UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

Pyrolysis of oil shale in a spouted bed pyrolyser Tam, Tina Sui-Man 1987

You don't seem to have a PDF reader installed, try download the pdf

Item Metadata

Download

Media
UBC_1987_A7 T35.pdf [ 8.03MB ]
[if-you-see-this-DO-NOT-CLICK]
Metadata
JSON: 1.0058776.json
JSON-LD: 1.0058776+ld.json
RDF/XML (Pretty): 1.0058776.xml
RDF/JSON: 1.0058776+rdf.json
Turtle: 1.0058776+rdf-turtle.txt
N-Triples: 1.0058776+rdf-ntriples.txt
Original Record: 1.0058776 +original-record.json
Full Text
1.0058776.txt
Citation
1.0058776.ris

Full Text

PYROLYSIS OF OIL SHALE IN A SPOUTED BED PYROLYSER by TINA SUI-MAN TAM B.A.Sc, The University of Toronto, 1978 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED SCIENCE in THE FACULTY OF GRADUATE STUDIES DEPARTMENT OF CHEMICAL ENGINEERING We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA July 1987 © TINA SUI-MAN TAM, 1987 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of C/)<?/rv' C ou2s QJ?-t / The University of British Columbia 1956 Main Mall Vancouver, Canada V6T 1Y3 Date DE-6(3/81) ABSTRACT Pyrolysis of a New Brunswick oil shale has been studied in a 12.8cm diameter spouted bed reactor. The aim of the project was to study the effect of pyrolysis temperature, shale particle size , feed rate and bed material on oil yield. Gas and spent shale yields were also determined. Shale of different particle size ranging from 0.5mm to 4mm was studied using an electrically heated reactor containing sand or spent shale which was spouted with nitrogen or nitrogen/carbon dioxide mixtures. For a given particle size and feed rate, there is a maximum in oil yield with temperature. For particles of 1-2mm at a feed rate of about 1.4kg/hr, the optimum temperature is at 475°C with an oil yield of 7.1% which represents 89.3% of the modified Fischer Assay yield. For the 2-4mm and the same feed rate, the optimum temperature is 505°C with an oil yield equal to 7.4% which is 94.3% of the modified Fischer Assay value. At a fixed temperature of about 500°C, the oil yield increases with increasing particle size. This trend is in agreement with the Fischer Assay values which showed oil yields increasing from 5.2% to about 8% as the particle size was increased. In the spouted bed, the oil yield decreases as the oil shale feed rate increases at a given temperature. The use of spent shales as the spouting solids in the bed also has a negative effect on oil yield. The gas yields which were low (less than 2.1% ) and difficult to measure do not seem to be affected by ii particle sizes, feed rate and bed material. Hydrogen, methane and other hydrocarbons are produced in very small amounts. C02 and CO are not released in measurable yield in the experiments. The trend of the spent shale yield has not been successfully understood due to the unreliability of the particle collection results. Attrition of the spent shale appears to be a serious problem. Results of the experiments are rationalized with the aid of a kinetic model in which the kerogen in the oil shale decomposes to yield a bitumen and other by products and the bitumen undergoes further decomposition into oil. The spouted bed is treated as a backmixed reactor with respect to the solids. A heat transfer model is used to predict the temperature rise of the shale entering the pyrolyzer. iii TABLE OF CONTENTS ABSTRACT ii LIST OF TABLES viLIST OF FIGURES ix ACKNOWLEDGEMENT X 1. INTRODUCTION 1 1.1 Objective of the Thesis 2 2. BACKGROUND 3 2.1 The Properties of Oil Shale 3 2.2 The Basic Principle of Oil Shale Pyrolysis 8 2.3 Oil Shale Pyrolysis Processes 8 2.4 Parameters Affecting Oil Shale Pyrolysis 15 2.5 Heat Transfer in Spouted Beds 23 3. KINETICS OF OIL SHALE PYROLYSIS 32 3.1 Literature Review of the Kinetics of Oil 32 Shale Pyrolysis 3.2 Kinetic-Model 38 4. EXPERIMENTAL EQUIPMENT AND PROCEDURE 47 4.1 Pyrolysis Apparatus 44.2 Properties of Oil Shale 54 iv 4.3 General Procedure 54 4.4 Detailed Operating Procedure 58 4.5 Oil Collection 60 4.6 Gas Analysis 1 4.7 Spent Shale Determination and Analysis 62 5. RESULTS AND DISCUSSION 63 5.1 General Considerations 65.2 Effect of Temperature on Oil Yield and 65 Composition 5.3 Effect of Oil Shale Particle Size on Oil 73 Yield and Composition 5.4 Effect of Oil Shale Feed Rate on Oil Yield 78 and Composition 5.5 Effect of Bed Material on Oil Yield 83 5.6 Effect of Pyrolyzing Gas on Oil Yield 90 5.7 Gas Yields 95.8 Spent Shale Yields 95 6. KINETIC MODEL 100 6.1 General Discussion 106.2 The Effect of Rate Constant on Oil Yield 104 6.3 The Effect of Oil Shale Feed Rate on Oil 107 Yield 7. CONCLUSIONS 109 v 8. RECOMMENDATIONS FOR FUTURE WORK 111 NOMENCLATURE 113 REFERENCES 116 APPENDIX A) Temperature History Model 121 APPENDIX B) Sample Calculations B.1 Isokinetic Gas Sampling Calculation 129 B. 2 Product Yield Calculations 130 APPENDIX C) Computer Programs C. 1 Profile 132 C.2 Entrance 149 C.3 Calculate 154 C.4 Model 8 C.5 Jac 162 C.6 Jac (Printout) 166 vi LIST OF TABLES Table 1 Inorganic Minerals Present in Typical 4 Medium Grade Oil Shale Table 2 Chemical Composition of the Inorganic 5 Portion of Oil Shale Table 3 Modified Fischer Assay for Typical Oil 6 Shale Samples Table 4 Conversion of Kerogen by the Fischer 7 Assay Table 5 Effect of Temperature on Oil Yield 18 Table 6 Effect of Particle Size on Oil Yield 21 Table 7 Particle Temperature History of the Oil 29 Shales (After One Pass) Table 8 Particle Temperature History of the Oil 30 Shales (After Two Passes) Table 9 Design Characteristics of Spouted Bed 48 Pyrolyzer System Table 10 Proximate and Ultimate Analysis of Blend 55 of Oil Shale A Table 11 Analysis of Oil Shale Ash and Carbon 56 Table 12 Modified Fischer Assay of Oil Shales 57 Table 13 Experimental Conditions for Each Run 64 Table 14 Effect of Temperature on Oil Yield 67 Table 15 • Effect of Temperature on Oil Yield and 72 Composition Table 16 Effect of Particle Size on Oil Yield 74 vii Table 17 Effect of Particle Size on Oil Yield and 77 Composition Table 18 Effect of Feedrate on Oil Yield 79 (Unsteady Height Expt.) Table 19 Effect of Feedrate on Oil Yield 80 (Unsteady Height Expt.) Table 20 Effect of Feedrate on Oil Yield (Steady 84 Height Expt.) Table 21 Effect of Feedrate on Oil Yield and 86 Composition Table 22 Effect of Bed Material on Oil Yield 88 Table 23 Effect of Pyrolyzing Gas Composition 91 Table 24 Gas Yields 93 Table 25 Spent Shale Properties and Yield 96 Table 26 Spent Shale Yields 98 Table 27 Effect of Temperature on Oil Yield (Predicted vs Experimental Values) 102 Table 28 Effect of Feed Rate on Oil Yield (Predicted vs Experimental Values) 108 Table 29 Coordinates of the Tridiagonal Matrix 126 Table 30 Correlations used for estimation of the 127 Hydrodynamic Properties for the Spouted Bed viii LIST OF FIGURES Figure 1 Effect of Pressure on Oil Yield Figure 2 Effect of Retorting Temperature on Oil Yield Figure 3 Effect of Particle Size on Tar Yield Figure 4 Schematic Diagram for Spouted Bed Figure 5 A Schematic Diagram for the Experimental Apparatus Figure 6 Oil Yield Versus Temperature Plot (d =1-2mm) P Figure 7 Oil Yield Versus Temperature Plot (dp=2-4mm) % Fischer Assay Vs Temperature Plot Oil Yield Vs Particle Size Plot Oil Yield Vs Feedrate Plot (d =1-2mm) P Oil Yield Vs Feedrate Plot (dp=2-4mm) Oil Yield Vs Feedrate Plot (Steady Height Expt.) Oil Yield Vs Spent Shale in Bed Hydrogen Gas Yield Vs Temperature Oil Yield vs Temperature Plot (Predicted vs Experimental values) Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 16 20 22 25 50 68 69 71 75 81 82 85 89 94 1 03 Figure 16 CR, Cg, CA and Oil Yield vs Time Plot 105 ix ACKNOWLEDGEMENT I wish to thank Dr. A.P. Watkinson and Dr. J. Lim, under whose supervision and guidance this research work was conducted, for their advice and encouragement in all stages of this work. I am also grateful to Dr. B. Bowen for his advice on the mathematical modelling; to Dr. G.K. Khoe for his assistance in the modifications to the apparatus and the carry out of some of the experimental runs; and to Dr. K.C. Teo for his help in doing the gas samples analysis. In addition, I wish to thank Mr. Michael Standbrook for his assistance in operating the experimental apparatus. Finally, my appreciation to the staffs of the Chemical Engineering Department workshop and stores for their continuing assistance through this work. X 1 1. INTRODUCTION Oil shales are widely distributed throughout the world with known deposits in every continent. The vast majority of known oil shale resources are found in United States (75% of the estimated world recoverable oil reserves), with other major deposits in China (about 11% of the estimated world reserves) and Canada (about 7% of estimated world reserves)' ' 1 . After the discovery of crude oil and petroleum, the oil shale industry which had previously become established could not compete. At present, oil shale is exploited in only two countries - the USSR and China. Synthetic crude oil can be obtained from oil shale. The organic matter in oil shale is composed of about 10% bitumen, and about 90% kerogen. Both are thermally unstable, and with the application of heat (250°C or greater), thermally decompose to form gaseous and liquid products that can be refined to synthetic crude. Therefore, many studies have been made of oil shale retorting. For the Western US shales, a high level of conversion can be achieved by a simple thermal retorting procedure, whereas for the Eastern US shales, rapid retorting or the use of hydrogen as a retorting gas is employed to achieve comparable organic matter recovery. By contrast, little attention has been paid to oil shales in Canada. Only a few research studies have been done on the shales from New Brunswick, Ontario, Quebec, Newfoundland and Nova Scotia. Since oil shale is one of the 2 promising alternate energy resources in parts of Canada, given the level of reserves, it is essential to investigate those parameters that will influence the overall yield of products derived from oil shale retorting, and which affect the distribution of products among gases, light oils and heavy oils. In this research, a spouted bed reactor that was constructed for coal pyrolysis*2> was used to study the pyrolysis of New Brunswick oil shale. 1.1.Objective of the Thesis The object of the study is to investigate the effect of pyrolysis temperature, shale particle size, shale feed rate and bed composition on oil,gas and spent shale yield from Albert Formation New Brunswick oil shale in a spouted bed pyrolyser. The shale is pyrolysed in either N2-C02 mixtures or N2, and in beds of either inert silica (Ottawa sand) or spent shale. Results are compared with predictions of the Fischer Assay, which is a standardized test for potential oilyield. * * The Fischer Assay method is used for determining the quantity of recoverable liquid oil and other products from oil shale . A 100 gm sample of finely crushed oil shale is heated at a rate of 12°C. per min to a final temperature of 500°C and held for an additional 70 minutes at 500°C in a sealed aluminum retort under controlled conditions. As kerogen is pyrolysed, the gaseous and liquid products evolved are collected and measured using standardized equipment. 2. BACKGROUND 2.1 The Properties of Oil Shale Oil shales are geologically classified as marlstones because of their large percentage of carbonates. Average shales are composed of about 86% mineral and 14% organic matter. Table 1 shows the inorganic minerals present in a typical medium grade oil shale and Table 2 shows the chemical composition of the inorganic portions of oil shale. The organic matter is present in the oil shale as a resinous solid, not as an oily liquid. It is composed of about 10% bitumen and 90% kerogen. The bitumen is a heteroatomic polymer soluble in many organic solvents, whereas the kerogen is a heteroatomic polymer having a molecular weight of greater than 3000 and is insoluble in most organic solvents. To the unaided eye, kerogen appears black in colour. Under the microscope, thin sections of kerogen appear yellow in colour with a minor portion appearing brown or black. It has no well designated structure, appearing as stringers, masses and irregular granules all intermixed with the inorganic materials in the rock. The kerogen subunits are cross-linked to one another by oxygen and sulfur. Upon application of heat, both kerogen and bitumen decompose to form gaseous and liquid products. Table 3 shows a modified Fischer assay for typical oil shale samples. Table 4 shows the conversion of kerogen by Fischer assay. TABLE 1: Inorganic Minerals Present in Typical Medium Grade Colorado Oi1 Shale Mineral Formula Wt % Dolomite (CaMg)CQ3 33 Calcite CaCOj 20 Plagioclase NaAlSiiOi and CaAliSizOi 12 Illite Kj0.3Alj0j.6Si02.2Hz0 11 Quartz SiOi 10 Analcite NaA1Si;0 $.H20 7 Orthoclase KAlSiiO. 4 Iron Fe 2 Pyrite (or marcasite) FeSi 1 Total 100 TABLE 2: Chemical Composition of the Inorganic Portion of Colorado Oil Shale Chemical Const i tuent S i 0 z,percent Al 203 CaO MgO SO 3 Na20 KzO Very Low Grade Shale 40. 9 4 . 3 9.4 1 1 .0 5.4 0. 1 1 .8 3.4 Med i um Grade Shale 26 . 1 2.6 6.5 17.5 5.3 0.6 2.6 1 .0 High Grade Shale 25 . 5 2.9 6.3 14.2 5.6 1 . 2 2.7 1 .9 Very High Grade Shale 26.4 3. 1 7.0 8.3 4 . 5 1 .4 1 .9 1 .0 TABLE 3: Modified Fischer Assay for Typical Colorado Oil Shale Samples Oil, gal/ton Oil, wt % Water, wt % Spent Shale, wt % Gas, wt % Loss, wt % For Very Low Grade Shale 10.5 4.0 0.5 94.4 1 . 1 For Medium Grade Shale 26 . 7 10.4 1 .4 85.7 2.0 0.5 For High Grade Shale 36.3 13.8 1 . 5 82. 1 2 . 2 0.4 For Very High Grade Shale 61.8 23 .6 1 . 1 70.4 4.2 0.7 TABLE 4: Conversion of Keroqen by the Fischer Assay Grade of Shale, gal/ton Conversion of Kerogen by the Fischer Assay to Oil, wt % Gas, wt % Organic Residue, wt % Water 10.5 26.7 36.3 51 65 69 14 12 11 35 23 20 (Excluded from calculations) 100 100 100 57. 1 61.8 75.0 66 69 71 12 12 11 22 19 18 100 100 100 8 2.2 The Basic Principle of Oil Shale Pyrolysis Oil shale pyrolysis involves the heating of oil shales in an inert atmosphere to cause decomposition. Over a long period of time, complete devolatilization can be achieved at temperatures of around 400-425°C. The mechanism usually given for oil shale decomposition is as follows: Kerogen > Bitumen + Gas, + Carbon Residue, Bitumen > Oil + Gas2 + Carbon Residue2 Typically at temperatures below 470°C the decomposition of kerogen into soluble bitumen is a fairly rapid step compared to the decomposition of bitumen to oil-. However, at temperatures above 470°C, the decomposition of bitumen appears to be rapid(a'. The kinetics of oil shale pyrolysis will be dicussed in Section 3.1. 2.3 The Oil Shale Pyrolysis Process There are many types of retorting processes described in the literature. Only the most developed ones are discussed in the thesis. Retorting processes can be classified into two types: the direct-heating processes and the indirect-heating processes. The direct-heating processes rely on internal combustion of fuel with air or oxygen within the bed of shale to provide all necessary process heat requirements. 