34 .99 129 82.2 130.7 61 243.35 2.98 15.42- 84 4 2.70 171 80.8 132.7 62 ' 309 . 7 3.10 15.30 83 50.35 211.5 76.0 137.5 64 378.45' 3.12 15. 28 83 57.99 252 74.2 139.3 65 448 .1 3.50 14 .9 81 6 5.44 293.5 76.0 137.3 64 516.85 4 .18 14.22 77 72.55 333.5 63.6 149.9 70 591.8 4.3 14 .10 77 79.60 377 55.6 157 . 9 74 6 7 0.75 4.3 14 .10 77 86.65 • 533.6 48.0 165.5 77 968.65 3.8 14 .6 79 ' 112.93 •-Jj C-9-2 TABLE 1 (continued) C o a l s i z e = 0.5331 nrr. = 1/4" TOTAL PKOSPIiATE -• ORTHOPHOSPIATE " l u e n t R e m o v a l % C u m u l a t i v e E f f l u e n t Removal % . C u m u l a t i v e E f f l u e n t C u m u l a t i v e % % :onc. o f Removal Removal c o n e . o f - 3 Rem o v a l Removal c o n e . R e m o v a l Removal D e t e c t . ng/1 T-P mgs mg/l PO mgs mg/l mgs Remc mg/l mg/l 2.9 1.83 •0 .05 2.00 0.9 31 0.45 0.53 1.3 71 0.65 <0 .02 >0.015 >80 100 2.00 0.9 31 0.90 0.6 1.23 67 1.27 <0 , .02 0.03 >80 100 2.00 0.9 31 1.35 0.9 0.93 51 1.73 <0. .02 0.045 >80 100 1.90 1.0 35 1.85 0.82 1.01 55 2.24 <0 . 02 0.06 >80 100 1.62 1.28 44 2.49 0.92 0.91 50 2.69 <0 . 02 0.075 >80 100 1.75 1.15 40 3.070 • 1.19 0.64 35 3.01 <0. ,02 0.09 >80 100 1.86 ' 1.04 36 3.59 1.29 0.54 30 3.28 • <0 . .02 ' 0.105 >80 100 1.90 1.0 35 4.09 1.26 0.57 31 3.57 <0 . 02 0.12 >80 100 2.05 0.85 29 4.51 1.28 0.55 30 3.84 <0 . 02 0.135 >80 100 2.11 0.79 27 4.91 1.25 0.58 32 4.13 <0. 02 0.15 >80 100 2.14 0.?6 . 26 5.29 1.25 0.58 32 4.42 <0 . 02 0.165 >80 100 2.15 0.75 26 5.66 1.30 0.53 29 4.69 <0. 02 0.18 >80 100 2.05 0. 85 29 7.19 1.24 0.59 32 4.98 <0 . 02 0.234 >80 100 APPENDIX D DATA RESULTS OF DESIGN APPLICATIONS. APPENDIX D - .1 TENTATIVE CALCULATION OF A COAL BED FOR IONA (VANCOUVER) SEWAGE TREATMENT 356. 1. Laboratory Experiment Three v e r t i c a l c y l i n d r i c a l columns of 1 1/2 i n . I.D. with 1 f t , 2 f t , and 4 f t lengths were f i l l e d with Hat Creek coa of 0.533 mm mean p a r t i c l e s i z e . A s o l u t i o n of lead (5 mg/l) was applied continually at 2 the rate of 1 gpm/ft . The data from t h i s experiment i s shown i n Table 23. The "break-through" point was determined when the e f f l u e n t s o l u t i o n reached a strength of 0.5 mg/l of lead. Theory The performance of a coal bed may be evaluated by the use of the Bohart and Adams r e l a t i o n s h i p (8) as shown i n the following equation: N V C O O B i n which t = service time (hours) V = l i n e a r flow rate (ft/hr) D = depth of carbon bed (ft) D = c r i t i c a l depth of carbon bed (ft) P 3 K = rate constant ( f t /lb/hr) 3 N Q = adsorptive capacity ( l b / f t ) CQ ~ i n f l u e n t solute concentration (mg/l) n = allowable e f f l u e n t solute concentration (mg/l) I f t (time hrs) i s pl o t t e d vs. D (depth of bed f t ) f o r the three columns a s t r a i g h t l i n e i s obtained as shown, i n Figure D - 1 - 1. From the experimental data obtained the mathematical r e l a t i o n s h i p i s applied i n the above equation. 3 5 7 . 1. C a l c u l a t i o n of the C r i t i c a l Depth, e.g. the t h e o r e t i c a l depth of coal carbon which i s s u f f i c i e n t to prevent the e f f l u e n t solute concentration to exceed Cfi at zero time: O B N = (slope of the li n e ) C V o c o From the graph Figure 76 slope = 538. c =  5 M g / 1 (62.4 f t 3 ) = 3.12 X 10~ 4 l b / f t 3 ° 10° V = 1 0 f t / h r (based on a contact time of 30 minutes 2 and 1 gpm/ft ) N = 538 X 3.12 X 10~ 4 X 10 = 1.679 l b / f t 3 o C q In = (_° - 1) = In (-| - 1) = 2.197 C B .5 where C Q = 5 mg/1 CL, - 0.5 mg/1 K may be calculated from the intercept of the l i n e graph: b the intercept from Figure 76 i s - 100. l c b = p i - m (_2 - i ) C o K CB C In (^ - 1) ° R K = -|-7bT = ~ = 70.42 ft: 3/lb/h:: S> 1 1 3.12 X 10 i X 100 M C Then D ( c r i t i c a l depth) = ~ - In (~ - 1) ° K N o CB 1 0 X 2.197 = 0.186 f t 70.42 X 1.679 3 5 8 . With a 1 f t bed depth and the above values calculated, the service l i f e would be: O O B 1.679 _ f l 10 X 2.197] 3.12 X 10~ 4 X 10 70.42 X 1.679 = 438 hrs = 18.25 days An a p p l i c a t i o n to Iona values where: Flow rate = 70 M.G.D. Lead content = 0.2 mg/l At 70 M.G.D. = 48,611.1 gpm At an inflow (applied to bed) rate 2 = 1 gpm/ft Area of bed = 48,611.1 f t 2 (1.1 acres) V = 1 0 f t / h r ° 3 N = 1.679 l b s / f t J o 3 K — 70.416 f f / l b / h r C Q = 0 . 2 mg/l = 0.1248 X 10~ 5 l b / f t 3 CL, (required) = 0.05 mg/l (max. drinking water a * standard for lead). In ( ^ - 1) = l n (^-^ - 1) = 1.0986 B * Contact time required i s 30 minutes, and 2 Flow rate = 1 gpm/ft = 0 . 