9 The indirect-heating processes rely on the heat provided by the injection of heated solid or gaseous heat-carrier media into the retort. Among the direct-heating processes are the Gas Combustion retorting process and the Union Oil retorting process'11' 51. The Gas Combustion retorting process features the continuous pyrolysis of coarsly crushed oil shale in a vertical kiln retort. The heat is provided by an internal combustion of the process-derived fuel with air within a downward-moving bed of shale. The kerogen in the shale is pyrolyzed or decomposed by heat in the retorting zone. The necessary heat is provided by the hot gases rising from the combustion zone. As the kerogen pyrolyzes, it yields oil (as vapour), gas, and a residual carbonaceous.product which adheres to the solid retorted shale. All vapours and gases are swept upward, and the solids descend into the combustion zone where oxidation of the carbon occurs to produce the hot flue gases. The oil recovery of the Gas Combustion process is in the range of 80 to 90 percent of the Fischer Assay. The Union Oil retorting process features a 'rock pump1 shale feeding device which pushes oil shale upward into an inverted-cone-shaped vessel which is open to the atmosphere at the top. The shale solids, after having been pyrolyzed, overflow the vessel walls at the top. Air enters the bed of shale at the top and supports combustion within the bed • of shale. The flow of air, combustion product gases and pyrolysis product vapors is downward, countercurrent to the upward flow of solids. The TOSCO II, the Petrosix, and the Lurgi-Ruhrgas processes use indirect heating( 1 ' (5 ' . The TOSCO II oil shale retorting process'6' features the use of a circulating load of heated ceramic balls as a heat carrying medium for transferring the necessary process heat to finely crushed oil shale for pyrolysis of the shale's kerogen in a rotating drum type of vessel. The vessel is kept under an internal pressure of about 135.8kPa to prevent admittance of air. No combustion occurs in the retort. The ceramic balls and the finely ground spent shale are first separated from each other by a trommel. Then the ceramic balls are reheated in a separate gas-fired furnace. Some of the balls break from repeated thermal shock of alternate heating and cooling. The TOSCO II retorting technology is well advanced and has been demonstrated at a semi-works scale. The Lurgi-Ruhrgas process requires finely crushed oil shale. It features the use of heat carrier solids of small particle size such as sand grains, coke particles, or spent shale solids derived from the shale retorting process. The hot heat-carrier solids are mixed with the oil shale in a sealed screw-type conveyor and pyrolysis occurs during the mixing operation. In the Petrosix retorting process( 1 ' (5 ' heated recycle gas rather than combustion air is injected into the bed of shale to provide the necessary heat for pyrolysis. The retort unit is 5.48m in diameter and is capable of processing about 2500 tons of oil shale feed/day. This scale of -operation is much greater than any other modern retorting process. This process utilises a vertical kiln retort very similar in design to the Gas Combustion retort. However, in this case, recycle gas heated in a separate furnace is used instead of combustion gas. Most of the processes described above are slow retorting processes in which large particles are slowly heated to reaction temperature. In theory, rapid pyrolysis processes tend to produce higher liquid yields than slow retorting processes due to the minimization of secondary cracking of the liquid to solids and gases. Typically, slow retorting processes have a particle heating rate around 12°C/min whereas the rapid retorting processes have a heating rate of upto 33,000°C/min. For liquid yield reasons, fluid bed technology has been suggested as a basis for an oil shale retort. Marshall J. Margolis'7' investigated the pyrolysis of Eastern U.S. Oil shales in a fluidized bed system. The fluid bed reactor provides a rapid heat-up of the oil shale particle because of its excellent heat transfer characteristics; and its short vapour residence time helps to mininize coking and oil decomposition. The basic unit consisted of a quartz reactor vertically mounted within an electrically heated tube furnace and was capable of operating at temperatures up to to 1200°C. The fluid bed capacity was approximately 15 grams of shale. Raw shale was fed into the fluidized bed through a 12 variable speed screw feeder which was mounted at the top of the reactor. Nitrogen gas was used to maintain fluidization. During operation, the spent shale was continuously displaced as raw shale was added to the reactor bed. Volatile products were swept from the reactor into a series of two cooled traps. The amount of oil produced was determined by weighing the amount of material collected in the traps and correcting for water and particulate matter content. The experimental results showed that there is an improvement over the carbon removal achieved under Fischer Assay conditions. Also, evaluation of spent shale carbon analyses and product collection data suggest that oil yield equivalent to 120-140 % of the Fischer Assay may be achieved. Salib, Barua and Furimsky(8> have studied the retorting of New Brunswick oil shales in direct and indirect modes in a pilot scale moving bed retort. The retort had a square cross-sectional area of 0.053m2 and a height of 2.4m. The crushed shale was fed by gravity through a rotary valve at the top of the reactor. The descending shale was heated by the ascending hot gas (air + recycle retorting gas). Oil was recovered from the off gases by hot cyclone, condenser, packed column and electrostatic precipitator. Spent shale was discharged by an extraction screw. The effect of shale grade, bed height, retort temperature profile, recycle gas and its distribution, and air feed rate on oil recovery were studied. The maximum oil recoveries are 81% and 89% of the Fischer Assay for direct and indirect mode retorting 13 respectively. Levy et al1'3 1 have investigated the vapour phase thermal behaviour of shale oil samples derived from the Condor, Nagoorin carbonaceous and Stuart deposits of Australia. The oil vapours released during retorting were passed through packed beds of sand, or the spent shale ash corresponding to the particular oil at temperatures between 500 and 600°C over a range of residence times. The results showed that there was minimal oil cracking over the sand. Oil degradation was attributed to thermal cracking. When the oil vapours were passed through the spent shale, their behaviour was quite different from that over the sand. The spent shale ash catalysed oil degradation greatly and resulted in major oil losses due to coking even at 500°C the lower range of the temperature studied. Dung et al'*"' report the pyrolysis behaviour of Condor and Stuart Shales in a 150mm diameter fluidized bed process development unit. The process used the hot shale ash as a heat carrier. The aim of the project was to determine if the recycle of the shale ash from this oil shale would adversely affect the oil yield. When the ash to shale recycle ratio was two, the results show an oil yield of loss of 28% compared to retorting in the absence of hot shale ash. The loss oils were mainly heavy fractions which adsorbed onto the shale ash. The loss seriously affect the economic feasibility of oil shale processing. Dung(1|5) has studied a new concept for retorting oil shales. The principle of the 14 proposed method was the transfer of heat through walls separating the heat source and the shales. The heat was supplied by combusting spent shale. The oil shale particles were conveyed by gas through heat exchange tubes, the heated shales then being retorted in the absence of ash. Calculations based on data and correlations in the literature demonstrated that shale particles can be heated effectively while being conveyed, in dilute phase, in heat exchanger tubes immersed in a fluidized bed of combusting spent shale. Experimental information about the performance and operation of the reactor is required to confirm the proposed advantages. One of the main disadvantages of the fluidized bed is the difficulties in handling relatively large particle sizes (>1 mm) which may lead to unstable fluidized bed operation. The employment of a spouted bed reactor could solve this problem. Spouted bed technology was developed in the 1950's in Canada to dry wheat with air prior to storage. The properties and applications of spouted beds are described in a book by Mathur and Epstein'9' and other literature' ,0|'(U1. Leite et al'16) have studied oil shale pyrolysis in a 8cm diameter spouted bed reactor. The oil shale of 1.11mm particle size is pyrolyzed at 600°C at a feed rate of 2.7 to 9.0kg/hr with nitrogen, steam and air mixture as spouting gas. 15 Jarallah'2' has studied coal pyrolysis in a 12.8cm diameter continuous spouted bed reactor. The effects of coal feed rate, particle size, reactor temperature and bed height on yields from two British Columbia bituminous coals and one Alberta sub-bituminuous coal were investigated. The spouting gases used were either nitrogen or a nitrogen-carbon dioxide mixture. Coal sizes between 0.6 and 3.36mm were fed at atmospheric pressure to the electrically heated reactor containing sand as spouting media. The tar yield was determined by sampling the outlet gas through a series of cooled impingers. In this thesis, the spouted bed developed by Jarallah12' was used to study the pyrolysis of New Brunswick oil shale. 2.4 Parameters Affecting Oil Shale Pyrolysis Studies show that the oil shale pyrolysis is affected by many parameters, such as pressure, temperature Sc heating rate, particle size and shale feed rate. Bae(17' has investigated the effect of pressure and surrounding atmosphere on the retorting of oil shale. He conducted batch experiments at 510°C using different retort gases such as N2, C02, H20, NH3, and H2 at pressures ranging from atmospheric to 2500 psig. Test results in Figure 1 indicate that high pressure reduces the oil yield significantly, but produces a larger volume of light hydrocarbon gases. High pressure favours the secondary reaction of the primary volatiles. Oil yields were generally 30 0 500 .1000 1500 2000 2500 PRESSURE, PSIG Fig 1: Effect of Pressure on Oil Yield ( Adapted from Reference No. 17 ) 17 similar in nitrogen than carbon dioxide atmospheres. As the aim of the present project is to find conditions for high oil yield, experiments have been conducted under atmospheric pressure. Furimsky et al(18' have studied the retorting of thirty oil shales samples form Eastern Canada by Fischer assay retort and pyrochem retort. The oil yield increased significantly with hydrogen as the retorting gas. This is due to the stablization of reactive radical intermediates by hydrogen which would otherwise polymerize to higher molecular weight species. The effect of temperature on oil shale pyrolysis, especially the oil yield, is very significant. Studies show that the kerogen in oil shale will begin to decompose at 250°C. and will even pyrolyse completely at temperatures around 400°C. Table 5 lists the results of a temperature study on Colorado oil shale by Hill* 19). It can be seen that for lower temperatures, a longer retorting period is required. From a practical standpoint, therefore a higher temperature is preferred to shorten the retorting period. The temperature affects both the decomposition of oil shale and the secondary reactions of the primary volatiles. In the absence of secondary reactions, the oil yield will increase gradually with temperature. In the presence of substantial secondary reactions, an increase in temperature will enhance the cracking of the oil into lighter volatiles. Therefore, typically there is a maximum oil yield at an TABLE 5: Effect of Temperature on Oil Yield Test Temperature CO Durat i on (hr) Oil Wt% Yield %Fischer Assay D-4 D-5 D-19 D-7 D-22 D-16 0-17 D-10 D-1 331 347 353 364 395 399 420 427 500 550 425 159 312 71 86 . 5 38 .0 37.5 13.5 4.0 4.8 4.3 6.0 7.6 8.0 8.8 8.9 7.6 33.6 40.4 39. 1 52.6 71.6 72.8 80.0 78 . 1 92 .6 Tests were performed at the University of Utah All experiments were carried out at atmospheric pressure 19 optimum temperature. This is in agreement with the findings of Liu et al(20>. They have studied the pyrolysis of 20-40 mesh Colorado oil shale in a twin fluidized bed reactor. A mixture of nitrogen and steam was used as the fluidizing gas. The feed rate of oil shale was 7.2Kg/hr. Figure 2 shows the test results. It indicates that oil yield increases from 60% Fischer Assay at 427°C to 67% Fischer Assay at 491°C. Beyond 491°C, oil yield decreases to 42% Fischer Assay at 548°C. The optimum retorting temperature for this condition is estimated to be approximately 477°C. The study of the effect of particle size on oil yield is necessary because the operational requirements of a retorting process frequently require the shale to be of a specific particle size range. For example, the TOSCO II process requires feed shale to be smaller than 1.27cm , so that the spent shale can be separated from the 1.27cm diameter heat-carrier ceramic balls by screening. Gas combustion and Petrosix processes require discrete particle larger than 0.64cm size. A series of Fischer Assays was made on 100 gram of a Colorado oil shale crushed to various sizes range from 2 to 65 mesh and pyrolysed according to the standard retorting rate. The results are listed in Table 6 and it can be seen that the effect seems to be very small. Jarallah<2) has also studied the particle size effect on coal pyrolysis and found that there is a higher oil yield with decreasing particle size. Figure 3 shows the plot of coal particle size versus tar yield. His explanation is that 100 O 20-i i 1 1 1 1 700 800 900 1000 1100 1200 . TEMPERATURE OF RETORTING CHAMBER °F Fig 2: Effect of Retorting Temperature on Oil Yield ( Adapted from Reference No. 20 ) ro O TABLE 6: Effect of Particle Size On Oil Yield Particle Size Number of Oil Wt% (mesh) determinations Minus 2  14.22 Minus 4  14.78 Minus 8 5 14.37 Minus 20  14.45 Minus 65  13.47 100.Ogm samples of Colorado oil shale No. 44L-69 were heated from room temperature to 500"C in 50 minutes and then maintained at 500'C for an additional 70 minutes. 22 Q LU AO LJL < 30 LL O 20 >-< 10 0 T r 580 C F0 = 1-1:0.2 Kg/h 4 0 1 2 3 PARTICLE DIAMETER, mm Fig 3: Effect of Particle Size on Tar Yield ( Adapted from Reference No. 2 ) 23 for smaller particles, the pyrolysis is more rapid and the opportunity for polymerization and deposition within the particle is reduced. However, the Fischer Assay values for the New Brunswick oil (Table 12) shale A indicate that the smaller oil shales particles have a smaller potential oil yield, and therefore comparisons of particle size effects should not be based on the magnitude of the oil yield alone. The study of shale feed rate on oil yield is of special interest in this case. Jarallah'21 found that increasing coal feed rate has negative effect on oil yield. The char accumulated in the reactor apparently enchanced the secondary cracking of tar to volatiles. Therefore, it is necessary to observe if the spent shale accumulated in the reactor over the time of the experiment would have a similar effect on oil yield. 2.5 Heat Transfer in Spouted Beds Because retorting is an endothermic process, it is very important to understand the heat transfer in a spouted bed. In our experiment, the oil shale is fed at room temperature to the apex of the spouted bed. It is necessary to find out the time required for the oil shale particle to reach the bed temperature, and whether a significant intraparticle temperature gradient exists. In other words, knowledge of the temperature history of the oil shale particle helps in understanding the pyrolysis kinetics. 