1 6 f t 3 / f t 2 / m i n = 0.16 f.p.m. .". Required depth f o r 30 minutes contact time i s 0.16 X 30 = 4.8 f t (say 5 f t bed depth) 359, Service L i f e would be: N • C O O B 1.679 ( 5 10 x 1 # 0 9 8 6 0.1248 X 10~ 5 X 10 70.42 X 1.679 = 66,017.5 hrs = 2750 days = 7.5 years Total Volume of Wastewater Handled: 70 M.G.D. X 2750 = 1.925 X 1 0 1 1 gals Annual Volume 70 X 10 6 X 365 = 2.555 X 1 0 1 0 gals L i f e of Bed = 1 , 9 2 5 X 1 Q l n =7.5 years 2.555 X 10 2 555 X l O 1 ^ Changes (renewal) per year = — = 0-1327 of 1.925 X 10 1 t o t a l bed Total Volume of Coal: 2 Surface area = 48,611 f t Volume = 48,611 X 5 = 243,055 f t 3 3 Density of coal - 42.7 l b s / f t Weight of coal = 42.7 X 243,055 = 5189.2 tons Quantity required/year - 5189.2 X .1327 = 688.6 tons Quantity required/day = 1.89 (say 2 tons) Total Lead removed d a i l y = 0.2 - 0.05 = 0.15 mg/l 0.15 X 70 X 10 6 10 l b / g a l = 1 Q 5 day 1 Q 6 E f f i c i e n c y of Coal Carbon Bed: 360. Total lead removed = 105 X 365 = 38,325 lbs T o t a l capacity/year = 1.679 X 2 4 3 / ^ 5 5 = 54,,-23.25 E f f i c i e n c y = f f - ^ y f f - ^ x 100 = 70.8% Additional laboratory experiments are necessary to for-tif} the above calc u l a t i o n s and estimates™ The experimental work requires a d d i t i o n a l time to complete the 0.5 e f f l u e n t value for the 4 f t column. Application rates of the lead solution at 2 2 2 gpm/ft and 5 gpm/ft would give a d d i t i o n a l r e l i a b l e values for c a l c u l a t i o n purposes. 1 . Coal Size: C.333 nrr. Celt: TT. dia: 1 7/8" (4.76 cn.) Day Volirro throughput Colt: per colunr. service inters cais. hrs 1 13.1 4.0 3 2 S7.2 19.3 24 3 32.6 13.3 20 4 109.7 24.3 22 5 75.4 16.7 23 6 79.9 17.7 22 7 79.9 17.7 20 8 58.7 13.0 18 9 45.2 10.0 18 10 45.2 10.0 17 11 43.2 10.0 17 Li. 60.1 13.3 20 •13 52.3 11.7 20 14 54.2 ' 12.0 24 IS 45.2 10.0 ' 16 16 67.7 15.0 20 £5. 5 ' 19.0 18 £ 7 -r 15.0 13 IS 43.2 12.0 15 20 72.2 16.0 20 45.2 10.0 16 22 76. 8 17.0 IS 23 81.3 18.0 20 24 67.7 15.0 20 25 63.2 14.0 18 TZSIE 1.. O0OTEUXS COLUMN ADSRPTION. PFCCESS KEM3VH, OF LEAD-EFFECT- OF BED DEPTH Influent cone. 4.26 4.76 5.14 4.65 5.2S 5.15 5.24 4.96 4.95 5.73 4.39 4.42 4.32 .4.35 4.30 4.18 4.06 4.14 4.38 4.36 4.47 4.71 4.48 4.72 4.67 Total of lead applied to each column nrrs. E f f l . cone. 76.60 491.83 916.61 1427.99 1826.19 2238.65 2557.5 2948.69 3172.23 3431.00 3651.31 3917.29 4145.55 4381.29 4575.48 4853.63 5206.99 5437.43 5724.79 £'.'39.83 .6241.7 6S03.3 6967.47 7237.2 7582.46 <0.014 0.037 0.031 0.091 0.126 0.162 0.183 0.212 0.236 C.273 0.244 0.22 0.22 0.22 0.22 0.258 0.466 0.159 0.167 0.214 0.233 0.470 0.500 0.530 0.555 of Pb Re-noval Pb re-roved mg/1 efficiency mcs. >4.245 >99.7 76.60 4.723 99.2 483.35 5.059 98.4 906.44 4.559 93.0 1407.84 5.154 97.6 1795.54 4.993 95.9 2196.05 5.057 96.5' 2600.27 4.743 95.7 2869.01 4.714 95.2 3091.89 5.457 ' 95.2 3338.33 4.645 95.0 3543.14 •4.200 5*95.0 3300.40 4.100 ' ''94.9 • ' '4017.03 4.130 94.9 4240.84 4.03 94.83 4425.09 3.922 93.8 4691.77 3.594 83.5 5000.15 3.981 96.1 ••• 5269.82 4.213 96.1 5493.13 4.146 95.1 •5797.70 • 4.232 • 94.7 59SS.S2 4.24 90.0 6314.33 3.98 83.8 6537.36 4.19 88.7 6921.69 4.114 88.1 7181.79 <0.01 <0.01 <0.01 <0.0i <0.01 0.027 <0.01 <0.01 <0.01 <0.01 0.02 0.02 0.03 0.03 0.03 0.03 0.04 0.048 0.057 0.067 0.071 0.167 0.30 0.33 0.324 >4.25 >4.75 >5.13 >4.65 >5.27 5.13 >5.23 >4.95 >4.94 >5.74 4.37 4.40 4.29 4.32 4.27 4.15 4: 02 4.092 .4.323 4.29 4.4 4.54 4.18 4.39 4.346 99.76 99.79 99.30 99.78 99.3 99.48 99.3 99.8 99.8 99.8 99.6 99.5 99.3 99.3 99.3 99.23 99'.'0 98.3 93.7 93.5 98.4 96.4 93.3 93.0 93.0 76.66 <0.01 >4.25 490.77 <0.01 >4.75 914.73 <0.01 >5.13 1425.01 <0.01 >4.65 1322.45 <0.01 >5.27 2232.46 <0.01 >5.15 2650.51 <0.01 >5.23 2941.11 <0.01 >4.95 3164.20 <0.01 >4.94 3393.42 <0.01 >5.72 3613.35 <0.01 >4.83 3377.63 <0.01 >4.41 4104.30 <0.01 >4.31 4338.41 <0.01 >4.34 4531.24 <0.01 >4.29 4812.36 <0.01 >4.17 5157.29 <0.01 >4.05 5334.43 <Q. CI >4.13 5667.75 <0.01 >4.37 5973.73 <0.01 • >5.35 6177.43 <0.01 >4.46 6525.97 0.048 4.66 6365.75 0.043 4.43 7163.13 0.105 4.62 7437.9 0.0925 4.58 99.3 99.3 99.3 99.3 99.8 99.8 99.8 99.3 99.3 99.8 99.3 99.3 99.3 99.8 99.3 99.8 99.3 99.8 99.8 99.3 99.8 93.9 93.9 97.9 93.0 76.77 - 491.63 . 915.61 1425.96 1823.35 2235.01 2653.06 2943.66 3165.75 3425.07 354 5.45 3910.33 ' 4163.06 4403.25 4595.99 4379.47 5226.93 5306.75 574 3.57 6057.S3 6259.29 6517.05 6977.16 7290.12 7579.69 ON TABLE I. (Continued) 5 T Volume throughput par column Liters gals. Column Service tins hrs. Influent cone. mg/1 26 27 23 29 30 "31 32 33 34 35 36 • 37 33 39 40 41 42 43 44 43 46 47' 48. 49 50 51 52 53 54 '55 56 57 53 49.7 63.2 63.2 53.2 37.2 70.0 76. S 45.2 ' 103.9 53.7 67.7 63.2 90.3 49.7 4.2 75.3 31.0 45.2 67.7 64.5 75. 3 72.2 63.2 31.5 67.7 67.7 67.7 117.4 63.2 45.2 67.7 11.0 14.0 14.0 14.0 19.3 15.5 17.0. 10.0 23.0 13.0 15.0 14.0 20.0 I.1.0 9.3 17.0 I I . 3 11.3 10.0 15.0 14.3 17.0 16.0 14.0 7.0 15.0 - 15.0 15.0 26.0 14.0 10.0 .15.0 826.0 16 17 20 13 24 20 24 16 24 13 24 24 24 24 16 20 16 10 18 22 20 24 24 23 8 20 18 20 35 20 24 20 4.71 4.71 5.04 4.76 4.6 ' 4.86 5.05 5.3 4.86" 5.53 4.46 5.25 4.85 4.38 5.12 4.43 5.04 . 5.00 5.05 4.77 4.91 , 4.37 4.73 4.48 4.45 4.45 ' 4.6 4.5 4.28 4.28 4.00 4.00 •iota! of lead applied to each column mgs. 1129 7316.43 8114.'2 8432.87 8733.82 9134.75 9474.94 9862.64 10101.99 10C06.79 10931.45 11233.57 11565.50 12G03.55 12245.97 12461.00 12804.94 13062.14 13317.29 13J45.35 13363.47 - 14183.55 14559.43 14904.81 15183.05 15323.72 15630.16 15941.76 16246.59 15749.13 17C19.73 17200.37 17471.33 17471.33 E f f l . cone. mg/1 0.510 0.602 0.64S 0.701 - 0.710 0.740 0.765 0.867 0.775 0.918 0.765 0.918 0 714 0.794 0.754 0.771 0.848 0.869 0.887 0.803 0.833 0.884 0.380 . 0.863 0.881 0.963 1.452 1.430 1.350 1.400 1.290 1.300 COAL BED Removal of Pb mg/1 1 FT. DEPTH Removal efficiency 4.200 4.103 4.392 4.059 3.890' 4.120 4.285 4.433 4.035 4.612 3.695 4.332 4.136 4.036 4.366 3.709 4.192 4.131 4.163 3.967 4.077 3.936 3.900 3.617 3.569 3.482 • 3.143 3.070 2.930 2.830 2.710 2.700 Cumulative Pb removed 89.0 37.2 87.1 85.3 84.6 , 84.7 84.8 33.6 84.0 83.3 82.8 82.5 85.2 33.7 85.2 82.7 83.1 82.6 82.4 83.2 83.0 81.8 81.5 80.7 80.2 73.2 68.4 68.2 63.4 67.3 67.7 67.5 7390.43 - 7650.15 7927.33 3134.46 8523.51 8811.90 9140.87 9341.06 9765.35 10036.12 10235.42 10560.31 10933.87 11136.85 11320.22 11604.97 11318.89 12029.7 12217.70 12435.99 12754.71 ' 13060.72 13342.52 13571.20 136S4.02 13919.89 14133.13 14341.09 14585.12 14367.21 14939.59 15172.49 15172.49 E f f l . cone. mg/1 CQAb HhJJ 2 FT. DEPTH- Removal ~% : of Pb 0.331 0.331 0.331 0.324 0.285 0.324 0.357 0.357 0.306 0.383 0.306 0.357 0.408 0.406 0.317 0.404 0.405 0.399 0.324 0.370 0.392 0.343 0.296 0.294 0.323 0.430 0.591 0.538 0.721 0.700 0.600 0.700 4.379 4.379 4.709 4.436 4.315 4.536 4.693 4.943 4.554 5.147 4.154 4.893 4.442 4.474 4.803 4.076 4.635 4.601 4.726 4.378 4.513 4.527 4.484 4.186 4.157 . 4.02 3.859 4.012 3.779 3.580 2.400 3.300 Removal Efficiency Cumulative Pb removed mcs. 92.97 92.97 93.43 93.19 93.80 93.30 92.93 93.20 93.70 93.00 93.10 93.20 91.60 91.60 93.80 90.98 91.96 92.02 93.5 91.78 92.01 92.95 93.8 93.4 92.70 90.30 85.72 87.21 . 83.98 83.6 85.0 82.5 7655.43 7932.29 8230.01 8510.47 8886.56 9204.04 9564.36 9787.58 10260.59 10562.76 10344.15 11153.51 11554.71 11776.96 11978.63 12291.60 125.28.13 12762.92 12976.35 13272.91 13564.63 13912.23 14236.22 14500.87 14632.28 14904.59 ' 15166.00 15437.77 15881.48 16107.82 16261.36 16484.90 16484.90 E f f l . cone. mq/1 CQAî  BUD 4 FT. DEPTH" 0.070 0.070 0.070 0.0925 0.0925 0.162 0.102 0.127 0.128 0.178 0.153 0.204 0.204 0.203 0.210 0.273 0.134 0.197 0.133 0.231 0.245 0.215 0.147 0.147 0.162 0.269 0.325 0.343 0.241 0.400 0.350 0.400 Removal of F mg/1 4.64 4.64 4.97 4.67 4.51 4.7 4.95 5.17 4.73 5.35 4.31 5.05 4.65 4.68 4.91 4.20 4.91 4.8 4.SI 4.54 4.67 4.66 4.63 4.33 4.29 4.21 4.28 4.16 4.04 3.88 3.65 3.60 . Removal Efficiency 93.5 98.5 98.6 93.1 93.0 96.7 98.0 97.5 97.3 96.7 96.7 96.2 95.9 95.9 95.9 93.8 97.4 96.0 97.2 95.1 95.1 95.7 96.8 96.6 96.4 94.0 93.0 92.4 94.3 90.6 91.2 90.0 Cumulative Pb removed ccs.. 7310.19 8103.55 3417.77 9713.03 91C5.04 94",5.03 9815.05 10043.53 10539.33 10852.92 11145.38 11465.16 ' 11385.15 12117.63 12323.34 12645.28 12896.84 13141.79 13353.74 13571.23 13972.36 14330.62 14665.17 14933.93 15074.55 15359.74 15649.57 15931.47 16405.33 16651.14 16815.97 17059.83 17059.83  APPENDIX D-2 FIELD STUDY ON IONA SEWAGE EFFLUENT. D-2 TABLE 1 - REDUCTION OF TOTAL AND VOLATILE RESIDUE BY HAT CREEK COAL 363. 