24 Work on spouted beds to 1974'can be found in the book by Mather and Epstein'9). The spouted bed consists of two distinct regions: the spout and the annulus. Figure 4 shows a schematic diagram of a spouted bed. In the spout, the average gas velocity is often one or two orders of magnitude higher than the annulus, whereas the volume fraction of particles, (1-e), is at most one-fifth of that in the dense phase annulus. An equation"9) for estimating the heat transfer coefficient in the spout for the particle Reynolds number higher than 1000 is, Nu = A + BPr1/3 + Re0-55 (2.1) where A = 2/[1 -(1 -e)1/3] and B = 2/3e For the annulus region, the packed bed correlation(9' for estimating the heat transfer coefficient where Re for the particle is generally smaller than 100 is, Nu = 0.42 + 0.35 Re0•8 (2.2) It should be noted that the above correlation is based on experimental data using air near room temperature. In this research, the reactor temperature is at least 450°C, therefore equation 2.2 may only give an estimate of the heat transfer coefficient. It can be shown that the heat transfer coefficient in the spout is much higher than in the annulus region. Fig 4: Schematic Diagram for Spouted Bed 26 However, the time which a particle spends in the spout is very small compared to that in the annulus. Therefore, the total heat transferred in the spout will be less than that in the annulus. The time required to bring a feed particle close to the bulk solids temperature is given by the following unsteady state equation, From this equation, the time required to heat up a typical size oil shale particle, say 2 mm diameter from room temperature to a bed temperature of 500°C was estimated to be of the order of 20 seconds. Since the practical mean residence time in the annulus is at least several minutes, the steady state concentration of bed particles reaching the bed temperature is high. Therefore, the overall heat transfer rate would not normally be limited by the external heat transfer. For equation 2.3, the temperature within the particle is assumed uniform. However, in the case of the spouted bed where large sized particles may be used, the intraparticle temperature gradient could not be ignored. The magnitude of the intraparticle temperature difference relative to the temperature difference between the particle surface and fluid is determined by Biot number, Bi =h r /k , H p p p provided that the Fourier number FoH=at/rp2 , which is a dimensionless time variable, exceeds a minimum value of 0.2. The relative magnitude of intraparticle temperature Tp Tpo Tb " Tpo - = 1 - exp[ * t (2.3) 27 difference decreases with decreasing Bi , the maximum value becoming less than 5% of the temperature difference between the fluid and particle surface at BiH= 0.1. For the oil shale particles used in our experiment, assuming that an intraparticle temperature gradient exists, the particle temperature profile can be predicted by the unsteady state conduction equation, 3T a 3(r23T/3r) = (2.4) 3t r2 3r and can be calculated as a function of time for the variable conditions along the 4 different regions of the spouted bed: spout, fountain (upward), fountain (downward) and annulus region, by a numerical solution of this equation as the longitudinal profiles of gas and particle velocities, gas temperature and spout voidage are known. The boundary condition in this case is, Kp(3T/3r)r=rp =hp(Tb - Tr=rp) (2.5) The details of the computer program are given in Appendix A. Table 7 and 8 list the particle temperature history for oil shale of 3mm, 1.5mm and 0.75mm diameter after one and two passes in the reactor respectively. The temperature history is estimated at a function of time along the spout, fountain (upward), fountain (downward) and annulus regions. The reactor temperatures chosen are 723, 28 773 and 823K. The velocity of the oil shale particle at the apex of the spout is assumed to be zero. From the typical results shown in Table 7, it can be seen that for the 3mm particle size oil shale, there is a considerable temperature gradient in the spout, fountain (upward) and fountain (downward) regions. But during the slow travel down in the annulus section, the temperature gradient is effectively relaxed. It should be noted that after the first pass through the four regions, the particle has not yet reached the reactor temperature. In fact, the temperature of the particle is only at 568.0 - 606.2K which is not even high enough for pyrolysis to start. The particle has to travel the cycle the second time in order to effectively reach the reactor temperature, and pyrolysis is expected to take place in the annulus. For the 1.5mm diameter size oil shale, a temperature gradient still exists in the particle but is less significant than for the 3mm particle size. For reactor temperature 773 and 823K, the particle reaches to 732.1 and 767.6K respectively in the annulus region, which is high enough for pyrolysis to begin. Again, pyrolysis is expected to take place in the annulus. For the 0.75mm particle size oil shale, intraparticle temperature gradient greater than 10K hardly exist. At the top of the spout, the particle has not reached the reactor temperature but the temperature is sufficient for pyrolysis to take place. As the 0.75mm oil shale is smaller than the Table 7: Particle Temperature History for 3.0, 1.5 and 0.75mm Oil Shale (After One Pass) Reactor Temperature (K) PartIcle S Ize (mm) Part icle Spout (K) Founta1n (Upward) (K) Founta i n (downward) (K) Annu1 us (K) 723.0 3.0 centre surface 361 .8 431 .4 367 . 4 422 . 3 372 .9 4 18.1 567 . 1 568 .0 1 . 5 centre surface 533 .8 566.2 543.6 559 . 3 550.0 557 . 9 690.0 690. 1 0. 75 centre surface 693 . 2 697.8 696 . 1 696.8 696 . 8 697 . 1 722.2 722 . 2 773.0 3.0 centre surface 359.8 439. 1 366 . 7 428 . 1 373 423 . 59 1 . 1 592 . 2 1 . 5 cent re surface 545 .0 584 . 3 557 . 8 575.6 565 . 574 . 731.9 732 . 1 0.75 centre surface 732 .3 738.7 736 .4 737 .3 737 . 737 . 771.9 771.9 823 . 0 3.0 centre surface 347 . 2 438 . 1 356 . 4 423 . 9 365 419 604 . 9 606 . 2 1 . 5 centre surface 533 . 584 . 552 . 8 572 .8 562 . 572 767 . 3 767 . 6 0. 75 centre sur face 757 . 767 . 764 .5 765.8 766 766 821.0 82 1.0 Inlet temperature of the particle 1s assummed to be at 298K The temperatures are calculated as particle leaving different regions of the spouted bed reactor to Table 8:Particle Temperature History for 3.0, 1.5 and 0,75mm Oil Shale (After Two Passes) Ktaac t or T empera t ure (K) Particle S i 2e (mm) Part icle Entrance (K) Spout (K) Founta i n (Upward) (K) Founta i n (downward) (K) Annu1 us (K) 7 2 3.0 3.0 centre surface 5G7 . 1 568 .0 590.9 6 16.4 593 .0 613.1 595 .0 6 11.5 666 . 3 6G6 . 3 1 . 5 cent re surface 690.0 690. 1 708 . 3 7 10. 9 709 . 1 7 10.3 709 . 6 7 10.2 7 20 . -1 720. 5 0.75 cent re surface 722 . 2 722 . 2 722.9 723.0 722 .9 723.0 723.0 723 .0 723.0 723 .0 7 7 3.0 3.0 centre surface 591 . 1 592 . 2 615.3 645 . 6 617.9 64 1 . 4 620. 5 639 . 6 703 . 6 704 .O 1 . 5 cent re surface 731 .9 732 . 1 753.3 756.7 754 .4 756 .0 755 . 1 755 .9 7G9 . 5 769 . 5 0.75 centre surface 771 .9 77 1.9 772.9 772.9 772.9 772.9 772.9 772 . 9 773.0 773 . 0 823.0 3 .0 centre sur face 604 . 9 606 . 2 625 . 9 663 . 7 629 . 8 657 . 8 633 . 6 655 . 8 732.7 733 . 2 1 . 5 centre surface 767 . 3 767 . 6 792 . 4 797 . 8 794 . 4 796.5 795 . 5 796 . 5 8 17.1 8 17.1 0.7 5 cent re surface 82 1 .0 821 .0 822 .8 822.8 822 . 8 822.8 822 . 8 822 . 8 823 .0 823.0 The temperatures are calculated as particle leaving different regions of the spouted bed reactor O 31 spouting sand, 1.11mm , it is expected that some of the oil shale will actually escape from the fountain (upward) region and be entrained to the cyclone. Even in this case, these particles will still undergo pyrolysis. In the actual experimental case, there is a 17.8cm long section between the feed point and the apex of the spouted bed. A supplementary program (in Appendix A) was written to calculate the particle temperature profile for this section. It was found that the oil shale particles are still essentially at room temperature as they leave this section. This indicated that the above assumption that the particle at the apex of the spouted bed is at room temperature is correct. 32 3. KINETICS 3.1 Literature Review of the Kinetics of Oil Shale Pyrolysis Several investigat ions(22'"( 34 > (39 1 " (* 1 ' have been carried out on the kinetics of the decomposition of kerogen in oil shale. The first comprehensive experimental study of the process was reported by Hubbard and Robinson(22>. They studied the decomposition of kerogen in Colorado oil shale at temperatures from 400 to 525°C by heating the shale sample in the absence of oxygen at atmospheric pressure and measuring the decomposition products. The first decomposition products to form were gas and bitumen. On further heating, the bitumen decomposed to form the final products: gas (the non-condensable vapors), oil (the condensable vapors) and carbonaceous residue. Hubbard and Robinson interpreted their data by assuming that the total amount of kerogen that decomposed was equal to the total amount of gas, oil and bitumen. Braun and Rothman'2"' studied the Hubbard and Robinson data and proposed to include a thermal induction period in the data analysis, and represented the kinetics of oil production by a simple mechanism involving two consecutive first order reactions. The thermal induction period was required to account for the non-isothermal heating effects in the Hubbard and Robinson experiments. The pyrolysis of kerogen can be expressed as: K => B + G, + C, (3.1) k2 and B > A + G2 + C2 (3.2) The rate of kerogen decomposition is given by, 3K = -k,K (3.3) 3t The net rate of bitumen formation and decomposition is, 3B = k , f ,K - k2B (3.4) 3t The rate of oil production is given by, 3A = k2f2B (3.5) 3t The rate of gas production is 3G = k,f3K + k2f,B (3.6 3t Integrating equation (3.3) for K=Kq at t=t gives: -k,(t-tQ) K = K0e (3.7) By combining (3.4) and (3.7), and integrating for B=0 34 c=tQ, then the amount of B, bitumen at any time is k,f,K0 -k,(t-t0) -k2(t-tG) B = [ e _ e ] (3.8) (k2-k,) Combining equations (3.5) and (3.8), and integrating for A = 0 at t=tQ , then the fraction of initial kerogen A/Kq that is converted to oil at any time t is: fA . r -k,(t-t0) -k2(t-t0) U2[ 1- e ] - k,[1- e ]} K0 (k2-k,) (3.9) Combining equations (3.6) and (3.8), and integrating for G=0 at t=tD' the fraction of initial kerogen G/KQ that is converted to gas at any time t is: G -k,(t-t0) — = f 3[1-e ] + fif« -k,(t-t0) -k2(t-tQ) i k2(l-e ] - k,[1-e ]} (k,-k2) (3.10) Braun et al'2"1 used equation (3.9) to analyse the data of Hubbard and Robinson1 ZZ) for production of oil from a Colorado oil shale having a Fischer Assay of 26.7 gal/ton. The measured and calculated values o£ A/KQ are found to be in agreement with each other. 35 Johnson et al(25) used thermogravimetric analysis (TGA) to study the pyrolysis of oil shale spheres. The sample weight was measured while the temperature was increased with heating time. They developed a complex kinetic model which incorporated both heat transfer and chemical kinetics, but the kinetic scheme required a series of ten coupled chemical reaction steps. Campbell et al(27) obtained kinetic data on Colorado oil shale pyrolysis by both the isothermal and the non-isothermal technique. The non-isothermal results show that the oil evolution process can be quite accurately represented as a first order reaction. Granoff and Nuttal<28> investigated the pyrolysis kinetics for large single particle (12.7mm diameter cylinder and sphere). The experiment was carried out at 384 to 520°C with nitrogen as pyrolyzing gas. The weight loss of the oil shale particle was continuously measured with a Cahn recording thermobalance. They also obtained the centreline temperature histories for the oil shale with a microthermocouple. The non-isothermal shrinking-core model and non-isothermal homogeneous model were developed in order to describe the pyrolysis process. For the non-isothermal shrinking-core model, it is assumed, that the reaction always occurs at the interface between the unreacted core and the surrounding spent shale layer. The model consists of the dynamic distributed energy balance, convective and radiant surface boundary condition, 36 and a first order kinetic controlled shrinking core material balance. The resulting equations must be solved simultaneously, since the rate of core shrinkage is strongly temperature dependent as indicated by the Arrhenius expression. The partial differential equation describing the dynamic temperature profile within a sphere, is, 3TS 1 3 3TS ba PsCps ~= M r2( ) ] + C( ) A Hrxn at r2 3r 3r at (3.11) (wQ-wt) a = (WQ-WOJ where the initial condition is, T = T. ... , at t=0 s initial Tg= constant steady-state value at t=0 and the boundary condition is, Qrp = hAp(Trp-Tg) + 5eAp(Tr?a-Tw') (3.12) The shrinking-core material balance equations are, 3rc AE kiexp( ) (3.13) at RTC 37 3a 47rrc2ki exp[ (-AE/RTC ) /C ] = - (3.14) 3t 0 . 757rrD3C therefore the appearance rate of individual species is given as: 3a 4rrrc2ki exp[ ( -AE/RTC ) /C{] •= ~ (3.15) 3t 0 . 757rrp3Ci The model fits very well at high temperature (520°C), but is not so good at the lowest temperature. The second model developed was the non-isothermal homogeneous model in which it is assumed that there are no temperature gradients within the particle. The particle temperature is given by: 3TS PsvpCps = hAp (Tg-Ts) + 5«p Ap(Tw«-Ts«) + k(l-a)VD 31 (3.16) The model was able to match both the high and low temperature conversion for small and moderate oil-sized spherical particles where the particle temperature is assumed to be uniform. Wang and Noble'31 1 carried out oil shale pyrolysis under non-isothermal conditions between 350 and 500°C. and at different pressures (78 and 765 kPa). They used a comprehensive analytical procedure to separate the oil shale into five individual components: polar, weak polar, 38 saturates, aromatics and olefins.•They proposed a simplified kinetic scheme that include the distribution of products as follows: 3Ci ki -Ei fKQ RT2 -EQ = exp[ -( )( ) exp( )] (3.17) at C RT C EQ RT Yang and Sohn<33) studied a Chinese oil shale, and found that the mechanism of kerogen decomposition can be represented by an overall first-order kinetics.. In view of the above survey, it appears that from an engineering standpoint, the rate of oil generation can be adequately described by an overall first order kinetics. 3.2 Development of the Kinetic Model A model was derived to predict the change of kerogen, bitumen and oil content of the oil shale with time. The basic idea is that upon the application of heat, kerogen in the shale particles is first decomposed to bitumen and gas. The bitumen is defined as the benzene-soluble organic material that does not vaporize but remains in the shale sample. Then the bitumen is heated to decompose to form oil and gas, and carbonaceous product adheaved to the shale mineral matrix. Oil is defined as the condensable hydrocarbons and other compounds escaping from the shale sample, whereas gas is defined as the non-condensable vapours escaping from the shale sample. The carbonaceous residue is the benzene-insoluble portion of the kerogen 39 remaining in the spent shale. On further heating, oil is decomposed to gas and carbonaceous products. The pyrolysis of kerogen is expressed as Kerogen > Bitumen + Gas + Carbonaceous residue Bitumen > Oil + Gas + Carbonaceous residue Oil > Gas The first two reactions take place in the solid phase and the time of reaction can be taken as the residence time of the solids. Whereas the oil decomposition occurs in the gas phase, and the time for reaction is very short i.e. the mean residence time of the gas (Vol of the gas phase/Flow rate of gas). The kinetic equations used to describe the reactions are taken from Braun and Rothman'13' and were presented in the beginning of Section 3.1. In the present research, the amount of oil produced is measured by sampling of the off-gas. Neither kerogen nor bitumen were measured. The structure of the spouted bed is not taken into account. However, a few assumptions are made based on the charactistics of the spouted bed. 1) F0, C,„, F . , Fi, F2, V are all constant. o,k0g,in,z 40 2) Bed solids and gases within the reactor are well mixed. 3) The intraparticle temperature gradient of the oil shale is ignored because the time required to heat up the particles (in the range of 20 seconds, Section 2.6) is insignificant compared to the average holding time of the particle in the reactor (in the range of 30 minutes). The configuration of the model is shown as below: F2 Fg,oUt CA^) <Vfc) CK*(t)A A CB(t) Unsteady State Material Balance weight weight weight weight weight of solid + of gas - of solid - of gas = Accumulated fed in inflow withdrawn outflow & entrained dW Fo + F(g,in)P(g,in) " <Fi + F2> " F(g,out)P(g,out) = (3 dt Assuming F . p . = F up , (as spouting gas accounts ^ g,in^g,in g,out g,out c for 97% of the total gas outflow), then (3.19) becomes, dW F, - F2 = (3.20) dt Kerogen Balance Kerogen Kerogen Kerogen Kerogen entering - withdrawn - decomposed = Accumulated with shale & entrained dCK" (3 21) F0CKo " F2CK2 - FICRI - rK = (J.^W dt Bitumen Balance B i tumen produced by kerogen Bi tumen decomposed Bi tumen w i thdrawn & entrained Bi tumen Accumulated 42 CB " F2CB2 " FiCB1 dCBW dt (3.22 Oil Balance Oil produc ed by bitumen Oil decomDOsed Oil entrained Oil Accumula ted rA " FgcA = dCav dt (3.23) Reaction Kinetics 1-f i Kerogen fl Gas 1<2 Bitumen l-f2 Gas Oil" k3 "> Gas (3.24) rB = f,k,CKW - k2CBW (3.25) rA = izkzCBU - k3CA V (3.26) 43 From the experiment, F0, F1,""F2, V, C,,n are known, and KU O o from the literature, k1f k2, E1( E2 f,, f2 are known, then W(t), CK(t),Cg(t) , c^(fc) can ^e solved from equations (3.20), (3.21), (3.22) and (3.23). A. simplified model with one less equation to solve was based on further assumption that W was constant at the average of the initial weight and final weight of the bed. This model can be used to work out k3, E3 and then solve for C„(t) , Cn(t) and C.