1 Throughput Volume ' G a l l o n s Samples T o t a l Residue mg/l V o l a t i l e Residue mg/l F i x e d Residue mg/l O r i g i n a l sewage 500 128 85 E f f l u e n t at 1 metre l e v e l 500 264 E f f l u e n t at 2 metre l e v e l 520* 230* t 290 (16%) O r i g i n a l sewage 544 176 368 34.0 E f f l u e n t at 2 metre l e v e l 4-50 (11%) 108 (39%) 3̂ 2 (7*) * I n c r e a s i n g of the l e v e l s more than the o r i g i n a l ( ) The percentage removal e f f i c i e n c y D - 2 TABLE 2 - TREATMENT OF IONA SEWAGE WITH COAL REDUCTION OF BOD^ • 1739-5 ( t o t a l ) 110.6 (average) 1+6.5 64.1 58.0 44.0 66.6 60.2 43-9 T o t a l BOD5 a p p l i e d T o t a l BOD5 removed at 0 . 5 metre l e v e l Average capacit y of the c o a l 893800 mgs. 518017 mgs. 95 mgs BOD5 per gram of c o a l • I n f l u e n t BCDe mg/l 0.5 metre l e v e l 1 metre l e v e l 2 m etre l e v e 1 Volume Throughput g a l s . E f f l u e n t BOD5 mg/l Removed B 0 D < mg/l * Removal E f f l u e n t BOD5 mg/l Removed B 0 D 5 mg/l Removal E f f l u e n t B O D 5 mg/l Removed BOD5 mg/l Removal Down. : 'low: 1 2 9 . 2 1 5 1 . 0 2 5 . 0 1 2 6 . 0 83 .^ 2 2 . 0 1 2 9 . 0 8 5 - ^ 19.5 131.5 87.1 157-6 - - ui5 f: .ow« 8 9 . 0 105.8 311.8 182.1 9 5 . 0 1 2 2 . 5 85-5 50.5 < 1 0 78.5 2 1.7 44.5 36.5 63-8 46.8 88.0 35-9 74.6 41.2 80.0 1 5 . 0 53-8 36.5 42.5 7 0 . 5 56.6 88.0 3^-7 82.5 38.3 < 1 0 8 6 . 0 1 0 . 0 56.7 36.5 36.5 75.5 59.7 83.0 29.8 88.3 A f t e r Bac 1 [washing: 192.5 209.3 412.2 86.3 150.8 152.3 35-3 5 9 - 2 9 7 - 2 5 1 . 0 91.6 55-1 59 - 1 60.7 3 6 . 2 \ 2 5 - 0 66.0 ' 97-6 61.3 84.8 5̂ -7 7 1 . 0 5 6 . 2 35.9 21.7 •76.4 9^.5 64.6 74.4 57-8 7^-9 49.3 38.0 66.7 60.3 D-2 TABLE 3 - TREATMENT OF IONA SEWAGE WITH COAL REMOVAL OF COD Volume |Throughput g a l s Down fjlowt 166.0 129.2 157.6 8 9 . 0 105.8 311.8 182.1 A f t e r Bacldwashing 192.5 209.3 412.2 I n f l u e n t COD mg, A 0W! 200.7 1 5 ^ 381.9 126.5 110.7 200.1 177.0 0.5 metre l e v e l E f f l u e n t COD mg/l Removed COD mg/l 79-0 83.8 92.6 129.7 55-3 4 7 . 4 9 6 . 3 87.0 111.9 61.8 3^.0 71.1 63.3 80.8 Removal 5^.4 55.8 40.0 56.3 57 .2 ^5.7 1 metre l e v e l E f f l u e n t COD mg/l 71.1 92 .6 61.8 MA 84.7 Removed COD mg/l 9^.9 108.1 9 2 . 6 67-3 9 2 . 3 Removal [Effluent COD mg/l 57-2 53.9 6 0 . 0 2 metre l e v e l 60.8 5 2 . 2 3.5 46.3 46.0 3 9 . 5 50.O 61.7 Removed COD mg/l 16.25 15^.4- 108.4 71 .2 150.1 115.3 1789-5 ( t o t a l ) I 8 9 . 6 101.6 (average) 88.0 46.6 70.7 118.9 62.7 41.6 T o t a l COD a p p l i e d T o t a l COD removed a t 0.5 metre l e v e l Capacity of the c o a l 148.0 1 ,532,200 mgs. 711,160 mgs. 130.4 mgs COD per gram c o a l 78-0 U l D-2 TABLE 4 - TREATMENT OF IONA SEWAGE WITH COAL REMOVAL OF TOC Volume I n f l u e n t 0.5 metre l e v e l 1 metre l e v e l 2 metre l e v e l Throughput g a l s . TOC mg/1 E f f l u e n t TOC mg/1 Removed TOC mg/l Removal E f f l u e n t TOC mg/l Removed TOC mg/l % Removal E f f l u e n t TOC - mg/l Removed TOC mg/1 Removal Down fl .ow: 129-2 47-5 16.0 31-5 66.3 17.0 3 0 . 5 64.2 14.0 3 3 . 5 70.5 157.6 - - - - - - - - • - - up f: .ow: 8 9 . 0 52 .5 31.0 21.5 41.0 35-0 17.5 3 3 . 3 33-0 19.5 37.1 105.8 4-9.0 36.0 13.0 26.5 34-.0 15.0 3 0 . 6 2 8 . 5 2 0 . 5 41.8 311.8 77.6 48.8 28.8 37.1 50.1 27.5 3 5 . ^ 4 7 . 6 3 0 . 0 38.7 182.1 52.6 39 .2 13.^ 25.5 4 0 . 8 11.8 22.4 39-2 13.4- 25.4^ A f t e r Bac: cwashingt 192.5 50.8 36.2 14.6 29.1 41.9 8.9 17-5 36 .1 14.7 28.9 209.3 - - - - - - - - - 412.2 1789.5 ( T o t a l ) TABLE 5 - FIELD STUDY ON THE SEWAGE TREATMENT WITH HAT CREEK COAL REMOVAL OF BOD5 j Hours Cumulative Service Hours Flow Gallons Charged Cumulative BOD5 in influent | Elapsed Rate ml/min Gallons Charged Cone. mg/l Cumulative Applied Grams 23-2 23-2 275 84.6 S4.6 151-0 57.7 2-. 0 1*7.2 140 44.6 129-2 82-5 74.3 2=. 5 75-7 290 109-8 239.0 117-0 132-3 - 2 . . ; . ' 7 7 2 - « 0 99-7 i f / 6 - ' - 7 ? 150 47.8 286.8 117-0 157-6 - " :'i 3*-c- 132.7 215 S9-0 375-8 95-0 195-8 . - D - - / 7 7 ' 2 ?. .0 157.7 295 105-8 431.6 <U.5 215-6 71 .  £ - ' 7 7 1 7 .̂5 232.2 315 311.8 793-» 122-5 388.1 -V.V. ' 7 - 43-5 275-7 315 182.1 975-5 85-5 458.4 :.- "=/77 2f. 0 301.7 315 103.8 10S4.3 85-5 500.4 - - . ' ; ' • ' " 20 321-7 315 83.7 1168.0 86.3 533-0 - , . , ' 7 - i 53 371-7 315 209-3 1377-3 150.8 675-5 4/7/7? j 93.5 470.2 315 412.2 1789-5 152-3 959-0 1 Total 30Dr removed at 0.5 metre l e v e l . * , 493200 capacity 01 coal = CKCK i n 70 KGD flow at BOD5 l e v e l of 150 mg/l, load of 3CD^ daily Therefore, quantity of coal required .'5 metre l e v e l •. 1 netre l e v e l 2 r.S'trs ~Lsvsi Cumulative Removed Grams * Removal Effluent EODc mg/I Cumulative Removed Grams Removal Effluent Cumulative Removed % Her. oval 48.1 56.1 91.3 105.8 83-4 75-<* 69.O 67.1 22.0 M-5 44.0 48.0 49-3 57-6 93-8 108.7 85-4 77-5 .70-9 69.O 19.5 32.3 41.0 41.0 50.2 55.1 95.3 113-2 75-5 73-2 71-2 127-4 144.3 206.8 259-3 290-7 65-1 67.2 53-3 56.6 58.1 41.2 10 80.0 15-0 15-0 130-3 147-7 207-5 265-5 300.1 66.6 63.5 53-5 57.9 60.0 40.5 10 36.0 10.0 10.0 135.1 152.5 203.9 266.0 303.1 70.2 52.5 52.0 6c. 5 304.8 '391.1* 493.2 57-2 57.9 51.* 35-0 66.0 97.6 319-5 399-7- 501-5 59-9 59.2 52.3 33-5 75.4 9^.5 323.1 393-^ 501.0 f j . i -2 .2 52.2 = 493200 mgs = 90.4 mgs BOD5 removed per gram of ccal = 47418 kgs = 47.42 tons/day = 526 tons ~-4 APPENDIX . D - 3 TREATMENT OF REFINERY EFFLUENT WITH COAL. 5 6 8 > D - 3 T A B L E 1 REMOVAL OF PHENOL AND CYANIDE P a r t i c l e s i z e o f c o a l 4 8 / 1 0 0 C o n t a c t p r o c e s s C o n t a c t t i m e 2 4 h r s A n a l y s e s S a m p l e c o d e E f f l u e n t c o n e m g / l Removed m g / l % Removed mgs R e m o v e d / gm C o a l 0 - F • 0. 326 0.5% c c 0.075 0.251 77.0 0.0502 1.0% c c 0.08 0.246 75.5 0.0246 P h e n o l 0.5% s c 0.266 0.06 18.4 0.012 1.0% s c 0.167 0.159 48.8 0.0159 0.5% a c + 0.005 N.D. 0. 321 98.5 0.0642 t o 0.0652 D e t e c t a b l e l i m i t 0. 002 m g / l S e n s i t i v i t y ± 0. 005 m g / l D - 3 T A B L E 1 ( c o n t ) ADSORPTION ' OF CYANID E A n a l y s e s S a m p l e C o d e E f f l u e n t c o n e m g / l REMARKS 0 - F, 0.01 T h e i n i t i a l CN c o n c e n t r a t i o n w as _L (N.D.) v e r y c l o s e t o t h e d e t e c t a b l e l i m i t 0.5 a c N.D. = 0 . 0 1 , know t h e w h i c h m a k e s i t d i f f i c u l t t o : e f f e c t i v e n e s s o f t h e c o a l C y a n i d e 0.5 c c N.D. f o r a d s o r p t i o n o f c y a n i d e , r u n n i n g c o n t a c t e x p e r i m e n t s w i t h s t a n d a r d 0.5 s c N.D. c y a n i d e s o l u t i o n s o f h i g h e r c o n c e n t r a t i o n w i l l b e more h e l p f u l t< g i v e i s o t h e r m s . D-3 TABLE 2. Contact Process AMMONIA NITROGEN NH -N AND KJELDAHL TOTAL NITROGEN K-N o NH3-N K-N mg/l 0 - F 1 2.7 6.6 0.5% ac 3.0 5.1 0.5% sc 3.3 5.9 1.0% sc 4.0 7.3 2.0% sc 5.3 8.0 4.0% sc 7.7 9.5 0.5% cc 2.5 4.4 1.0% ̂ cc 2.6 5.9 2.0% cc 2.1 5.8 4.0% cc 1.8 5.1 A n a l y s e s T o t a l R e s i d u e D - 3 T A B L E 3 . C o n t a c t p r o c e s s REMOVAL OF S O L I D S 370. A. T o t a l R e s i d u e 1 Sample Code E f f l u e n t Removed % Removed mgs Removed/ Cone mg/l gm C o a l mg/l 0 - F l 3490.0 0.5% ac 3200.0 290 8.3 58 0.5% s c 3180.0 310 8.9 62 1.0% s c 3440.0 50 1.4 5 2.0% s c 3740.0 -250 - - 4.0% s c 3730.0 -240 - - 0.5% c c 3120.0 370 10.6 74 1.0% c c 3080.0 410 11.75 41 2.0% c c 3560 - 70. - - 4.0% c c 3650 -160 - - V o l a t i l e S o l i d s D- - 3 T A B L E 3 REMOVAL ( C o n t ) OF SO L I D S B. V o l a t i l e S o l i d s Sample Code E f f l u e n t - Cone mg/l Removed mg/l % Removed mgs Removed/ gm C o a l 0 - F 1 301 0.5% ac 120 181 60.1 36.2 0.5% s c 200- 101 33.6 20.2 1.0% s c 230 71 23.6 7.1 2.0% s c 270. 31 10.3 1.55 4.0% s c 450- - - - 0.5% c c 240 61 20.3 12.2 1.0% c c 130 171 56.8 17.1 2.0% c c 250 51 16.9 2.55 4.0% c c 565 _ _ _ D-3 • T A B L E 4 C o n t a c t P r o c e s s REMOVAL OF ORGANIC MATTER 3 7 1 . A n a l y s e s Sample Code B0D c A v . 5 BOD Removed % Removal mgs Removed/ gm C o a l 0 - F 1 26.10 o.5% ac 4.80 21.3 82 4.26 o.5% s c 19.20 6.9 26 1.38 BOD,. R e m o v a l 0 1.0% s c 2.0% s c 18.00 11.70 8.1 14.4 31 55 0.81 0.72 4.0% s c 5.70 20.4 78 0.51 0.5% c c 18.30 7.8 30 1.56 1.0% c c 17.70 8.4 32 0.84 2.0% c c 14.40 11.7 45 0.59 4.0% c c 12.90 13.2 51 0.33 D-3 TABLE 4 ( C o n t ) A n a l y s e s Sample Code COD COD % mgs Removed/ Removed Removal gm C o a l 0 - F 1 234 0.5% a c 181 53 23 10.6 COD R e m o v a l 0.5% s c 181 53 23 10.6 1.0% s c 170 64 27 6.4 2.0% s c 275 - - - 4.0% s c 294 - - - 0.5% c c 94.3 140 60 28 1.0% c c 89.9 144 62 14.4 2.0% c c 43 191 82 9.5 4.0% c c 45 189 81 4.7 372. D-3 TABLE 4 (Cont) Sample Code FIRST EXPERIMENTS SECOND EXPERIMENTS TOC i.e. TOC % TOC i.e. TOC % A n a l y s e s Removal Removal Removal Removal ppm ppm ppm ppm ppm ppm 0 - F 87 40 70 55 T o t a l O r g a n i c Carbon X 0.5% ac 0.5% sc (un f i l t e red ) 55 50 46 <10 32 37 37 43 ( f i l t e r e d ) 68 64 50 12 2 6 3 9 1.0% sc 55 <10 32 38 73 10 - - 2.0% sc 60 <10 27 31 81 <10 - - 4.0% sc 90 <10 - - 108 <1Q - - 0.5% cc 48 23 39 45 57 <10 13 19 1.0% cc 48 23 39 45 58 40 12 17 2.0% cc 40 20 47 54 42 28 28 40 4.0% cc 41 <10 46 53 43 28 27 39 NOTE: TOC = To ta l organic carbon I.C. = Inorganic carbon. D-3 T A B L E 5 REMOVAL OF O