(t) . KB A For Kerogen Recall equation (3.21), dCKW F0CKo ~ F2CK2 - F,CK1 " rK = (3.21) dt By assumption CK1 = CK2 = CK because of backmixing, and W=constant then equation (3.21) becomes, dCK F0CKo - F2CK - F,CK " rK = W (3.27) dt Substitute (3.24) into (3.27),. dCK F0CKo - F2CK ~ F,CK - k,CKW = W (3.28) dt Rearranging (3.28) gives, F0CKo F, F2 dCK - (k, + + )CK = (3.29) W W W dt 44 and A = FoKo W Fi F2 B = (k,+ — + —-) W W dCK = A - BCK dt (3.30) For Bitumen Recall equation (3.22), dCBW rB - F2CB2 " FiCB1 = (3.22) dt For CB1 = CB2 = Cg, and taking W constant, and substituting (3.25) into (3.22), gives dCB f,k,CKW - k2CBW -(F, + F2)CB = W (3.31) dt Rearranging (3.31) gives, F1 F2 dCB f,k,CK " ( + * k2)CB = (3.32) WW dt Let C = f , k , F, F2 D = + —+ k2 W W To solve for C„, equation (3.30) and (3.32) have to b b taken together. Using Laplace transformation, these become, A -Bt CK =—(1 - e ) (3.33) B -Dt -Bt CB = CA( Cn+ C12e .+ C13e ) (3.34) 1 where C\]= BD 1 C]2: (D2-BD) C13= (B 2-BD) Then Kerogen = KBW (3.35) (mass) Bitumen = CBW (3.36) (mass) For Oil Recall equation (3.23), dCAV rA " FgCA = dt (3.23) 46 Substitute (3.26) into (3.23), dCAV f2k2CBW - k3CAV - FqCA = (3.37) dt f2k2CBW Fg dCA - CA( —+ k3) = (3.38) V V dt Let P f2k2CBW . F g v Q = — + k3 v v therefore, P -Qt CA = — ( 1- e ) (3.39) Q Total oil accumulated over time, t=0 and t=t t Oil = / CAFqdt (3.40) 0 Yield Predictions of equation 3.40 will be compared with the accumulated oil yield determined by sampling the outlet vapour. 47 4. EXPERIMENTAL EQUIPMENT AND PROCEDURE* 4.1 Pyrolysis Apparatus The apparatus used in this thesis was originally designed and built by A. Jarallah'21 for coal pyrolysis. A number of modifications were made to improve the operation and reliability of the apparatus. The design characteristics of the major units are listed in Table 9. A schematic diagram of the experimental apparatus is shown in Figure 5. A new feed system was installed to replace the original vibratory feeder which was. difficult to control and was not designed to handle particles below 1mm diameter. The new system includes a plexi-glass hopper, a rotary feeder and a inclined glass section. The feed hopper was 305mm high x 165mm diameter. It had a conical bottom which was fitted with a 12.5mm diameter ball valve. A plastic tube connected the feed hopper and the inclined inlet pipe section to balance the pressure in the feed hopper with that in the reactor in order to get a constant feed rate. A syntron magnetic vibrator (Model V-2-B) was mounted on the bottom of the hopper which aided the flow of the oil shale out of the rotary valve. The valve rotation speed was controlled by the G K Heller motor controller. Because of the low feed rate required, a 30:1 gear reductor was installed. The controller was always set * The author is indebted to Dr. G.K. Khoe who assisted with the modifications to the apparatus, and made many of the improvement in techniques and helped carry out some of the experimental runs. TABLE 9: Design Characteristics of Spouted Bed Pyrolyzer System Reactor: Material - 317 Stainless Steel Inside diameter - 128mm Wall Thickness - G.Gmm Cone Angle - 70' Disengaging Section Diameter - 255mm Height (Includes cone and disengagement sect ion) - 1.22m Spent Shale Receiver: Material - Mild Steel Outside Diameter - 305mm Height - 0.91m 0 i1 Sha1e Hopper: Material Steel - Plexi-glass Outside Diameter - 165mm Height - 305mm Spouted Bed Furnace: Electrical Rating - 6.9kW Maximum Temperature - 1200'C Heaters: 6 1/4-Round 304mm high x 178mm I.D. Heated Length - 0.69m Spouted Gas Preheater: Electrical Rating - 8.45kW Maximum Temperature - 1200'C Heaters: 4 semi-cy1inderica1 69.85mm x 44.45mm I.D Flexible electrical heating tape Heated Length - 0.69m 0 I 1 Sha1e Feeder: Rotary Feeder 00 Gas-Sol id Cycl Condenser: 0 i1 Rece i ver : Oil F i1ter: P i p i ng: Material - Stainless Steel Diameter - 150mm Cylinder Height - 500mm Cone Height - 300mm Shell - 316 Stainless Steel Inside Diameter - 128mm Wall Thickness - 6.6mm Tubes - 6 U-tubes 0.86m long Diameter - 12.7mm Area - 4130 cm1 Material - Glass and Stainless Inside Diameter - 229mm Height - 305mm Materia! - Stainless steel Diameter of orifice - 19.1m Ma ter I a 1 - 316 Stainless steel 5: A Schematic Diagram for the Experimental Apparatus 51 below 10% of the maximum speed rate and slight fluctuations were recorded. For this reason, a higher gear ratio reducer is recommended. The oil shale dropped from the rotary valve through the rubber tubing onto the copper pipe that was fitted inside a 25.4mm x 150mm QVF glass tube. A second syntron vibrator was attached to the end of the copper pipe to promote transfer of the oil shale directly to the inlet pipe of the reactor. Trials had been done in which the oil shale dropped directly onto the glass tubing itself, i.e. in the absence of the copper pipe, but accumulation of the solids and eventual blockage at the entrance of the inlet occurred. The off-gas sampling train from which the oil yields were to be determined was completely rebuilt from Jarallah's design123. Instead of stainless steel impingers, glass impingers were used. These were easier to handle and provided a clear view during the experiment. The impinger train was immersed in a tank filled with cracked ice and water. The whole system rested on a trolley which could be carried to a fume hood for oil recovery. The position of the off-gas sampling point was also relocated. Previously, it was at the outlet pipe of the drying column that was placed after the last impinger. However, some of the methylene chloride solution had evaporated with the gas and therefore affected the gas chromatograph results. The off-gas sampling point was therefore located at the upstream of the first impinger (refer to Figure 5). 52 The heating system was also modified. The preheater had to be rebuilt because the original semi-cylindrical heaters were burnt out and as the heaters were touching the surface of the stainless steel pipe, a hole had been made in the pipe as well. An electric forced air duct heater element enclosed in a fluidized sand bed was then tried. The sand was used to improve the heat transfer and avoid hot spots in the heater box. This system failed as the electrical element overheated and melted. Finally, the Lindberg half circle heating unit was used. These consisted of 4 semicylindrical heaters of 44.5mm ID which were clamped around the 3.8cm diameter pipe to give a heated length of 698.5mm. The total electrical rating of these heaters was 7.2kW. To avoid a short circuiting of these heaters as occurred in the previous case, an air gap of 1.5mm was left between the heating element and the pipe section. To increase the rate of heat transfer, the pipe section was filled with ceramic Raschig rings. A thermocouple was inserted in the air gap, and the temperature was controlled by an Omega controller. As it was the temperature in the air gap that was measured, the control was a bit difficult. In the original design, the main heater on the spouted bed reactor consisted of 16 quarter-cylindrical electrical elements each of 178mm ID and 152mm height. These were mounted around the main cylindrical section of the reactor to form a shell. An air gap of 18mm existed between inside of the heaters and the outside surface of the reactor. This 53 reduced the efficiency of heat transfer and the time for heating up was lengthy. After rearrangement, 6 quarter-cylindrical electrical elements were used. The heated section was 609.6mm high and the total electrical ratings for these heaters was 6.9kW. The air gap was reduced to 1.5mm, therefore the rate of heat transfer was improved and the heating up time was halved. The temperature was controlled by an Omega controller mounted on the control panel. There was a serious heat loss between the preheaters and the main heater, therefore a flexible electrical heating tape (Heavily insulated Samox) was wrapped around the conical section of the reactor. The total electrical rating was 1.25 kW, and the power applied was adjusted by a variac. Both the reactor and the downstream pipe were insulated by 5-7.5cm ceramic blanket to prevent heat loss to the surroundings. Other modifications included provision of new gaskets in all joints; and the installation of an insert in the horizontal pipe upstream of the cyclone to reduce the cross-sectional area available for flow, so as to avoid the settling of solids in this region. The temperature throughout the appartus was measured by by chromel-alumel thermocouples with 316 stainless steel sheath of 1.6mm diameter. In the reactor, and the preheaters, more rugged K-type thermocouples of 6.3 mm diameter were used. 54 4.2 Properties of the Oil Shale The oil shales studied in this project were supplied by the Research Productivity Council of New Brunswick. The original coarse oil shale, as received was reduced in size using a jaw crusher. It was then screened to 3 different sizes: 2-4mm, 1-2mm and 0.5-1mm which were stored in separate plastic buckets. Representative samples of the oil shales were sent to the General Testing Laboratories of Vancouver for proximate and ultimate analyses. The results are listed in Table 10. Table 11 gives the analysis of oil shale ash and carbon. It can be seem that there is slight variation among the different sizes. Table 12 lists the modified Fischer Assay results for the different sizes of oil shale A and reports that larger size fractions have better oil yields. These analyses were carried out at the Research and Productivity Council of New Brunswick. 4.3 General Procedure The basic mode of operation with this pyrolysis unit is to fill the reactor with inert solids (sand or spent shale), heat to the required temperature with air, then switch the gas to N2/C02 or N2. The velocity of gas is set at 10% above the minimum spouting velocity. (The calculation for mimumum spouting velocity is included in the computer program -Profile.) The oil shale is fed into the reactor over a period of 1 1/2 hour. In this case, the height of the bed will graduately rise with time. The oil is recovered from TABLE 10: Proximate and Ultimate Analysis of Blend of Oil Shale A Proximate Analysis % Moisture % Ash % Vol at 11es % Fi xed Carbon Ultimate Analysis (Dry Basis) % C % H % N % S •/. Cl 7. Ash % Oxygen (diff) 1 .69 72 . 53 25 . 17 0.61 100.00 15.91 2.05 ' 0.51 0.92 0.01 73.78 6 .82 100.00 TABLE 11: Analysis of Oil Shale Ash and Carbon Size Fraction (mm) 0.5-1.0 1-2 2-4 Total Organic Carbon (%) 10.2 10.6 12.4 Total Carbon (%) 12.3 13.3 14.7 SiO, (wt%) 43.4 41.9 41.6 A' '0> 10.6 10.4 10.3 Fe;0, 4.56 4.38 4.36 Can 8.32 9.03 8. 10 M9n 3.38 3.57 3.2Na'° 0.95 1.05 1.05 K'° 1.63 1.60 1.57 so> 1 .70 1 .87 2.22 Loss on Ignition 24.1 25.1 26 1 Ba (ppm) • 3 10 306 283 Mn 602 568 508 Sr 309 333 302 T1 2910 2560 2890 * Digested samples In mixture of acids, analyzed solution by inductively coupled Argon Plasma Spectrograph Carbon and Sulphur by Leco Induction Furnace Analyses by Can-Test Ltd. TABLE 12: Modified Fischer Assay of Oil Shales Shale Sample A Shale Sample B Size Fraction (mm) 0.5 0.5-1 .0 1-2 2-4 4 0.5-1.0 1.0-2.0 Oil Yield (wt0/.) 5 . 2 5.5 7.8 8 . 1 7 .95 8 . 1 7.6 7 . 85 7 .6 2 . 9 4 . 5 Wa ter Yield- (wt%) 2 . 1 2.0 2 . 2 2 . 3 2 . 25 2 . 2 1 .8 2.0 1 .6 3.2 2 . 4 Gas Lost (wt*/.) 1.2 5.5 3.0 1 .6 2 . 3 1 . 7 3.6 2 . 7 4 . 8 1 . 4 3 . 1 Char Yield (diff.) 91.5 87 .0 87 .0 88 .0 87 .0 88 .0 86 .0 92 . 5 90.0 Oil Yield (I.gal/ton) 12.1 12.7 18.0 18.6 18.9 17.4 17.4 6 . 7 10.4 Oil Density (g/ml at 15.5'C) 0.85G2 0. 8G70 0.8670 0.8563 0.8752 0.8573 0.8634 0.8678 0.8763 Analysed at Research and Productivity Council, Frederiction 58 the off-gas sampling train which is activated 5 minutes after the oil shale feeding begins. The gas samples are obtained by syringe during the experiment. Other sets of experiments were carried out in which the height of the bed material was kept constant. This was achieved by releasing part of the overflow material through a side pipe at the concial section of the spouted bed at specific time intervals (5 or 10 minutes). The overflow material dropped through a ball valve into a stainless steel pipe section with an end-cap. After closing the ball valve, the end-cap was unscrewed to release the overflow material. Then the end-cap was put on again, and the ball valve was opened to allow more material to be removed. In this way the reactor operated in a quasi-steady state, rather than having the solids holdup steadily increasing. 4 . 4 Detailed Operating Procedure The screened oil shale (about 2 kg) was loaded into the feed hopper. The required amount of inerts (Ottawa sand -14 +20 mesh, 5.9kg) was charged into the reactor from the top. This give a static bed height of 33cm. During charging, the air was turned on at a low rate to prevent the sand from dropping into the spouting gas inlet pipe and creating a blockage. To conserve nitrogen and carbon dioxide, air was first used for spouting to heat up the sand to the desired temperature. The tube section of the off-gas sampling line was installed and the ball valve closed. Then the air flow 59 was adjusted to the operating • flow, and the main reactor heater, spouting gas preheater, tape heater and the cooling water for the condenser were all turned on. During the heating up period, the assembly of the remaining parts including the impinger train was carried out. The impingers were prepared as explained in Section 4.5. Soon after the required temperature of about 500°C was reached, the air was replaced by a mixed gas stream of C02 and N2 (volume ratio 15:85), and a period of 15 minutes was allowed to purge the air before oil shale feeding was started. It was recognised that when the temperature reached above 500°C. the air stream should be replaced with inert gas, as there was some oil which had been deposited in previous experiments along the pipe, which could be ignited if the temperature became too high. Before the oil shale feeding was begun, a zero feed rate gas sample was obtained. This was done by opening the ball valve of the impinger train, followed by extracting a blank gas sample using a syringe. The ball valve was then closed. The sample was injected into the gas chromatograph. The oil shale feeder controller was set at the desired point and the feeder turned on. The time at which oil shale feeding started was recorded. After 5 minutes, the ball valve of the impinger train was opened and the gas sample pump was then turned on and oil collection started. The five minutes delay was designed to exclude the non-steady state effects during the initial minutes of feeding. Gas sample 60 flow rate was adjusted to the desired value and the gas sample rotameter reading was recorded. Gas samples were extracted at respectively 15, 30, 45, 60, 75 and 80 minutes. After the last extraction, the feeder, gas pump and heaters were turned off. Oil collection lasted for 75 minutes (5 to 80 minutes). All temperatures and pressures throughout the system were recorded, and the spouting gas rotameter reading was taken. The nitrogen inlet gas stream was used to cool the system. The feed hopper was emptied of unused oil shale to determine the oil shale feed rate. 4.5 Oil Collection The oil vapour is collected by isokinetic sampling of the off-gas. The velocities of the gases in the main pipe and the sampling tube are set equal. The first impinger was a 9.5mm x 30mm QVF glass tube filled with glass wool to provide a large contacting surface for condensation and filtering effects. This also helped to retain heavier oil fraction. The second to the fifth impingers were filled with a mixture of methlylene chloride and water (2:1 volume ratio). The sixth impinger contained methanol to trap the remaining oil-mist and entrained methlyene chloride. The last impinger contained water to trap any entrained methanol. The containers were interconnected in the last minute before the sampling line was activated inorder to prevent a backspill of methlyene chloride from the second impinger into the 61 first one. This could contaminate' the gas samples that were extracted through a septum at the upstream of the first impinger. For this reason, a slight vacuum was always maintained during an interruption, and the ice was added to the water bath just before the start of the oil collection. The day after the experiment, the impingers, interconnecting pipes and the tube sections of the sampling lines which connected to the main off-gas line were thoroughly rinsed with solvents (methlyene chloride and methanol), and then cleansed and dried before the next experiment. The solution in the impingers and the washing solution would then be filtered to remove all fine particles. The water was separated from the methyl chloride and methanol -oil solution by using separation funnel. Any remaining trace of water was removed by adding sodium sulphate to the solution. The solution was then filtered and evaporated in a rotrary evaporator (at 55°C, 20mmHg) to recover the oil. The recovered oil was weighed and the weight was recorded. 4.6 Gas Analysis The gas analysis was performed on a Hewett-packard 5710A gas chromatograph with a 3388A automatic integraton system. The column separates hydrogen, oxygen, nitrogen, methane, carbon dioxide and carbon monoxide. Because of the limitation of this gas chromatograph, the hydrocarbons with molecular weight higher than methane cannot be detected. For 62 a few experiments , the gas analysis was done by using a another chromatograph by K.C. Teo<35) which was able to resolve upto C6 hydrocarbons. The gas sample was extracted by a syringe through a septum at the upstream of the first impinger. The gas samples were analyzed and the values reported for each run. 4.7 Spent Shale Determination and Analysis After the experiment, the reactor and the cyclone receiver were emptied and the contents of each one were separatly weighed. The weight of the spent shale produced was obtained by subtracting the weight of original Ottawa sand from the total weight of above. Although some solids have passed through the cyclone and were not recovered, the weight of the material from the dust receiver was taken to represent the solid entrained. 63 5. RESULTS AND DISCUSSIONS 5.1 General considerations There were 26 successful experiments done on the New Brunswick oil shale A. The experimental conditions for each run are listed in Table 13. The oil yield is calculated from the weight of oil collected from the sampled gas, multiplied with the ratio of the mass flow rate of the sampled gas streams to the total gas output from the reactor, and then divided by the oil shale feed rate. Care was especially required in washing the impinger train and sampling lines to recover oil from the sampled gas because the final oil product weighed about 1-4 gm. The gas yield by species is calculated from the individual gas analysis, the total gas output from the reactor and the oil shale feed rate. Because of the limitation of the gas chromatograph, hydrocarbon gases of molecular weight higher than methane and gaseous sulphur, and nitrogen compounds are not detected. However, it is expected that the quantities of these gases are very small. The spent shale yield is calculated from the weight of shale remaining in the reactor and cyclone receiver vessel after the run and the oil shale feed rate. Data indicated that about 2/3 of the oil shale feed remained in the reactor and cyclone receiver , and 1/3 had passed through the cyclone as entrained fines. Because the cyclone is oversized, the collection efficiency is not high. Since a TABLE 13: Experimental Conditions for Each Run Expt. Particle Temperature Shale Initial Bed Pyrolyzlng Gas No Size Bed Inlet Feedrate Sand/Spent Shale Ni/COi mm CO (kg/hr) (kg) (vol'/.) 2 0.5-1 509 509 1 . 49 5.9/0.0 85/15 3 0.5-1 505 505 1 .37 5.9/0.0 85/15 4 1-2 503 503 1 . 65 5.9/0.0 85/15 5 1-2 501 501 1 . 33 5.9/0.0 85/15 6A 2-4 507 518 1 . 25 5.9/0.0 85/15 6B 1-2 540 528 1 . 29 5.9/0.0 85/15 7 1-2 554 554 1 .33 5.9/0.0 85/15 8 1-2 454 450 1 . 39 5.9/0.0 85/15 9 1-2 530 530 1 . 39 5.9/0.0 85/ 15 10 2-4 506 505 1.21 5.9/0.0 85/ 15 1 1 1-2 477 470 1 . 52 5.9/0.0 85/15 12 2-4 506 502 2.71 5.9/0.0 85/15 12A 2-4 506 502 1 .94 5.9/0.0 85/15 14 1-2 500 491 1 . 35 5.9/0.0 100/0 15 1-2 480 470 1 . 37 0.0/5.0 85/15 16 1-2 470 470 1 .26 0.0/5.0 85/15 17 1-2 500 500 1 .27 5.9/0.0 100/0 18 0.5-1 501 498 1 . 27 5.9/0.0 85/15 19 1-2 470 480 3 . 39 0.0/5.0 85/15 20 1-2 472 476 4 .45 0.0/5.0 85/ 15 2 1 2-4 5 18 5 18 1 . 3 5.9/0.0 85/15 22 1 -2 470 480 1 .63 2 . 4/3.0 85/ 15 23 1-2 474 474 1.13 4.1/1.5 85/15 24 1-2 500 500 1 .89 5.9/0.0 85/15 25 1-2 505 506 3.32 5.9/0.0 85/ 15 26 2-4 47 1 476 1 . 35 5.9/0.0 85/15 ON 65 significant amount of fines passed through the cyclone, therefore an overall mass balance could not be closed. It was found that a small fraction of the fines were stuck onto the wall of the cyclone, and mechancial brushing was employed in Runs 16 to 26 to recover as much of the fines as possible to obtain a more reliable spent shale yield. 5.2 Effect of Temperature on Oil Yield and Composition The study of the temperature effect was done on two feed sizes: 1-2mm and 2-4mm, at a constant feed rate of 1.40 and 1.28kg/h respectively. All of these experiments were done in a bed of silica sand, with pyrolyzing gas of 15% C02 and 85% N2. The height of the bed increased gradually as the feed shale accumulated in the reactor during the experiment. There are two temperatures of potential importance in the oil shale pyrolysis experiments; the inlet temperature and the bed temperature. The inlet temperature refers to the temperature of the preheated gas where it meets the shale at the bed inlet, and the bed temperature refers to the average temperature in the annulus of the spouted bed itself. If the heating rate in the inlet region is low, the particle will reach pyrolysis temperature only after passing into the bed. Then the bed temperature will govern the oil yield. If the heating rate in the inlet region is high and the particle begins to pyrolyze before reaching the bed, the inlet temperature will be important. In all experiments, the inlet temperature and the bed temperature were kept to the same 66 value within experimental error except for Run 6B. The calculated temperature history for the oil shale particles was presented in Section 2.5. It was shown that the particles are still near room temperature at the entrance of the spouted bed. In other words, pyrolysis of the shale particles does not start before the particles are in the bed, thus the inlet temperature is less important in this case. Table 14 lists the results. Figure 6 and 7 are plots of oil yield versus temperature. It can be seen that a maximum oil yield exists at some optimum temperature. For particles of 1-2mm, the optimum temperature is around 470-490°C. The oil yield is 7.1% which represents 89.3% of the modified Fischer Assay yield. It can be seen that the result for Run 6B in Figure 6 is slightly above the smooth curve through the other results. If the oil yield is plotted against the inlet temperature the curve will seem to be smoother, so it was thought that the temperature difference of 12°C between the inlet temperature and the bed temperature has produced this result. However, the temperature history calculation suggested little effect of inlet temperature. Experiment 6B should be repeated to verify the reliability of this data point. For the 2-4mm particle size, the small number of data points preclude the determination of an optimum temperature. The few results in Figure 6 suggest an optimum somewhere between 490 and 510°C. At 505°C the oil yield was 7.4% which TABLE 14: Effect of Temperature on CHI Yield Expt Particle Temperature Shale Oil Yield No. Size Bed Inlet Feedrate wt% %Fischer (mm) CO (kg/hr) Assay 1 1 5 4 9 6B 7 1-2 1-2 1-2 1-2 1-2 1-2 1-2 454 477 501 503 530 540 554 450 470 501 503 530 528 554 1 . 39 1 .52 1 . 33 1 . G5 1 . 39 1 . 29 1 . 33 54 . 1 89 .3 79 73 4 1 66 30 26 10 6A 2 1 2-4 2-4 2-4 2-4 47 1 506 507 518 476 505 518 518 1 . 35 1.21 1 . 25 1 . 30 4 . 2 7 . 2 7 . 4 3 . 3 53 . 3 9 1.7 94 . 3 42.0 Initial Bed Compostlon: Ottawa sand -14 +20 mesh Initial Weight : 5 .9 kg Spouting Gas: 85% N, - 15°/. CO; Fig 6: Oil Yield Versus Temperature Plot 10 Dp = 2 -4 mm Fo = 1.21 - 1.35 kg/hr 2-0 -| ,—, 1 -, , 1 ! 420 440 460 480 500 520 540 560 BED TEMPERATURE (C) Fig 7: Oil Yield Versus Temperature Plot 70 represents 94.3% of the modified Fischer Assay yield. However, more experiments are required to quantify the temperature optimum. Figure 8 shows a plot of the percentage of the Fischer Assay oil yield versus temperature plots for both 1-2mm and 2-4mm particle sizes. It can be seen that the curve for the 2-4mm is shifted slightly to the right, reflecting a higher optimum temperature for maximum oil yield compared to the 1-2mm size. This might arise because the 2-4mm particle is larger and will have larger internal temperature gradients, and will require a longer heating period or higher temperature to heat up the entire particle for complete pyrolysis. As mentioned earlier, more experiments are required to be done for 2-4mm sizes at 500-550°C. However, the trend of the Fischer Assay oil yield - Temperature curve in Figure 8 is in agreement with those observed by Liu et al<20> (refer to Figure 2). They have also concluded that that there is an optimum temperature corresponding to a maximum oil yield. Table 15 lists the composition of the oils produced at different temperatures for particles of diameter 1-2mm. Typical oils contain 81.5-83.0% C, 10.6-10.9% H, 1% N and 5-6.8% is not accounted for. It was first thought that the unaccounted species present in the oils was either methanol or methylene chloride from the solvent train. An investigation was carried out by dissolving the oil in ethylbenzene and injecting into a 50m long DB5 capillary I—' Fig 8: % Fischer Assay VS Temperature Plot TABLE 15: Effect of Temperature on Oil Yield and Composition Expt Temperature No. Bed Inlet (' C) Shale Oil Feedrate wt% (kg/hr) Yield %FIscher Assay Oil Analysis* (wt%) HNS A torn i c Ratio H/C 8 454 450 I .39 4.3 54. 1 11 477 470 1.52 7.2 90.6 5 501 501 1.33 6.3 79.2 4 503 503 1.65 5.8 73.0 6B 540 528 1.29 5.3 66.6 7 554 554 1.33 2.4 30.2 Oil Shale Particle Size: 1-2mm Initial Bed Composition: Ottawa Sand -14 +20 mesh Initial We ight: 5.9 kg Spouting Gas: 85% Ni - 15% COi 83.03 10.55 1.25 5.17 1.51 82.46 10.66 1.13 0.63 5.12 1.54 81.47 10.70 1.02 6.81 1.57 81.92 10.91 0.88 6.29 1.59 81.77 10.92 0.81 6.50 1.59 * MIcroana1yt1ca1 Analysis ** Unaccounted 73 column in a chromotograph. Results indicated that neither methanol nor methylene chloride was present. The unaccounted species are as yet unidentified. As the pyrolysis temperature increases, the atomic H/C ratio increases. At the optimum temperature, H/C is 1.54, which seems to be in agreement with the expected values for shale oils produced by pyrolysis. 5.3 Effect of Oil Shale Particle Size on Oil Yield and  Composition The study of the particle size effect on oil yield and composition was carried out for 2-4, 1-2, and 0.5-1mm sizes. All of these experiments were done at about 506°C with 15% C02 and 85% N2 as pyrolyzing gas. The bed was initially filled with silica sand, and the bed height increased gradually with time as the feed shale accumulated during the exper iment. Table 16 lists the results. Figure 9 shows the oil yield versus mean particle sizes. It can be seen that oil yield increases with increasing particle size. This is exactly opposite to the observation made by Jarallah*2' on coal pyrolysis. He found that the tar yield decreases with increasing particle size, and his explanation is that there is an increased extent of secondary reactions which consume tar for larger particles. The extent of secondary reactions may be less significant in oil shale pyrolysis. If the experimental temperature is higher than the optimum TABLE 16: Effect of Particle Size on 011 Yield Expt Particle Temperature Shale Spent Shale Oil Yield No. Size Bed Inlet Feedrate In Bed wt'/. '/.Fischer (mm) CO (kg/hr) (gm) Assay 18 0.5-1 501 498 1.26 681.0 2.4 43.6 3 0.5-1 505 505 1.37 454.0 4.2 76.4 2 0.5-1 509 509 1.49 510.8 2.4 43.6 5 1.0-2 501 501 1.33 681.0 6.3 79.2 4 1.0-2 503 503 1.65 539.1 5.8 73.0 10 2.0-4 506 505 1.21 652.6 7.2 91.7 6A 2.0-4 507 518 1.25 908.0 7.4 94.3 Initial Bed Composition: Ottawa Sand -14 +20 mesh Initial WeIght : 5.9 kg Spouting Gas: 85% Ni - 15% CO, 10 Fig 9: Oil Yield VS Particle Size Plot 76 temperature, the chance is greater that the oil is further decomposed to secondary volatiles. In the present case, the optimum temperature for 1-2mm particle size is around 475°C which is about 31°C lower than the experimental temperature in Figure 7. The extra temperature has enhanced secondary reaction, and therefore the oil yield obtained at 6.3% is lower than the maximum of 7.1%. Whereas for the 2-4mm size, the optimum temperature is around 505°C which is approximately the same as the temperature in Figure 6. For the 0.5-1mm particle size, although the optimum temperature was not studied, it is expected to be lower than 475°C. With the same argument, therefore the greater difference between the experimental and optimum temperature results in an even lower oil yield for the smallest particles. Based on these observations, the dependance of oil yield on particle size will be different if the comparision is made at say 475°C. In this case, the 2-4mm particles will produce a lower oil yield as the optimum temperature has not been attained, whereas for the 0.5-1mm particle, the gap between the optimum and experimental temperature is reduced, so a higher oil yield is expected. Certainly, more tests at lower temperature should be carried out to provide a more complete picture. Table 17 lists the elemental composition of the oils produced. There is no consistent trend among the three samples analyzed. The 2-4mm sized shale has the highest atomic H/C ratio and lowest unaccounted for species. TABLE 17: Effect of Particle Size on Oil Yield and Composition Expt Particle Temperature Shale Oil Yield Oil Analysis* (wt%) Atomic No. Size Bed Inlet Feedrate wt% '/Fischer C H N S ** Ratio (mm) CO (kg/hr) Assay H/C 2 0.5-1 509 509 1.49 2.4 43.6 8 1.58 11.02 0.7 6.70 1.61 3 505 505 1.37 4.2 76.4 82.18 10.73 1.05 6.04 1.56 4 1-2 503 503 1.65 5.8 73.0 81.47 10.70 1.02 6.81 1.57 5 501 501 1.33 6.3 79.3 82.46 10.66 1.13 0.63 5.12 1.54 6A 2-4 507 518 1.25 7.4 94.3 82.73 10.66 1.14 5.47 1.54 10 506 505 1.21 7.2 91.7 82.64 1 1.35 1.12 4.89 1.64 Initial Bed Composition: Ottawa Sand -14 +20 mesh * Microanalyt1ca1 Analysis Initial Weight: 5.9 kg *+ Unaccounted Spouting Gas: 85% N> - 15% CO> 78 5.4 Effect of Oil Shale Feed Rate on Oil Yield and  Composition The feed rate study was carried out for 2 sizes: 2-4mm and 1-2mm. All of these experiments were done at 500-506°C, using 15% C02 and 85% N2 as pyrolyzing gas. The bed initially consisted of silica sand and the bed height increased gradually as the feed shale accumulated during the exper iment. Tables 18 and 19 list the results. Figures 10 and 11 show the plots of oil yield versus shale feed rate. Both curves indicate that there is a marked decrease of oil yield with increasing feed rate. For 1-2mm shale, the oil yield has dropped from 6.3% to 2.9% as the feed rate was increased from 1.33 to 3.32kg/h, which is a drop of 79.2 to 36.5% of modified Fischer Assay values. Similar results were observed for the 2-4mm sized shale where feed rate increases from 1.53 to 2.71kg/h resulted an oil drop from 7.4 to 2.0%, which is a drop of 94.3 to 25.5% of modified Fischer Assay values. It can be seen in Figure 10 that the first three points are in a straight line, indicating a linear decreasing effect and then the line approaches an asymptotic value. The reason for the decrease is presumably that the hot spent shale accumulated in the reactor has acted as a surface on which the secondary oil-consuming reactions occur, or perhaps as a catalyst for oil decomposition. This effect will be demonstrated further below. The trends in Figure 10 and 11 are in the same direction as those observed TABLE 18: Effect of Feedrate on Oil Yield (Unsteady Height Expt.) Expt No . Temperature Bed Inlet CO Shale Feedrate (kg/hr) Spent Shale In Bed (kg) 01 1 Yield wt % % F1scher Assay 24 25 501 503 506 505 501 503 506 506 1 .33 1 .65 1 .90 3.32 0. 68 O. 54 1.31 1 . 46 6 . 3 5 . 8 3 . 