I L AND GREASE 373. Sample Code E f f l u e n t Cone mg/l Removed mg/l % Removed mgs Removed/ gm C o a l ° - F l 0.5% c c 0.5% s c 100.0 16.5 30.0 83.5 70.0 83.5 70.0 16.7 14.0 D-3 T A B L E 6 C o n t a c t P r o c e s s E F F E C T OF TREATMENT ON pH Sample Code Bat c h Exp. ( 1 ) . pH Batch Exp. (2) pH 0 - F^ ( o r i g i n ) 8.20 7.62 0.5% ac 8.35 7.50 0.5% c c 7.35 6.95 1,0% c c 7.30 6.85 2.0% c c 6.80 6.85 4.0% c c 7.18 6.75 o.5% s c 5.6 5.05 1.0% s c 4.48 4.25 2.0% s c 3.90 3.72 4.0% s c 3.65 3.41 A M O U N T O F C O A L U S E D % W / W -p- CORE COAL NON-OXIDIZED 14/20 MESH to -P o CO oo -P to o -p cn CO o -~1 CO t—1 K> O CO Cn co co — j .p CO co co .oo oo M N) M M co o to to IO to t- 1 cn o H cn CO O CO o H1 l-O o -P o tO to to H H I—• H o - J M to . cn I—1 • 1 to OO cn oo cn cn O O H co Cn U0 SURFACE COAL OXIDIZED 14/20 MESH CO CO rO CO CO CO to tO CO CO IO H IO IO CO H cn 1 IO o CO CO to to o cn CO CD o CO o CO to CO CO o OD O CO so to Cn CO to o I CO to o cn cn co 4r o to -F ~j O -<! CO OO CO to o CO CO cn CO oo O CO OO CO f—' Cn CO •P o •p — ] o H CO M to CO to to on o CO -p H o to o on —1 h-1 •P IO I 0O IO CO CO I—' cn OO CO to CO oo -P oo on (—1 oo o o CO co 00 0O CO CO CO CO oo o to 2^ i < CO i-3 co • o co p 5? o DB 13 O HI o o O 5d O O O O 9 S3 s o o H APPENDIX D-4 : DESIGN OF A COAL BED FOR REMOVAL OF PHENOL, CYANIDE, AND AMMONIA. D-4 • TABLE 1. CONTINUOUS COLUMN ADSORPTION PROCESS. HAT CREEK SURFACE COAL SIZE 4/14 TYLER >ESH PHENOL REWVAL BREAK-THROUGH 0.2 cg./l Voli me Service I n f l u e n t Cumula- 1 FOOT DEPTH 5 FEET DEPTH 5 1/2 FE ET DEPfri Throuchout Time PhoH t i v e E f f l . Removal Cumula- \ 0 E f f l . Removal Cumula- §. 0 E r f l . Removal Cumula- Xo. L i t e r s Gals Hours Cone. Total Cone. PhoH t i v e Cone. PhoH t i v e Cone. PhoH t i v e Removal Phenol Phenol Removal Phenol Removal Phenol Applied Removed E f f i c i e n c y Removed E f f i c i e n c y mg/l Removed E f f i c i e n c y mg/l mgs mg/l mg/l mgs mg/l mg/l mgs mg/l rcgs 1 45 10 1 1.S7 84 0.84 1.03' 46 54.8 0.138 1.732 78 92.9 0.08 1.79 80.6 93.9 2 1039 . 230 22 2.38 2450 0.98 1.40 1438 58.7 0.138 2.242 2307 94.2 0.03 2.30 2367 96.6 3 10 S4 240 24 2.38 2557 1.73 0.65 1467 57.4 0.180 2.200 2406 94.1 0.08 2.30 2471 96.6 A 1355 500 29 • 2.38 5202 1.85 0.53 1611 50.3 0.74 1.640 2850 89.0 0.11 2.27 30S6 96.4 1649 365 36 2.26 3S66 1.26 1.00 1904 49.3 0.75 1.51 3294 85.2 0.14 2.12 3709 96.0 6 1945 450 43 2.14 4496 1.24 0.90 2170 48.3 0.76 1.38 3700 82.3 0.17 1.97 428S 95.4 - 24 99 555 55 2.58 5930 - - - - 0.78 1.80 4701 79.3 0.24 2.34 55S9 94.3 S 3574 791 79 2.SS S703 - 0.42 2.16 7911 91.0 9 39S0 SSI S8 2.58 9751 - —= nrr^l •—— 0.82 1.76 8626 SS.5 - Flow rate = 1 gpm/ft^ - Contact time = 30' minutes • w - Bed s i z e = 6" diam., 5 1/2 f t . depth. ~ j • D-4 HAT CREEK SURFACE COAL SIZE 4/14 TYLER t€SH TABLE 2. CONTINUOUS COLU>N ADSORPTION PROCESS. CYANIDE RE îOVAL olume Service I n f l u e n t Cumula- 1 FOOT DEP1H 3 FEET DEPTH 5 1/2 FEEl DEPTH R L T . ougnput Time CN" t i v e L i f l . Removal Cumula- 0. E f f l . Removal Cumula- (\ •» E f f l . Re-oval Cumuia- L i t e rs Gals Hours Ccnc. Tot a l Cone. CN" t i v e Removal Cone. CN" t i v e Removal Ccnc. O i " t i v e Removal CN Removal E f f i c i e n c y Removal E f f i c i e n c y Removal E f f i c i e n c y Applied mg/l mg/l mg/l mgs mg/l mg/l mgs mg/l mg/l mgs mgs 1 45 10 1 1.42 64 N.D. 1.42 64 100.0 0.01 1.41 64 100.00 N.D. 1.42 63.4 CrlOO.OO -> 1039 230 22 1.42 1476 N.D. 1.42 1476 100.00 N.D. 1.42 1476 100.00 N.D. 1.42 1476 ~100.00 3 10S4 240 24 1.42 1540 0.62 0.80 1512 98.2 N.D. 1.42 1540 100.00 N.D. 1.42 1540 ^100.00 4 1335 300 29 1.42 1925 . 0.58 0.84 1740 90.4 N.D. 1.42 1925 100.00 N.D. 1.42 1924 <vi00.00 1649 365 36 1.51 2369 0.10 1.41 2155 91.0 N.D. .1.42 2342 98.9 N.D. 1.51 2369 sUOO.OO 6 1943 430 43 1.45 2795 0.4 1.05 2464 88.2 0.12 1.33 2733 97.8 N.D. 1.45 2795 CrlOO.00 - .499 553 55 1.53 3646 0.34 1.19 3395 93.1 N.D. 1.53 3646 ^100.00 s 3374 791 79 1.52 52S0 - - 0.17 ' 1.35 5097 96.5 c 39S0 SSI SS 1.52 5897 - i 0.54 , 0.88 5454 92.5 - Flow rate = 1 gpm/ft" - Contact time = 30 minutes - Bed s i z e = 6" diam., 5 1/2 ft. depth D-4 HAT CREEK SURFACE COAL SIZE 4/14 TYLER MESH TABLE 3. CONTINUOUS COLUMN ADSORPTION PROCESS AMNiQNIA REMOVAL Vol urns Service I n f l u e n t Cumula- 1 FOOT DEPTH 3 FEET DEPTH 5 1/2 FEET DEPTH Run No. Throu L i t e r s ghput Gals Time Hours NH. Cone. t i v e T o t a l NH 3 E f f l . Cone. Removal NH 3 Cumula- t i v e Removal \ Removal E f f i c i e n c y E f f l . Cone. Removal NH 3 Cumula- t i v e Removal Removal E f f i c i e n c y E f f l . Cone. Removal NH. Cumula- t i v e Removal Removal E f f i c i e n c y mg/l Applied gm mg/l mg/l gm mg/l mg/l gm mg/l mg/l gm 43 10 1 43.61 1.96 37.32 6.29 0.28 14.4 31.89 11.72 0.53 26.9 25.04 18.57 0.G4 42.6 1 1039 230 22 43.61 45.31 37.32 6.29 6.53 14.4' 31.89 11.72 12.18 '26.9 25.04 18.57 19.30 42.6 3 10S4 240 24 45.00 . 