4 2.9 79 . 2 73 .0 42.8 36 . 5 Oil Shale Particle Size: 1-2mm Initial Bed Composition: Ottawa Sand -14 +20 mesh Initial WeIght: 5.9 kg Spouting Gas: 85% N, - 15% CO: vO TABLE 19: Effect of Feedrate on 011 Yield (Unsteady Height Expt.) Expt No . Temperature Bed Inlet CO Shale Feedrate (kg/hr) Spent Shale In Bed (kg) 01 1 wty. Yield % Fischer Assay 10 506 505 1.21 0. 65 7 . 2 9 1.7 6A 507 5 18 1 . 25 0.9 1 7 . 4 94 . 3 I 2 A 12 506 506 502 502 1 .94 2.71 1 .02 1 . 28 4 . 5 2.0 57 . 3 25 . 5 Oil Shale Particle Size: 2-4mm Initial Bed Composition: Ottawa Sand -14 +20 mesh Initial Weight: 5.9 kg Spouting Gas: 85% Ni - 15% COi Co o 10 8 Dp = 1 - 2 mm Tb = 501 - 506 C 1 6 Q _J UJ >- 4 _J o 25 0.5 1 1.5 2 2.5 3 FEED RATE, (kg/hr) 3.5 4 Fig 10: Oil Yield VS Feed Rate Plot 82 o CL CD •f-* CO DC ~u CD CD UL > CD >-O (%1AA) 'CTBA 110 83 by Jarallah121 on coal pyrolysis. Another series of feed rate experiments was carried out in a bed consisting initially of spent shale with the bed height kept constant by releasing the accumulated spent shale periodically through the bed overflow line. Table 20 lists the results. Figure 12 shows the oil yield versus feed rate plot. Results indicate that the oil yield has remained quite steady at 2.4-2.6% regardless of the feed rate. This value is very close to the lowest yield in previous Figure 10. This implies that the presence of spent shale has indeed enhanced secondary rections of the oil (such as cracking), therefore dropping the oil yield significantly. A careful study of the two figures leads to the conclusion that with increasing feed rate in a sand bed, the oil yield will drop linearly in the beginning, and then gradually approach an asymptotic value of around 2.4%. Table 21 lists the composition of the oil produced for the 2-4mm size. The hydrogen content decreases, but the hydrogen/carbon atomic ratio seems to increase from 1.46 to 1.56 as the oil yield falls off with increasing feed rate in the sand bed experiments. 5.5 Effect of Bed Material on Oil Yield The study of the bed material effect on oil. yield was carried out on shale of 1-2mm size at 470-477°C with 15% C02 and 85% N2 as the pyrolyzing gas. For all experiments, the volume of the initial bed was kept the same (vol=3735cm3, TABLE 20: Effect of Feedrate on Oil Yield (Steady Height Expt.) Expt No . Temperature Bed Inlet CC) 16 470 470 470 480 20 472 476 Shale Feedrate (kg/hr) Oil Yield % Fischer Assay 1 .26 3 . 39 2.4 2 .6 30. 2 32 . 7 4.45 2.5 31.4 Oil Shale Particle Size: 1-2mm Initial Bed Composition: Spent Shale Initial Weight: 5.9 kg Spouting Gas: 85% Ni - 15% C0> * Periodic release of spent shale from the reactor to keep bed height steady co •o-10 8 STEADY BED HEIGHT Dp = 1 - 2 mm Tb « 470 - 472 C Initial Bed : Spent Shale £ 6 UJ >-2-16 19 20 0 r 0 1 2 3 FEED RATE, (kg/hr) Fig 12: Oil Yield VS Feed Rate Plot oo TABLE 21: Effect of Feedrate on 011 Yield and Composition Expt No . Temperature Bed Inlet CO Shale oil Feedrate wt% (kg/hr) Yield %Flscher C Assay Oil Analysis* (wt%) H N A torn 1c Rat io H/C 10 12A 506 506 505 502 1 .2 1 .94 7 . 2 4 . 5 91.7 57 . 3 82.64 83.65 1 1 . 35 10. 77 1.12 1 . 23 4 .89 4 . 35 1 .46 1 . 53 12 506 502 2.7 1 2.0 25.5 83 . 42 10.89 1 . 29 4 .40 1 . 56 Oil Shale Particle Size: 2-4mm * Microana1yt1ca1 Analysis Initial Bed Composition: Ottawa Sand -14 +20 mesh ** Unaccounted Initial Weight: 5.9 kg Spouting Gas: 85% Ni - 15% COi Co ON 87 initial bed depth=33cm), but the amount of spent shale in the bed ranges from 1 to 6.9kg. The remainder of the bed was silica sand. As the experiment proceeded, the bed height increased gradually as spent shale accumulated in the reactor. Table 22 lists the results. Figure 13 shows the plot of the oil yield versus the final spent shale mass in the reactor after the run. The final mass represents the spent shale accumulated during the experiment. The results show that there is a marked decrease in oil yield with increasing spent shale mass in the bed. These experiments show essentially the same effect as the feed rate experiments. As more and more spent shale becomes available in the bed, the oil yield drops because the hot spent shale has acted as a sorbent for the oil or a catalyst for the secondary reactions. When the initial bed is comprised solely of spent shale, the oil yield drops to 2.4% which is equivalent to the asymptotic value for Figure 12. It can be concluded that the presence of spent shale has a negative effect on the oil yield. This is in agreement with the observation made by Levy et al(*3). In their study, vaporized oil was passed through a packed bed of sand, or spent shale ash at temperatures between 500 and 600°C. In the case of sand bed, cracking was minimal at 500°C and gradually increased at higher temperatures. In the case for spent shale ash bed, coking was prevalent at all temperatures studied, and a major oil losses was resulted even at 500°C. The ash has TABLE 22: Effect of Bed Material on Oil Yield Expt. Temperature Shale Initial Bed Final Oil Yield No Bed Inlet Feedrate -Spent Shale Sand Spent Shale wt7- 7.F l scher CC) (kg/hr) (kg) (kg) 11 470 477 1.52 0.0 5.9 1.0 7.1 89.3 23 474 474 1.13 1.5 4.1 2.25 3.9 49.0 22 470 470 1.63 3.0 2.4 3.73 2.7 34.0 16 470 470 1.26 5.0 0.0 6.84 2.4 30.2 Oil shale Particle Size: 1-2mm Spouting Gas: 85% N, - 15% COi 00 00 Dp = 1 - 2 mm Tb - 470 -474 C Fo = 1.13 - 1.63 kg/hr • 11 2 3 4 5 SPENT SHALE MASS, (kg) Fig 13: Oil Yield VS Spent Shale In Bed 90 catalysed the oil degradation greatly. On the other hand, this sorbent effect presumably is specific to the oil shale, as Floess et al.(36) found no difference in oil shale yields in fluidized beds of silica sand and calcined dolomite of surface area 6.3m2/g. It should be noted that the feed rate actually fluctuated from 1.13 to 1.63kg/hr. This should not have affected the oil yield result because Figure 10 of Section 5.4 already shows that the oil yield remains around 6% in that feed range. 5.6 Effect of Pyrolyzing Gas on Oil Yield Two experiments were done in the 1-2mm sized shale at 500°C using N2 instead of the mixture of 15% C02 and 85% N2 as pyrolyzing gas. Table 23 lists the results. The data are very reproducible, and both reflect a lower oil yield at 3.4% in nitrogen compared to 6.3% when using the N2 / C02 mixture. An explanation of this unexpected result is not available yet. Bae117' observed that at atmospheric pressure, the oil yield is not affected by the nature of pyrolyzing gas (refer to Figure 1). 5.7 Gas Yields The spouted bed retorting technique in which a large volume of gas is needed for spouting is not particularly well suited for measurement of gas yields, as concentration of produced gas in the off gas will tend to be very low. TABLE 23: Effect of Pyrolyzing Gas Composition Pyro1yz i ng Gas 85% N,- 15% COV 100% N> Expt. No Temperature (Inlet/Bed) 'C Feed Rate (kg/hr) Oil Yield (wt%) Oil Yield (%Fischer Assay) Oil Analysis (wt%) C H N S Unaccounted 503/503 1 .65 5.8 73.0 81 .47 10.70 1 .02 501/501 1 .33 6.81 6.3 79.2 82 .46 10.66 1.13 0.63 5. 12 14 49 1/500 1 .35 3.4 42.8 82.49 10. 89 1.17 0.75 4 .70 17 500/500 1 . 27 3 . 4 42 . 8 Atomic H/C Ratio 1 .57 1 .54 1 .57 Oil Shale Particle Size: 1-2mm Initial Bed Composition: Ottawa Sand -14 +20 mesh Initial We ight: 5.9 kg 92 Nevertheless some results were obtained. As stated in Section 4.6, two chromatographs were used. For most of the runs, the GC used was set for concentration of H2, CO, C02, and CH„ in the percent range. A few analyses were also done on the second GC, which permitted determination of the above species and addition information on C2H2, C2H„, C2H6,C3H8 and C«H10. Table 24 lists the results. Hydrogen is produced during pyrolysis of oil shale. The yield ranges from 0.02 to 0.045%, and does not seem to be affected by particle sizes, feed rate and bed material. Figure 14 shows the plot of hydrogen yield versus temperature. The profile seems to be marked by two peaks although the data is scattered. According to Campbell et al<37), the peaks are associated with 'secondary' pyrolysis reaction of the carbon residue remaining after the primary bitumen decomposition. Methane yields are recorded in a few experiments. Campbell et al (37) observed that methane is released during the oil generation, and higher temperature pyrolysis of the spent shale. The methane released during the secondary pyrolysis (above 500°C) may result primarily from the cleavage of methyl and methoxyl groups bonded to aromatic structures and possibly, from cleavage of methylene bridges between aromatic rings. The evolution of C2 and C3 was determined by the second GC. Campbell et al(37) observed that these gases are evolved TABLE 24: Gas Yields Expt Particle % Gas Yield (kg/kg shale) No Size (mm) Hi t CH. Ci iH. Ci r H s C: IHI C * H i o Ci 1 H | 4 Tota 1 2 0.5-1 0. .028 0. 028 3 0.5-1 4 1-2 0, .023 0.065 0 ,059 0, .059 0. 460 0. 666 5 1-2 0. .033 0.062 0, .04 2 0 .045 0. ,760 0. 942 SA 2-4 0, .037 0.098 0. .049 0, .060 0. ,820 1 . 064 6B 1-2 0 .027 0.079 0 068 0 .075 0. .631 0, . 880 7 1-2 0, .02 1 0.077 0. ,082 0 .052 0. ,914 1 . , 146 8 1-2 0, .032 0.057 0. , 160 0. .095 0. , 190 0.2 1 0, , 744 9 1-2 0 .038 0.068 0 .028 0 .045 0. , 4 10 0. 220 0 . 170 0 . 979 10 2-4 0. 036 0.088 0. 027 0. ,064 1 .650 0. 330 2 . 195 1 1 1-2 0. 03 1 0.080 0. 038 0. 07 4 0. 400 1 . 220 0 3 10 2 . 153 1 2 2-4 0. .042 0. 042 12A 2-4 0, ,024 0. 024 14 1-2 0. 037 0. 037 15 1 -2 0. .022 0. 022 16 1-2 0, .034 0. 034 1 7 1-2 0 .018 0. ,018 18 1-2 19 1-2 0 038 0 038 20 1-2 0 .039 0.029 0 . 06C 2 1 2-4 0 .019 0. .019 22 1-2 0. .015 0 .015 23 1-2 0 .033 0 .033 24 1-2 0 .030 0 .030 25 1-2 0 . 038 0.020 0 .058 26 2-4 0 .030 0 .030 * The experimental conditions for each run are listed 1n Table 12 0.07 0.06 c£ 0.05 Q _J LU 0.04 z LU § 0.03 CC Q X 0.02 11 6B 0.01-0.00 440 460 480 500 520 540 BED TEMPERATURE, (C) 560 580 Fig 14: Hydrogen Gas Yield VS Temperature vO 95 during the oil generation, i.e. between 350-550°C. The evolution of C« and C6 was determined in a few experiments only, therefore no conclusion can be drawn. In most experiments, carbon dioxide was included in the pyrolyzing gas at a level of 15%. Because of the fluctuations of the gas inlet flowrate, it was difficult to determine its yield. However, it was noted that for the run done with nitrogen alone as pyrolyzing gas, there was no C02 nor CO produced. These results agreed with the findings of Campbell et al13". They found that no C02 and CO were released during pyrolysis below the temperature of 550°C. The release of C02 and CO occurs primarily above 600°C. Carbon dioxide is produced during the decomposition and reaction of carbonate minerals present in the oil shale, and carbon monoxide is then produced by the subsequent reaction of C02 with carbon. 5.8 Spent Shale Yields As mentioned in the beginning of the section, there was a substantial loss of entrained spent shales particles. Some had escaped to the atmosphere due to the inefficiency of the cyclone, and some had stuck onto the wall of the cyclone. From experiment 14 onwards, mechanical brushing had been used to recover the fines from the cyclone, and thus higher percentages of fines were recovered. Table 25 lists the compositions of spent shales found in the bed and recovered from the cyclone catch for three different particle sizes. TABLE 25: Spent Shale Properties and Yield Run T emperature (' C) Particle Size (mm) 505/505 0.5-1.0 503/503 1-2 10 506/505 2-4 Bed Shale Cyc1 one Catch Bed Sha 1 e Cyc1 one Catch Bed Shale Cyc1 one Catch Total Carbon (%wt) 4.91 Organic Carbon (%) 3.48 6.84 4 .77 4 .64 2.37 6.87 4 . 30 5 . 33 2 . 36 5 . 89 3 . 20 S10> (%wt) Al ,0, Fe t 0 i CaO MgO Na.O K, 0 56 . 7 16.6 10. 1 3 . 34 2 . 24 1 . 35 2 . 64 61.2 9.33 3.96 6.54 2.50 0.95 1 .58 51.6 14.5 5.66 9 . 30 3.97 1 .6 2.23 52.4 11.2 4 . 80 8 . 77 3.45 1.31 1 . 83 50. 3 13.1 5 . 52 10.9 4 . 28 1 .38 2.17 59 . 8 8.81 3 . 84 7.42 2 . 93 1 . 10 1 . 55 Ba (ppm) Mn Sr T 1 440 790 175 2960 373 402 290 2440 390 690 340 3430 373 570 368 2970 376 705 385 3 180 300 446 3 10 2340 97 Mass balances using several species (Sr, Ba, Ti, Fe203) present in the shale, the bed material and the cyclone catch, all showed that the uncollected material which passed through the cyclone was about one-third of the oil shale feed. Also it can be observed that the cyclone catch contains higher carbon content than does the bed material which indicates that the entrained particles are generally incompletely reacted. It was intended that the spent shale yield be calculated from the weight of the shale in the shale-sand mixture remaining in the reactor plus the weight of entrained fines in the cyclone after the run. In practice, the actual weight of shale remaining in the reactor cannot be obtained simply by weighing the total solids due to the fact that some of the sand was also entrained to the cyclone. Therefore, the method chosen to obtain the yield is by combining 'the weight of entrained particles in the cyclone receiver plus the weight of the bed after the run minus the weight of inert material orginally present in the bed. Table 26 lists the results of the spent shale yield. Due to the incomplete recovery, the trends of the spent shale yield with process variable were not meaningful. Attrition is obviously a serious problem for processing these oil shales in a spouted bed. TABLE 26: Spent Shale Yields Expt Temperature Particle Shale Spent Shale Total Spent No Bed Inlet Size Feedrate Cyclone Bed Spent Shale Shale Yield (*C) (mm) (kg/hr) (gm) (gm) (wt%) 2 509 509 0.5-1 1 . , 49 68 1 .0 510.8 119 1.8 60.0 3 505 505 0.5-1 1 . . 37 652 .6 454 .0 1106.6 60.4 4 503 503 1-2 1 . ,65 68 1 .0 539 . 1 1220.1 55 . 3 5 501 501 1-2 1 . . 33 397 .5 681 .0 1078 .5 60.8 GA 507 518 2-4 1 . . 25 56.8 908 .0 964 . 8 57 .8 GB 540 528 1-2 1 , . 29 397 . 5 68 1 .0 1078.5 62 . 6 7 554 554 1-2 1 , .33 368 .9 766 . 1 1 135 .0 62 .8 8 4 50 4 50 1-2 1 . .38 539 . 1 595.9 1135 .0 6 1.0 9 530 530 1-2 1 . , 39 567 . 5 567 . 5 1135.0 6 1.0 10 506 505 2-4 1 . ,21 454 .0 652 .6 1106 .6 68 .4 1 1 477 470 1-2 1 , , 52 737 . 7 68 1 .0 14 18.7 70.O 12 506 502 2-4 2. . 7 1 1135 .0 127G . 8 2411.8 66 .8 12A 506 502 2-4 1 , .94 567 . 5 102 1 . 5 1589.0 6 1.4 14 500 491 1-2 1 . 35 835 . 2 500.0 1335 . 2 74 . 2 15 480 472 1-2 1 . . 37 1779. 1 (1135.0)* 664 . 1 66 .0 16 470 470 1-2 1 . 26 948 . 6 0 948 . 6 56 . 5 17 500 500 1-2 1 , . 27 62 1 .0 510.7 113 1.7 66 .8 18 500 498 0.5-1 1 . 26 449 . 3 681 .0 1130.3 67 19* 470 480 1-2 3 .39 1602.7 1021.5 3298.0 82 . 1 20* 472 476 1-2 4 .45 1906.8 (170.25)' 4823 . 7 84 . 3 00 21 518 518 2-4 1.30 514.0 1078.3 1592.3 91.8 22 470 480 1-2 1.63 803.7 1163.4 1967.1 90.0 23 474 474 1-2 1.13 736.4 595.8 1332.2 88.5 24 500 500 1-2 1.89 824.8 1305.3 2 130.1 84.3 25 500 506 1-2 3.32 981.0 1459.2 2740.2 86.9 26 471 476 2-4 1.35 1161.8 170.3 1332.1 73.8 * Discharge for expt 19 1s 673.8gm * Discharge for expt 20 1s 2746.6gm * For experiments 15 and 24, the bed actually had a lost in weight of 1135.0 and 170.25gm respectively 100 6. Kinetic Model 6.1 General Discussion From the simplified model developed in Section 3.2, equations ( 3. 33 ),( 3. 34) , ( 3.39) and (3.40) have been derived, A -Bt CK = — (1 - e ) (3.33) B " -Dt -Bt CB = CA( C, ,+ C12e + C13e ) (3.34) P -Qt CA = — (1- e ) (3.39) Q t Oil = / CAFgdt (3.40) Yield 0 with the Arrhenius relationships, o -E,/RT k, = k,e (6-D o "E2/RT k2 = k2e (6.2) c -E3/RT k3 = k3e (6-3) Taking k,, k2, E, and E2 from the literature2" and F0, F,, a F2, V, CKo and oil yield from the experiments, k3 and E3 can be solved for using UBC Library Program NL2SOL. The computer 101 program is included in Appendix C."' ^able 27 lists the experimental data and literature values used for the generation of k3 and E3. The predicted oil yield values and the experimental data are plotted in Figure 15. It can be seen that the model predicts a trend similar to the experimental data although the experimental oil yield drops more sharply at low tempartures. The predicted maximum oil yield occurs at a temperature of 440°C, which is some 37°C lower than that found by experiment. No measurements of kerogen and bitumen are available for checking the model. The values of C„, C^, CT and oil yield as functions of K B A 2 time can be calculated by UBC Library Program Jacobian using the following equations: dCK FQCRO fo - . = ( +k, )CK (3.44) dt W W dCB F0 = f,k,CK " ( + k2)CB (3.45) dt W dCA f2k2CBW Fg = ( + k3)CA (3.46) dt V V Oil = / CAFqdt (3.47) • 0 TABLE 27: Effect of Temperature on Oil Yield (Predicted vs Experimental Values) Expt No. Part icle Size (mm) Temperature Bed Inlet CC) Shale Feedrate (kg/hr) Exper imental Oil wt% Pred i cted Oil wt% (Unsteady Height Experiment) 8 1-2 11 1-5 1-2 4 1-9 1-2 7 1-454 477 501 503 530 554 450 470 501 503 530 554 1 . 39 1 .52 1 . 33 1 .65 1 .39 1 . 33 4.3 7 . 1 6.3 5.8 3.3 2.4 6 . 6 6.4 5.7 5.6 3.9 2.2 From Literaturet23) k' = 14.4 s- 1 Ei = 44560 kJ/mol ki = 2.025E10 s-1 Ei = 177580 kJ/mol From Calculation k" = 1 . 7E14 s-1 EJ = 244319.45 kJ/mol O NJ PREDICTED VALUES "1 1 1 1 1 I 350 400 450 500 550 800 BED TEMPERATURE (C) Fig 15: Oil Yield Versus Temperature Plot Predicted Values VS Experimental Values 104 The results are plotted in Figure 16 for one experimental run. As expected, , the concentration of kerogen, increases with time and then remains steady as a fraction of the kerogen is decomposed to form bitumen. Cg starts from zero and increases to some value, and then gradually remains constant as the bitumen is decomposed to oil. Oil concentration begins at zero, and gradually increases as it is produced by the decomposition of bitumen. At the same time, the oil degrades to form gas on further heating. The cumulative oil yield increases rapidly at the beginning, and then more slowly as time goes on and gradually approaches a constant value. 6.2 The effect of Rate Constant on Oil Yield The effect of individual rate constants k,, k2 and k3 on oil yield was studied using the UBC library program Jacobian to solve the model. The k,, k2 or k3 of the Arrhenius relationship (eqn. 6.1-6.3) is multiplied by a factor while holding all other values constant. The computer printout for one experimental run is shown in Appendix C.6. The model gives the same final oil yield results even for different values of k, and k2. As k, increases, the time required for the kerogen to decompose to bitumen decreases. The time effect is also true for k2. As k2 increases, the time for bitumen to decompose to oil is shorter. Changing k3, however, will affect the quantity and rate of oil degradation. For this reason, it can be seen that only k3 105 1000 2000 3000 4000 5000 1000 2000 3000 4000 5000 0.002 0.001 1000 2000 3000 4000 5000 2000 3000 Time (sec) 4000 5000 Fig. 16: CR, CQ, CA and Oil Yield vs Time Plot 106 and E3 have an effect on the maximization of the oil yield. If some data of kerogen and bitumen were taken, a better model could be obtained. 107 6.3 The effect of Oil Shale Feed Rate on Oil Yield Using the UBC Library Program Jacobian to solve the model, the effect of oil shale feed rate on oil yield was studied. Table 27 shows the comparison of the predicted oil yield results with the experimental values. Instead of a decreasing trend, the model predicted a constant oil yield value at 5.8 wt% for 2-4mm, and 5.5-6.0 for 1-2mm particle size. For the feed rate experiment carried under the steady height condition, again the model predicted a constant value at 6.6-6.7 wt % oil yield which is higher than the experimental value of 2.4-2.6 wt%. The predicted values indicate that the oil yield should be proportional to the feed rate. However the model does not take into consideration the effect of spent shale that acts as a catalyst for oil degradation. For future development of the model, the effect of spent shale should be included by putting the rate of oil decomposition proportional to the mass of spent shale. TABLE 27: Effect of Feedrate on Oil Yield (Predicted vs Experimental Values) Expt No . Part 1c1e Size (mm) Temperature Bed Inlet CC) Shale Feedrate (kg/hr) Exper i menta1 Oil wt% PredIcted Oil ut% (Unsteady Height Experiment) 10 2-4 6A 2-12A 2-4 12 2-501 503 50G 505 501 503 506 506 1 . 33 1 .65 1 . 90 3 . 32 7.2 7 . 4 4 . 5 2.0 5 . 8 5.8 5 . 8 5 . 8 5 4 24 25 1 -2 1-2 1-2 1-2 501 503 506 505 501 503 506 506 1 . 33 1 . 65 1 .90 3 . 32 6 . 3 5 . 8 3 . 4 2 . 9 5 . 7 5 . 5 6.0 6.0 (Steady Height Experiment) 16 1-2 19 1-20 1 -2 470 470 472 470 480 476 1 . 26 3 . 39 4 . 45 2 . 4 2.6 2.5 6 . 8 6 . 7 6.6 O 00 109 7. CONCLUSION The experimental studies have shown that New Brunswick oil shales can be pyrolyzed in a spouted bed reactor. At optimum pyrolysis temperature, shale particle sizes and feed rate, oil yields up to 94% of the Fischer Assay value were achieved. The temperature effect was studied using two particle sizes: 1-2mm and 2-4mm. The optimum temperatures are around 457°C and 505°C respectively, and above this temperature the oil yields fall off. Three particle size range were tested: 2-4mm, 1-2mm and 0.5-1mm. At a given feed rate and temperature, the oil yields increase with increasing mean particle size. There is a marked.decrease of oil yield with increasing shale feed rate in beds of sand. The hot spent shale which accumulates in the reactor appears to act as a sorbent for oil or a surface for the secondary oil-consuming reactions. Results of a series of experiments at fixed feed rate show that as the ratio of spent shale to sand in the initial bed increases, the oil yields decrease. For experiments in which the bed initially consisted only of spent shale, the oil yields remained at a constant low value regardless of the feed rate, over the range tested. All the experiments were done using 15% C02 and 85%N2 as pyrolyzing gas except for two experiments where N2 was used alone. For the latter two runs, the oil yields decreased by 50%. No logical explanation for this result is 110 apparent, and some confirmation of this result is required. Gas species produced in the pyrolysis are H2, CH„, C2H»-C2H6/C3H8 and C«H10. Carbon dioxide is not produced in the temperature range studied. The yields do not seem to be affected by shale particle sizes, feed rate and bed material. The reported gas yields were generally lower than the Fischer Assay values although for many runs the analytical equipment available did not detect hydrocarbons heavier than methane. There is a substantial loss of shale which is entrained in the gases and passes through the cyclone. Due to the low percentage recovery, trends of the spent shale yield were not reliable. A kinetic model which involves release of bitumen from the shale kerogen, and the subsequent decomposition of bitumen into oil accounts for the basic trends of the experimental results. Ill 8. RECOMMENDATIONS FOR FUTURE WORK As mentioned in the previous Sections 4 and 5, there are a few areas that need further studies. Modifications to the equipment and future work include: 1) An electrostatic precipitator should be installed downstream to enable better collection of oil from the pyrolysis of oil shale. 2) A more efficient cyclone should be used in order to collect all the entrained particles so as to do a better study on the spent shale trend. 3) A higher gear ratio reducer is recommended for the feed system to enable a more constant feeding rate during the experiment. 4) Modifications are recommended to the fountain section of the reactor in order to catch the spent shale ash to enable experiments to be carried out without interference of the spent shale which act as a catalyst for oil degradation. 5) More pyrolysis experiments should be carried out at the lower temperature range, specifically at 380-450°C in order to permit a better comparison with the model developed in Section 3.2. 6) Attempts should be made to collect some data on kerogen and bitumen content so as to obtain a better correlated model as discussed in Section 6. 7) The effect of the spent shale should be included in the future development of the model. 112-8) A set of oil yield vs temperature experiments should be carried out for the 0.5-1mm oil shale particle size so as to obtain the optimum temperature and compare the optimum oil yield with the Fischer Assay value. 113 NOMENCLATURE A Oil mass, kg Ap Surface area of particles, m2 B Bitumen mass, kg Bi„ Heat transfer Biot number, h r /k H p p p C Concentration of pyrolysable mass, kg/kg C^ Carbonaceous mass, kg CA Concentration of oil, kg/kg C_, Concentration of bitumen, kg/kg CR Concentration of kerogen, kg/kg Cp£ Heat capacity of fluid, KJ/kg-K Cp Heat capacity of particle, KJ/kg-K Cps Heat capacity of oil shale, KJ/kg-K E Activation energy, KJ/mol f, Weight fraction of kerogen that yields bitumen f2 Weight fraction of bitumen that yields oil f3 Weight fraction of kerogen that yields gas f„ Weight fraction of bitumen that yields gas F0 Mass feed rate of oil shale, kg/s F, Mass flow rate of entrained particles, kg/s F2 Mass flow rate of oil shale in the side line, kg/s Fg ^n Spouting gas flow rate, m3/s Fou Fourier number, at/r 2 H p Gas mass, kg 114 hp Heat transfer coefficient between fluid and particle, J/m2-s«K AH Heat of pyrolysis (assumed to be zero) rxn fi i Thermal conductivity of fluid, J/m-s-K k Thermal conductivity of solid particle, J/m-s-K P K Kerogen mass, kg k. Frequency factor for kerogen, 1/s k2 Frequency factor for bitumen, 1/s k3 Frequency factor for oil, 1/s k. Rate constant for kerogen, 1/s k2 Rate constant for bitumen, 1/s k3 Rate constant for oil, 1/s Mp Mass of a particle, kg Nu Nusselt number, h d /k, p p/ f Pr Prantl number, Cp^u/k^ Q_ Heat transfer rate at particle surface, J/s r Radius, m Radius of particle, m r„ Overall rate of Kerogen production, 1/s rg Overall rate of Bitumen production, 1/s r Overall rate of Oil production, 1/s R Gas rate constant, 8.3143J/mol•K Re Reynold number, dpUpP^/^ 115 t Time, s t0 Initial time, s T Temperature, K T^ Bulk bed solid temperature, K Tc Temperature of shrinking core surface, K Tg Temperature of gas, K Tp Temperature of particle, K TR Temperature of particle surface, K Tg Internal particle temperature, K Tw Wall or heater temperature, K V • Volume of the vapor reaction zone, m3 V Particle volume, m3 P W Weight of spent shale in bed, kg w0 Initial weight of particle, kg wfc Weight of particle at time t, kg WQ Final weight of particle, kg a Thermal diffusivity of particle, k /(p -Cp ), m2/s p s p ev Voidage e Effective emmissivity (0.9) n Viscosity of fluid, g/cm-s Ps Average density of oil shale, g/m3 a Stefan-Boltzmann constant, 5.673X10"12 J/cm2«s-K* 116 REFERENCE 1. Ranny, M.W., Oil Shale and Tar Sands Technology - Recent Developments , Noyes Data Corp., 1979. 2. Al-Jarallah, A.M., "Pyrolysis of Some Western Canadian Coals in a Spouted Bed Reactor," PhD thesis, University of British Columbia, 1983. 3. Stanfield, K.E., "Properties of Colorado Oil Shale," USBM Report of Investigations 4825, 1951. 4. Allred, V.D., "Kinetics of Oil Shale Pyrolysis," Quarterly of the Colorado School of Mines, Vol 62, No. 3, 657-669 (1967). 5. Henderick, T.A., Synthetic Fuels Data Handbook , Cameron Engineers Inc., 1975. 6. Pease, L.R., "Tosco Technology Applied to Eastern US Oil Shales," Eastern Oil Shale Symposium Proceedings (1981). 7. Margolis, M.J., "Fluidized Bed Oil Shale Retorting: A Bench Scale Evaluation for Eastern Oil Shale," Eastern Oil Shale Symposium Proceedings (1981). 8. Salib, P.F., Barua, S.K., and Furimsky, E., "Retorting of Oil Shale from New Brunswick, Canada," Energy Research Laboratories , Energy, Mines and Resources, CANMET, Ottawa (1986). 9. Mathur, K.B., and Epstein, N., Spouted Beds , Academic Press, 1974. 10. Kmiec, A., "Simultaneous Heat and Mass Transfer In Spouted Beds," Can. J. Chem. Eng., Vol 53, 18-24 (1975). 11. Grace, J.R., and Mathur, K.B., "Height and Structure of Fountain Region Above Spouted Bed," Can. J. Chem. Eng., Vol 58, 533-537 (1978). 117 12. Epstein, N., Lim, C.J., and Mathur, K.B., "Data and Models for Flow Distribution and Pressure Drop in Spouted Beds," Can. J. Chem. Eng., Vol 56, 436-447 (1978). 13. Foong, S.K., Lim, C.J., and Watkinson, A.P., "Coal Gasification in a Spouted Bed," Can. J. Chem. Eng., Vol 58, 84-91 (1980). 14. Smith, K.J., Arkun, Y., and Littman, H., "Studies on Modelling and Control of Spouted Bed Reactor - I," Chem. Eng. Sci., Vol 37, 567-579 (1982). 15. Vaid, R.P., and Sen Gupta, P., "Minimum Fluidised Velocities Beds of Mixed Solids," Can. J. Chem. Eng., Vol 56, 292 (1978). 16. Leite, A.C.B., Wodtke, R.M.P., Lisboa, A.C.L., and Restini, F., "Pyrolysis of Oil Shale Fines in a Spouted Bed Reactor," VI Congresso Brasileiro de Engenharia Quimica, Campinas, Julho (1984), XVI Congresso Latino Americano de Quimica, Rio de Janeiro, Octubro (1984). 17. Bae, J.H., "Some Effects of Pressure on Oil Shale Retorting," Annual Fall Meeting of the Society of Petroleum Engineers (AIME), 1968. 18. Furimsky, E., "Hydrogen Retorting of Oil Shales from Eastern Canada," Fuel Processing Technology, 8, 293-306 (1984). 19. Hill, G.R., "The Direct Production of a Low Pour Point High Gravity Shale Oil," ACS Symposium on Pyrolysis Reactions of Fossil Fuels, Pittsburgh (1966). 20. Lui, A.P., Mei, J.S., Shang, J.Y., and Zhang, G.Q., "Application of a Twin Fluidized-Bed Reactor for Retorting Combustion and Gasification /Combustion Processes," Proc. 7th International Conference on Fluidized'Bed Combustion, 1270-1281 (1983) 118 21. Stanfield K.E., and Frost I.C, "Method of Assaying Oil Shale by Modification Fischer Retort," US Bureau of Mines Report of Investigation 4477 (1949). 22. Hubbard, A.B., and Robinson, W.E., US Bureau of Mines Report of Investigations 4744 (1950). 23. Cook, E.W., "Green River Shale-Oil Yields: Correlation with Elemental Analysis," Fuel, Vol 53, 16-20 (1974). 24. Braun, R.L., and Rothman, A.J., "Oil Shale Pyrolysis Kinetics and Mechanism of Oil Production," Fuel, Vol 54, 129-131 (1975). 25. Johnson, W.F., Walton, D.K., Keller, H.H., and Couch, E.J., Proceeding 8th Oil Shale Symposium, Colorado School Mines, 70(30), 237 (1975). 26. Finucane, D., George, J.H., and Harrist, H.G., "Perturbation Analysis of Second Order Effects in Kinetics of OilShale Pyrolysis," Fuel, Vol 56, 66-69 (1977). 27. Campbell, J.H., Keskinas, G.H., and Stout, N.D., "Kinetics of Oil Generation from Colorado Oil Shale," Fuel, Vol 57, 372-376 (1978). 28. Granoff, B,, and Nuttall, H.E., "Pyrolysis Kinetics for Oil-Shale Particles," Fuel, Vol 56, 234-240 (1977). 29. Shih, S.M., and Sohn, H.Y., "Nonisothermal Determination of the Instrinsic Kinetics of Oil Generation from Oil Shale," Ind. Eng. Chem. Pro. Des. Dev., Vol 19, 420-426 (1980) . 30. Wen, C.S., and Koby1inski, T.P., "Low Temperature Oil Shale Conversion," Fuel, Vol 62, 1269-1273 (1983). 31. Wang, CC, and Noble, R.D., "Composition and Kinetics of Oil Generation from Non-isothermal Oil Shale Retorting," Fuel, Vol 62, 529-533 (198 3 ) . 119 32. Burnham, A.K., and Happe, J.A., "On the Mechanism of Kerogen Pyrolysis," Fuel, Vol 63, 1353-1356 (1984). 33. Yang, H.S., and Sohn, H.Y., "Kinetics of Oil Generation from Oil Shale from Liaoning Province of China," Fuel, Vol 63, 1511-1514 (1984). 34. Pan, Z., Feng, H.Y., and Smith, J.M., "Rates of Pyrolysis of Colorado Oil Shale," AlChe Journal, Vol 31, No. 5, 721-728 (1985). 35. Teo, K.C., Watkinson, A.P., and Jung, D.J., "Characterization and Storage Stability of Untreated and Hydrotreated Liquids from Spouted Bed Pyrolysis of Canadian Coals," Dept. of Chem. Eng., University of British Columbia, DSS File No. 20ST 23440-4-9074 , DSS Contract Serial No. OST84-0015-1 , Pg. 22-32 (1985). 36. Floess, J.K., Plawsky, J., Longwell, J.P., and Peters, W.A., "Effects of Calcined Dolomite on the Fluidised Bed Pyrolysis of a Colorado Oil Shale and a Texas Lignite," Ind. Eng. Chem. Proc. Des. Dev. Vol 24, 730-737 (1985) 37. Campbell, J.H., Koskinas, G.J., Gallegos, G., and Gregg, M., "Gas Evolution during Oil Shale Pyrolysis: Nonisothermal Rate Measurements," Fuel, Vol 59, 718-725 (1980). 38. Wu, Stanely W.M., "Hydrodynamic of Gas Spouting at High Temperature," MASc. thesis, University of British Columbia, 1986. 39. Ekstrom, A., and Callaghan, G., "The Pyrolysis Kinetics of some Australian Oil Shales,", Fuel, Vol 66, 331-337 (1987). 40. Parks, T.J., Lynch, L.J., and Webster, D.S., "Pyrolysis model of Rundle Oil Shale from in-situ H n.m.r. data," Fuel, Vol 66, 338-344 (1987). 120 41. Wall, G.C., and Smith, S.J.C., "Kinetics of production of Individual Products from the Isothermal Pyrolysis of Seven Australian Oil Shales," Fuel, Vol 66, 345-349 (1987). 42. Gannon, A.J., and Henstridge, D.A., "Pyrolysis Stoichiometry for Three Kerogen Types," Fuel, Vol 66, 350-352 (1987). 