47.34 33.54 11.46 7.05 14.9 28.11 16.89 12.94 27.3 22.68 22.32 20.30 42.9 4 1335 300 29 45.00 59.54 35.67 9.33 9.58 16.1 32.13 12.87 16.43 27.6 25.75 19.25 25.52 42.9 5 1649 365 36 45.00 • 72.77 40.59 4.41 10.88 15.0 - 57.56 7.44 27.71 38.1 6 1943 430 43 43. S4 85.66 ) 43.38 0.46 11.27 10.24 36.14 7.7 54.26 31.1 7 7'.~ 353 55 43.84 110.04 ) S 3574 791 79 45.00 15S.42 - 41.68 3.32 - - 41.80 3.2 37.7 23.8 0 5930 SSI 88 39.79 174,57 37.42 2.37 - - 36.47 3.32 39.05 22.4 10 4295 951 95 39.79 187.14 - 37.42 2.37 36.47 3.08 40.02 21.4 - I n i t i a l cone v. 50 ppm - Allowable break-through = 5 ppm cw - Bed s i z e = 6" diara., 5 1/2 f t . depth ^ D-4 FIGURE 1(a) BREAK THROUGH CURVE FOR ADSORPTION OF PHENOL 3Y HAT CREEK COAL D-4 FIGURE 2(b) BREAK THROUGH CURVE FOR ADSORPTION OF CYANIDE BY HAT CREEK COAL INFLUENT Coal Bed Size: 2 m X 15% cm I.D. Average Particle Size of the Coal = 4/14 Mesh Tyler. 5 f t depth APPENDIX D- 5 DESIGN PATMMETERS. - 7 ; 8 1 # The Bohart Adams r e l a t i o n s h i p was appli e d i n t h i s work to o b t a i n the design parameters of a c o a l bed to t r e a t such e f f l u e n t w i t h respect to the adsorptive c a p a c i t y of the c o a l . The equations are as follows:. * • r r [" - m - l n & ' « i 0 o B •The t h e o r e t i c a l depth D q at t = 0 o B where t = s e r v i c e time (hours) V = l i n e a r flow rate ( f t / h r ) D = depth of carbon bed ( f t ) D q = c r i t i c a l depth of carbon bed ( f t ) K = rate constant ( f t / l b / h r ) N q = adsorptive c a p a c i t y ( l b / f t ) C Q = i n f l u e n t s o l u t i o n c o n c e n t r a t i o n (mg/l) Cg = allowable e f f l u e n t s o l u t i o n c o n c e n t r a t i o n (mg/l). I f t i s p l o t t e d vs. D f o r the d i f f e r e n t l e v e l s along the bed, a s t r a i g h t l i n e i s obtained as shown i n Figures 1 and 2, the slope N of the l i n e would be equal to a " d the i n t e r c e p t b. o -i C 1 / o 382. 1. C a l c u l a t i o n of Design Parameters to Remove Phenol C Q = 2 mg/l C B '= 0.2 mg/l V = 9.6 f t / h r (based on contact time .30 min and 1 gpm/ft2) From the s t r a i g h t l i n e shown i n Figure 1, slope = 12.5 and i n t e r c e p t b •= 13. c . = 2 rcg/1 (62.4 f t 3 ) = 1.248 X 10" 4 l b / f t 3 0 10 • N q = (12.5) X 1.248 X 10~ 4 X 9.6 = 0.015 l b / f t 3 . C ? In (-2. - i ) = In ( ~ - 1) •= 2.1972 B U' C In (^ - 1) K = = 2 , 1 9 7 . = 1354.3 f t 3 / l b / h r o l J 1.248'X 10 q X 13 Then D Q = ^ In ( ^ - 1) o B D Q = Y^^r^ X 2.1972 = 1.0382 f t . For treatment of a r e f i n e r y e f f l u e n t at the rate of 2 8 I gpm/lOOO Bbl of crude with an i n f l o w rate of 1 gpm/ft 2 an 8 f t area f o r the c o a l bed i s r e q u i r e d ; and to apply contact time of 30 minutes, the l i n e a r v e l o c i t y of the flow would be 0.16 f t / m i n , i . e . 9.6 f t / h r . Therefore, the required depth f o r 30 minutes contact = 0.16 X 30 = 4.8 f t (say 5 f t ) . To c a l c u l a t e the s e r v i c e l i f e f o r t h i s bed to remove phenol: o The q u a n t i t y of flow per day = 11,5 20 gals/day based on a 24 hr ope r a t i o n . .'. The flow per week = 80,640 g a l s , based on 7 days per week operation. [ 5 - u u 4 (n r n ry X 2.197] 1.248 X 1<T4 X 9.6 1 ' 1 3 5 4 ' 3 ' ° - 0 1 ' ^ .'. t 5 0 hours T o t a l volume of flow w i t h i n t h i s p e r i o d = 8(60) (50) = 24,000 gals Annual volume = 8 X 60 X 24 X 365 = 4,204,800gals/year No. of c o a l changes = ^ l ° A i l ° P = 175.2 times/year 3 Volume of c o a l per change = 5 X 8 = 40 f t .'. T o t a l c o a l volume required = 175.2 X 175.2 X 40 = 7,008 f t 3 / y e a r Since th edepth of the bed = 5 f t ; therefore the area of the 2 bed r e q u i r e d = 1,402 f t , and weight of the c o a l = 7,000 X 36 = 127 tons coal/ye a r . A c c o r d i n g l y , the suggested dimensions f o r the c o a l bed based on phenol removal would be 30 X 50 f t 2 area and 5 f t depth Quantity of c o a l required per day to t r e a t 8 gpm/ 1,000 b a r r e l e f f l u e n t =0.35 ton/day = 700 l b s . Total phenol (2 - 0.2 mg) removed from t h i s e f f l u e n t d a i l y = 0.210 7 l b s . 384 . C a l c u l a t i o n of the E f f i c i e n c y of the Bed Tot a l phenol to be adsorbed = 75.5 lb s / y e a r 8.34 lbs X 1.2 (̂£4̂ 10 ^ b a r r e l crude T o t a l c a p a c i t y = 0 . 0 1 5 ( l b / f t 3 ) X 7,000 = 105 lbs/year Experimental E f f i c i e n c y = X 100 = 72% 105 Computed from D D - D T h e o r e t i c a l E f f i c i e n c y = — g — - X 100= 5 - J--^-3bj X 100 = . 79% Removal of Cyanide N C c^v t D " K > T L N Ccr " c o B For cvani de,C Q = 1 mg/l C B = 0.1 mg/l C = -ir (62.4) = 0.624 X 10" 4 l b / f t 3 o l p o V = 9.6 f t / h r Slope = 1 4 . 8 N q = (14.8) X 0.624 X I O - 4 X 9.6 = 0.00887 l b / f f C l n = (-— - 1) = In (—y - 1) =2.19 72 B U • 1 K = - 2 ' 1 9 7 2 _ A = 35,212 0.624 X 10 4 X 1.0 Then D q = 35,212 xVoOSST X 2 • 1 9 7 2 = ° ' 0 6 7 " f t 3 8 5 . 2 Required depth f o r the r e f i n e r y e f f l u e n t f o r 1 gpm/ft flow r a t e and v e l o c i t y = 0.16 f t / m i n , f o r 30 minute contact time. The required'depth = 0.16 X 30 = 4.8 f t (say 5 f t ) The Service L i f e t •= [D - D Q] o t = - 0 , 0 0 8 8 7 j- '•— [ 5 - 0.06753] = 73.0 hours 0.624 X 10 X 9.6 T o t a l Volume = 8(60) X 73 = 35040 gals Volume of Coal = 8 f t 2 X 5 ='40 f t 3 Annual volume = 8 x 60 x 24 x 7 x 52 = 4,193,280 gals XT r i 4,193,280 , n _ No. of changes per year = — — — — - = 119.7 per year 3 Volume of c o a l per change = 40 f t Annual c o a l volume = 119.7 X 40 = 4,787 f t 3 T o t a l cyanide removed = (0.9 mg/l) X (LillA^^S^ll) ,8.34 lbs X 1.2 Imp/U.S., 10 gals/mg/1 =' 57 lb s / y e a r from each 1,000 b a r r e l E f f i c i e n c y T o t a l cyanide adsorbed = 37 lbs/ y e a r T o t a l c a p a c i t y = 0.00887 X 4787 = 42.46 lbs E f f i c i e n c y = ^ A 6 X 100 - = 87.1% Computed from D , E f f i c i e n c y i - ' 0.06753 = 9 8 - 6 o Consumption per day =0.238 Consumption of c o a l per year = 87 tons 3 8 6 . I •' r o m c a r l i c r c a 1 c u 1 a t :i. o n For phenol, coa l required/year = 127 tons (0.35 tons/day). .'• The suggested, bed to t r e a t r e f i n e r y wastes co n t a i n i n g both phenol and cyanide i s 29 X 49 X 5 f t (7,000 f t 3 ) I t w i l l serve 1 year to remove phenol and 1.5 years f o r cyanide. 3. Comparison Between the Adsorptive C a p a c i t i e s of Coal Towards Phenol and Cyanide i n the Mixture (a) Adsorption of Phenol ( i ) Adsorptive c a p a c i t y c a l c u l a t e d from the Bohart Adams r e l a t i o n s h i p (as before) = 0.015 l b / f t 3 = •0.4139 mgs PboH/gm co a l ( i i ) Computed from the a p p l i e d research: T o t a l phenol removed during the s e r v i c e period at the 5 1/2 feet l e v e l (bottom of the bed) 5,589 m i l l i g r a m s . T o t a l grams of co a l = 17,750 gms .'. Adsorptive c a p a c i t y at break-through of 0.2 mg/l phenol ~]_*y ' y = 0.3149 mg/gm coal (b) Adsorption of Cyanide . ( i ) Computed from the Bohart Adams r e l a t i o n s h i p : Capacity - 0.00845 l b / f t 3 = 0.2333 mgs/gm/coal ( i i ) Computed from the ap p l i e d research: T o t a l cyanide removed during the s e r v i c e period at the 5 1/2 feet l e v e l = 5,079 5 0 79 Capacity =-̂ yz-yg-Q = 0 . 2 8614 mgs/gin c o a l  60 E" FIGURE 1 EFFECT OF THE DEPTH OF THE COAL BED ON THE SERVICE L I F E , FOR BREAK THROUGH AT 0 2 r n P / l PHENOL AND INFLUENT CONCENTRATION 2 n W l " PHENOL. b 388. 3 i* DEPTH OF BED, FT. Slope = 12.5 *>89. 3 . Removal of Amnion.ia By applying an i n f l u e n t of 40-45 mg/l range concen- t r a t i o n , the e f f l u e n t c o n c e n t r a t i o n never decreased to the allowable l e v e l of 5 ppm NH . A maximum e f f i c i e n c y of 42.9% removal was obtained at the 5 1/2 feet l e v e l and throughput volume of 300 g a l l o n s , a f t e r t h a t , the e f f i c i e n c y dropped r a p i d l y to 21%. A very small value of 14.4% e f f i c i e n c y was obtained from the f i r s t foot l e v e l . The data show that Mat Creek coal i s a very poor adsorbent for ammonia and therefore i s not recommended to be used f o r that purpose. T o t a l volume run-through 951 gals T o t a l a p p l i e d ammonia 187.14 grams T o t a l ammonia removed i n the 5 1/2 feet l e v e l 40 . 02 grams Capacity of c o a l = 40,020 .17,750 2.25 mgs NH,/gram coal E f f i c i e n c y = 40 . 02 187.14 X 100 21.4%

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