43. Levy, J.H., Mallon, R.G., and Wall, G.C., "Vapour Phase Cracking and Coking of Three Australian Shale Oils: Kinetics in the Presence and Absence of Shale Ash," Fuel, Vol 66, 358-364 (1987). 44. Dung, N.V., Wall, G.C. , and Kastl G., "Continuous Fluidized Bed Retorting of Condor and Stuart Oil Shales in a 150mm diameter Reactor," Fuel, Vol 66, 372-376 (1987) . 45. Dung, N.V.,"A New Concept for Retorting Oil Shales," Fuel, Vol 66, 377-383 (1987). 46. Charlton, Brian G., "Comparative Fluidized Bed Combustion Kinetics of some Australian Spent Oil Shales," Fuel, Vol 66, 384-387 (1987). 121 APPENDIX A Temperature History Model The heat transfer in a spouted bed has been discussed in Section 2.6. It is shown that the particle temperature profile is governed by the unsteady state diffusion equation, 3T a 3(r23T/3r) = (2.4) 3t r2 3r with the boundary condition for r=R, KpOT/3r)r = rp = hp(Tb - Tr = rp) (2.5) From equation 2.4, the temperature profile of a particle as a function of time can be estimated along the longtitude height of the "4 regions of a spouted bed: the spout, fountain (upward), fountain (downward) and annulus. The sketch of the different regions are shown in Figure 4. The equation can be written as a tridiagonal matrix. The radius of the particle is divided into 10 sections with r(l)=r , ie. the centre of the particle, and r(l0)=R, ie. the surface of the particle, and the longtitude height of the bed is also equally divided into 10 sections, thus forming a matrix of 10 x 10. To put the equation in a matrix form, equation 2.4 has to be differentiated and put into finite series form, a 3T 32T — (2r — + r2 ) = r2 3r 3r2 3T dt (A.l ) 2a3T d2T 3T + a = (A.2) r3r dt2 dt where 3T Tn+i »- - Tn_i t 3r 2Ar 32T Tn+1>t - 2Tn>t + Tn-!>t 77 = A 2 (A-4) 3r2 Ar2 3T Tn «. - T n,t An,t-1 (A.5) 3t At therefore equation (A.2) becomes, 2a, Tn+1,t - Tn_lft Tn+,ft - 2Tn,t + Tn-!,t ( ) + a( 2Ar Ar Tn,t Tn,t-1 At (A.6) 123 Rearranging equation (A.6) gives, a a 2a 1 a a <"— +—)Tn-1,t + — >Tnft + ( + ") Tn+,,t rAr Ar2 Ar2 At rAr Ar2 Tn,t-1 At 3a 6a 1 3a — " —) Tn,t + — Ar2 At Ar — Tn-1,t + (-— " —) Tn,t + — Tn+1#t Ar' Ar2 At Ar2 (A.7) At the boundary condition when r=rc=0, then (A.2) becomes, 32T 3T 3a7T =T~ <A-8) 3r2 3r Ar2 At = _ Tn'fc 1 (A. 10) At 3T The boundary condition at r=0 is = 0 (A.ll) dr Tn+1,t" Tn-1,t ( ) = 0 (A.12) 2Ar or Tn+1,t = Tn_|ft (A.13) 124 Therefore, 6a 1 6a Tn,t-1 3r kp (A. 14) ( )Tn,t + ^Tn+1,t Ar2 At Ar2 At The boundary condition at r=R is = —(Tg - T) (A. 15) or T"*,'t " T""''t = - T„,t) (*.,6> 2Ar kp hp •n+l,t = Tn-l,t + 2 r <Tg " Tn,t> (A-1?) Substituting the result into the general form of the (A.7) yields: a a 2a 1 ( + )T + ( ) Tn/t rAr Ar2 Ar2 At ( + )[Tn-ift+' (Tg-Tnft)] = 2Arhn Tn,t-1 rAr Ar' Kp (A.18) 125 2a 2a 1 2Arhp a a or -Tn-l,t + I , < + :^Tn,t Ar2 Ar2 At kp rAr Ar2 Tnft-i 2Arhp a a ( + ) Tq (A.19) At kp rAr Ar2 The coordinates of the matrix are listed in table 29. A library program TRISLV is used to solve the tridiagonal equations. Table 30 lists the correlations used for estimation of the hydrodynamic properties for the spouted bed. There are a few assumptions made: 1) The velocity of the particle at the apex of the spouted bed is assumed to be zero. 2) The particle at the apex of the spouted bed is assumed to be at room temperature, 298°K, ie. the inlet temperature effect on the particle is ignored. 3) The calculation of the hydrodynamic properties of the spouted bed is based on sand as spouting media. The oil shale particle is assumed to follow the flow pattern of the sand. 4) The reactor temperature is assumed to be constant. There is assumed to be no heat loss to the surroundings. Table 29: Coordinates of the Tridiaqonal Matrix of spouted bed b, 2a Ar' 1 At c, -2a ArJ n, t ~ I Ac Ar4 rAr 2a I Ar» Ac rAc Ac' ln,c- i Ac 2a Ar; 2ahp 2ahpAr cKp Ar'kp Ar* At 2ahpTq 2ahpTq Tn<c_, rUp drlcp AC 127 Table 30: Correlations used to estimate the properties of spouted bed hydrodynamic Dc . .. Dc. . . .Dc 0. 105( )° 75( )° , Dp Di pp,/2 Reference (9) 2gHH(pp-pg) urns £ 2 )o.s DC Dc Pg (9) 0.118(G)°'9(Dc)°-«' (9) um( 0.5(nbf + Mtf) (10) nebf nebf•u DpPg netf•M DpPg Dp3Pg(Pp-Pq)g ut [18.1J + 0.0192(—-—- 2 )]i/» _ 18. ( 10) netf [24.02 + 0.0546( Dp3Pg(pP-pg)g )]1/* - 24.0 (10) (Eo'-'M(VPmax)Mps) 2g (ps~Pg) (12) (0.3X0.2) (Vmax)DIS J (spouc) {1-o.2) HH Vmax2 " 2g(DISJ)(pP-pg) [ . L_] o. 5 (fountain > o Pp [ 2g(Pp"Pg) (falling; E0'-'6pp •(H - DISJ)]°-5 128 5) The oil shale particle is assumed to be a perfect spherical particle. The computer program consists of three sections. Section 1 specifies all the data and information of the spouted bed reactor, the properties of sand (spouting media), oil shale and spouting gas. It also calculates the hydrodynamic properties . for the spouted bed. Section 2 of the program calls the subroutine Temp2 to Temp5 to calculate and print out the solutions. Section 3 of the program stores all the subroutines. The calculations were done on three average oil shale sizes: 3mm, 1.5mm and 0.75mm; and three reactor temperatures: 450, 500 and 550°C. Other profiles can be obtained by simply changing the data information in line 44, 45 and 46 of the program. 129 APPENDIX B B.1 Calculations for Isokinetic Gas Sampling Isokinetic sampling means that the velocities of the gases in the main pipe is the same as the velocities of gases in the sampling tube. To ensure this, the volumetric flow rate of the gas in the main pipe is first estimated, and the volumetric flow rate of the sample is then calculated and adjusted to the temperature of the sampling gas rotameter. A sample calculation for Run #2 is shown as below: Oil shale particle size = 0.5-1.Omm Temperature of the reactor = 501°C Temperature of the sampling tube = 400°C Mass flow rate of spouting gas = 4.95g/s Mass flow rate of oil shale (as received) = 0.369g/s Mass flow rate of oil shale (MAF) = 0.095g/s Water vapor and gas expected to evolve from oil shale = 0.0l9g/s Total mass flow rate of gases = 4.969g/s It can be seen that the spouting gas accounts for 99% of the gases, hence the mass flow rate and density of spouting gas are used for the purpose of this calculation. Density of spouting gas at 501°C = 0.0004793g/cm3 Volumetric flow rate of gases = 10367.20cm3/s Main pipe flow rate = 23.58cm2 130 Velocity of the spouting gas = 439.66cm/s Sampling tube cross-sectional area = 0.7cm2 Volumetric flow rate of sample gas, 500°C = 307.76cm3/s Volumetric flow rate of sample gas, 21°C = 1l7.0cm3/s Hence the sample gas rotameter setting is adjusted accordlingly. B.2 Product Yield Calculation The procedure used to calculate oil, gas and spent shale yields is outlined as below, and a simple computer program is written for this purpose. oil Oil Yield: x 100% Feed Spent Shale Yield: spent x 1 00% Feed TG - SG Total Gas Yield: x 1 00% Feed TG = SG = Total gas output, g/s Mass flow rate of spouting gas, g/s APPENDIX C Computer Programmes Profile 133 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC i d = TITA 1 2 c • C 2. . 2 r NAME OF THIS PROGRAM: PROFILE • 2 . . 4 C * 2. 8 c * 3 C THIS PROGRAM IS USED TO WORK OUT THE TEMPERATURE HISTORY OF * 4 C AN OIL SHALE PARTICLE IN THE 5 REGIONS OF A SPOUTED BED: * 6 C 1 ) SPOUT REGION * 7 C 2) FOUNTAIN REGION * 8 C 3) FALLING REGION 9 C 4) ANNULLUS REGION * 10 C * 1 1 c THIS PROGRAM IS CONSISTED OF 3 SECTIONS: * 12 c SECTION 1) SPECIFIES ALL THE INFORMATION OF THE SPOUTED BED * 13 c BED REACTOR. PROPERTIES OF SANO (SPOUTING MEDIA) * 14 c AND PROPERTIES OF OIL SHALE. IT ALSO WORKS OUT 15 c THE HYDRODYNAMIC PROPERTIES (HM. UMS, UMF ETC) 16 c FOR THE SPOUTED BED * 17 c * 18 c SECTION 2) CALLS THE SUBROUTINE TEMP2. TEMP3. TEMP4 AND 19 c TEMP5 TO CALCULATE AND PRINT OUT THE TEMPERATURE * 20 c HISTORY FOR THE OIL SHALE AT A GIVEN SIZE AND * 21 c REACTOR TEMPERATURE * 22 c * 23 c SECTION 3) STORES ALL THE SUBROUTINE TEMP2 TO TEMP5 * 24 25 c * 26 c 27 c 28 IMPLICIT REAL*8 (A-H.O-Z) 29 c 30 DIMENSION DP(3),TEMPG(3).TERM(3) 31 DIMENSION BI0T2(2O),BIOT3(2O).BI0T4(2O).BI0T5(2O) 32 DIMENSION DIS1(20). DIS2(20), DIS3(20). DIS4(20). DIS5(20) 33 OIMENSION DTIME1(20).DTIME2(20).DTIME3(20).DTIME4(20) 34 DIMENSION DTIME5(20) 35 DIMENSION HP2(20).HP3(20).HP4(20).HP5(20) 36 DIMENSION Ri(20).R2(20).R3(20),R4(20),R5(20) 37 DIMENSION T1(20.20),T2(20.20),T3(20.20).T4(20,20).T5(20.20) 38 DIMENSION UP2(20).UP3(20).UP4(20),UP5(20) 39 c 40 REAL KP.KPP.NU 4 1 c 42 c READ DATA 43 c 44 DATA DP/0.3DO.O.15DO.0.O7500/ 45 DATA TERM/567.96DO.784.3500.355.200/ 46 DATA TEMPG/723.DO.823.DO.773.00/ 47 c 48 c USE DO-LOOP TO ESTIMATE THE TEMPERATURE PROFILE 49 c FOR 3 DIFFERENT SIZES AT DIFFERENT TEMPERATURES 50 c 51 c DO 9999 MM=1,3 52 TG=TEMPG(3) 53 c DO 999 M=1.3 54 DIA=DP(3) 55 UT=TERM(3) 56 134 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC1d=TITA 57 C 58 59 C 60 C 61 c SECTION 1) SPECIFY THE BASIC INFORMATIN OF THE SPOUTED BED 62 c REACTOR. SAND PARTICLES. OIL SHALE AND SPOUTING 63 64 c 65 c 66 c INFORMATION OF THE SPOUTED BED REACTOR 67 c 68 DI=1.5800 69 DC=12.8DO 70 DPIPE=1.58D0 71 HPIPE=17.8D0 72 APIPE = 3. 14 1600*(DPIPE**2.DO)/4.00 73 HH=33.DO 74 AC0L = 3. 1416DO*(0C*-2.DO)/4.DO 75 ES=0.95DO 76 EA=0.42DO 77 E0=0.7D0 78 c 79 c PROPERTIES OF THE SAND PARTICLES 80 c 81 DPS=0. 1 121D0 82 RRS=0PS/2.DO 83 DENS=2.68D0 84 c 85 c PROPERTIES OF THE OIL SHALE 86 c 87 RR=DIA/2.D0 88 DEN=2.0O 89 KPP= 1 . 25D-2/4. 18600 89. 5 CPP=1.1300/4.186D0 90 c 91 c PROPERTIES OF GAS 92 c 93 CP=(6.76D0+((0.606D-3)*TG)+((0.13D-6)*(TG**2.DO)))/28.DO 94 DENG=1.00*((28.000*0.85DO)+(44.000*0.15D0))/82.05D0/TG 95 KP=0.0001257D0 96 VIS=0.00033D0 97 c 98 c FURTHER INFORMATION 98. 5 c THE FOLLOWING DATA ARE TAKEN FROM STANELY WU'S THESIS 99 c 100 DIS5(1 ) =33.DO 100. 5 DIS5(2)=32.DO 101 DIS5(3)=25.DO 102 DIS5(4 )=20.00 103 DIS5(5)=15.D0 104 DIS5(6)=10.DO 105 DIS5(7)=5.DO 106 c 106 . 5 UP5(2) = 1 .335DO 107 UP5(3)=1 .28900 108 UP5(4 ) = 1 . 188D0 109 UP5(5)=1.05900 1 10 UP5(6 )=2 . 176D0 135 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC i d=TITA 111 UP5(7)=0.83800 1 12 C 1 13 C TO CALCULATE THE HYDRODYNAMIC PROPERTIES OF THE SPOUTED BED 1 14 C BASED ON SAND AS SPOUTING MEDIA 1 15 C 1 16 C TO CALCULATE MAXIMUM SPOUTABLE BED HEIGHT. HM 117 C 1 18 HM=0. 105D0*((DC/DPS)**0.75DO)*((DC/DI)•*0.400)*DC/( DENS' * 1 .200) 1 19 C 120 C TO CALCULATE MINIMUM SPOUTING VELOCITY. UMS 121 C -122 UMS=(DPS/DC)*((DI/DC)**(1.DO/3.DO))*((2.DO*980.DO*HH* 123 & (DENS-DENG)/DENG)* * ( 1.DO/2.DO)) 124 U=1.1D0*UMS 125 0=U*ACOL 126 C 127 C TO CALCULATE THE DIAMETER OF SPOUT. DS 128 C 129 EMF=0.5D0 130 DENB=OENS*(1.DO-EMF) 131 G=DENG*U 132 DS=(0.11800*((G*10.D0)**0.49D0)*((DC/100.DO)* *0.68D0)/ 133 & (0ENB**0.41D0))*100.00 134 AS = 3. 1416DO*(DS**2.DO)/4.00 135 C 136 C TO CALCULATE MINIMUM FLUIDISATION VELOCITY. UMF 137 C 138 CONST=(DPS**3.DO)*(DENG*(DENS-DENG)*980.D0)/(VIS**2.DO) 139 NEBF = (( ( 18.1DO**2.DO) + (O.O192DO*C0NST))**0.5D0)- 18 . 1D0 140 U8F=NEBF*VIS/DPS/DENG 141 NETF = (((24.DO* * 2.DO) + (0.0546DO*C0NST))* *0.5D0)-24.DO 142 UTF=NETF*VIS/DPS/DENG 143 UMF=0.5D0*(UBF+UTF) 144 C 145 WRITE(6,991 (DIA 146 991 FORMAT(1H1,/, '01A OF OIL SHALE PARTICLE = ' ,F6.4. 'CM') 147 WRITE(6.992)UMS 148 992 FORMAT(//. 'MIN SPOUTING VELOCITY ='.F8.4,'CM/SEC') 149 WRITE(6.993)U 150 993 FORMAT(//. 'SPOUTING VELOCITY =',F8.4,'CM/SEC' ) 151 WRITE(6.994)HM 152 994 FORMAT(//. 'MAX SPOUTABLE HEIGHT =' .F7 . 4 , ' CM' ) 153 WRITE(6.995)DS 154 995 FORMAT(//,'DIAMETER OF SPOUT ='.F6.4.'CM') 154.3 WRITE(6.996)TG 154.6 996 FORMAT(//.'REACTOR TEMPERATURE ='.F7.3.'DEG K') 155 C 156 157 C 158 C * 159 C SECTION 2) CALL THE SUBROUTINES TO PERFORM THE CALCULATION AND * 160 C PRINT OUT THE RESULTS 161 C * 162 163 C 164 C INITIALISE ALL TEMPERATURES 165 C 166 DO 111 1=1.10 136 Listing of PROFILE at 11:37:26 on MAY 28: 1987 for CCid=TITA 167 T1( I . 1 ) = 771 .900 167.011 C 168 111 CONTINUE 209 C 210 C 211 C ««•»««*« * ...................... 212 C 213 C CALL SUBROUTINE TEMP2 TO WORK OUT THE * 214 C TEMPERATURE PROFILE IN THE SPOUT 215 C 2 *| 6 c **********|***'************* + **************** 217 C 217.2 C 217.4 WRITE(6.606)CP 217.6 606 F0RMAT(//,F1O.5) 217.8 C 218 CALL TEMP2(TG.DIA,CP,DENG,KP.VIS.RR.DEN,CPP.KPP,HH,AC0L.HM.Q, 219 & AS.ES.EA.T1.UMF.T2.DTIME2.DIS2.R2.UP2.TT2.HP2.BI0T2) 220 C 221 C WRITE TITLE 222 C 223 WRITE(6,200)DIA 224 200 FORMAT(1H1, 'IN THE SPOUTING REGION FOR SIZE =' ,2X,F6.4 . 'CM' ) 225 C 226 C WRITE OUT THE SOLUTIONS OF T2(I.d) 227 C 228 WRITE(6.201) 229 201 F0RMAT(//2X.'VEL CM/SEC'.20X,'TEMP DEG K',28X.'HEIGHT CM', 230 & 3X,'TIME',5X,'HP',4X,'BIOT NO') 231 C 232 DO 202 KK=1 , 10 233 J=11-KK 234 WRITE(6,203)UP2(J),(T2(I,J ) ,I = 1,10).DIS2(d).DTIME2(J).HP2(J ) . 235 & BI0T2(J) 236 203 FORMAT(//2X.F7.2. 1X. 10F6. 1 , 2X.F6.3,2X.F7.5.2X,F7.4,2X.F5.2 ) 237 C 238 202 CONTINUE 239 C 240 C WRITE OUT THE DELTA RADIUS FOR THE PARTICLE AT BOTTOM LINE 24 1 C 242 WRITE(6.204)(R2(I).1=1.10) 243 204 F0RMAT(//10X.10F6.3) 244 C 245 C TO WRITE OUT THE SUB-TIME FOR PARTICLE TO REACH TOP LINE 246 C OF THE SPOUT 247 C 248 WRITE(6.205)TT2 249 205 FORMAT(///, 'SUB-TIME=',F8.4, 'SEC' ) 250 C 251 C 252 C **«*•**«««««» « .««.«....*.«,.....«....» 253 C 254 C CALL SUBROUTINE TEMP3 TO WORK OUT THE 255 C TEMPERATURE PROFILE IN THE FOUNTAIN REGION 256 C • 257 C • •- •• -258 C 259 CALL TEMP3(TG.DIA,DENG.'KP.VIS,DENS.RR.DEN.CPP.KPP,U.UP2.T2.H, 137 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC1d=TITA 260 & T3,0TIME3.DIS3.R3.UP3.TT3.HP3,BI0T3) 26 1 262 C 263 C WRITE TITLE 264 C 265 WRITE(6.300)DIA 266 300 FORMAT(1H1.'IN THE FOUNTAIN REGION FOR SI ZE = '.2X.F6.4.'CM' ) 267 C 268 WRITE(6.301)H 269 301 F0RMAT(//2X,'FOUNTAIN HEIGHT='.F6.3.'CM') 270 C 273 C WRITE OUT THE SOLUTIONS OF T3(I.J) 274 C 275 WRITE (6.302) 276 302 F0RMAT(//2X, 'VEL CM/SEC',20X . 'TEMP DEG K'.28X, 'HEIGHT CM', 277 & 4X,'TIME'.4X,'HP',4X.'BIOT NO') 278 C 279 DO 303 KK=1, 10 280 d=11-KK 281 WRITE(6.304)UP3(J).(T3(I,d) ,1 = 1. 10),DIS3(d),DTIME3(J) , 282 & HP3(d),BI0T3(J) 283 304 FORMAT(//2X.F7.2,1X.10F6.1.2X.F6.3.2X.F6.4.2X.F7.5.2X.F5.2) 284 C 285 303 CONTINUE 286 C 287 C WRITE OUT THE DELTA RADIUS FOR THE PARTICLE AT BOTTOM LINE 288 C 289 WRITE(6.305)(R3(I),I=1,10) 290 305 F0RMAT(//1OX.10F6.3) 291 C 292 C TO WRITE OUT SUB-TIME FOR PARTICLE TO REACH THE FOUNTAIN 293 C 294 WRITE(6.306)TT3 295 306 FORMAT(///. 'SUB-TIME=' .F6.4. 'SEC ) 296 C 297 C 298 C *•-••* ,.,..,.......,«......... « 299 C 300 C CALL SUBROUTINE TEMP4 TO WORK OUT THE * 301 C TEMPERATURE PROFILE IN THE FOUNTAIN FALLING REGION « 302 C 303 C **----«*«-*««••**«.«»*«*•«*.««-««««••«-•.**---««----«-*•* 304 C 305 C 306 CALL TEMP4(TG.DENG.KP.VIS.DIA.DEN,CPP.KPP,DENS.H.E0.U.UP3. 307 S T3,T4,DTIME4,DIS4.R4,UP4,TT4,HP4,BI0T4) 308 C 309 C WRITE TITLE 310 C 311 WRITE(6.400)DIA 312 400 FORMAT(1H1,'IN THE FALLING REGION FOR SIZE -',2X.F6.4,'CM') 313 C 314 WRITE(6.401) 315 401 FORMAT(//2X. 'VEL CM/SEC'.20X,'TEMP DEG K' ,28X. 'HE IGHT CM'. 316 8. 4X ,' TIME '. 4X , 'HP' , 4X , 'BIOT NO') 317 C 319 C 320 00 402 KK=1.10 138 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CCid=TITA 322 WRITE(6.403)UP4(KK). (T4( I.KK), I = 1 . 10),DIS4(KK) .DTIME4(KK), 323 & HP41KK).BI0T4IKK) 324 403 F0RMAT(//2X.F7.2.1X.10F6.1.2X.F6.3.2X.F6.4.2X.F7.5.2X. 325 & F5.2) 326 C 327 402 CONTINUE 328 C 329 C 330 c WRITE OUT THE DELTA RADIUS FOR THE PARTICLE AT BOTTOM LINE 331 c 332 WRITE(6.404)(R4(I),I=1,10) 333 404 F0RMAT(//10X.10F6.3) 334 C 335 C WRITE OUT SUB-TIME FOR PARTICLE TO DROP FROM FOUNTAIN 336 C 337 WRITE(6.405)TT4 338 405 FORMAT(///. 'SUB-TIME='.F6.4. 'SEC ) 339 C 340 341 C • 342 C CALL SUBROUTINE TEMP5 TO WORK OUT THE TEMPERATURE -343 c PROFILE IN THE ANNULUS REGION 344 c 345 346 C 347 CALL TEMP5(TG.01A,DENG.KP,VIS.RR,DEN,CPP.KPP.HH.EA.ES.ACOL.AS 348 & UMF,HM,UP5,DIS5,T4.UP4.T5.DTIME5.R5.TT5.HP5.BI0T5) 349 c 350 c WRITE TITLE 351 c 352 WRITE(6.500)DIA 353 500 FORMAT(1H1,2X,'IN THE ANNULUS REGION FOR SIZE=',F6.4.'CM') 354 C 355 WRITE(6,501) 356 501 F0RMAT(//2X. 'VEL CM/SEC'.20X,'TEMP DEG K ' , 28X . 'HEIGHT CM'. 357 & 4X,'TIME',4X,'HP',4X,'BIOT NO') 358 C 359 DO 502 KK=1.7 360 WRITE(6.503)UP5(KK),(T5(I.KK).I = 1,10).DIS5(KK).DTIME5( KK) . 361 & HP5(KK>.BI0T51KK) 362 503 FORMAT(//2X.F7.2. 1X. 10F6. 1.2X.F6.3.2X,F6 . 4.2X.F7.5.2X. 363 & F5.2) 364 C 365 502 CONTINUE 366 C 367 C WRITE OUT THE DELTA RADIUS FOR THE PARTICLE AT BOTTOM LINE 368 C 369 WRITE(6.504 )(R5(I).1 = 1. 10) 370 504 FORMAT(//10X.10F6.3) 371 C 372 C WRITE OUT TOTAL TIME FOR PARTICLE TO GO DOWN TO ANNULUS 373 C 374 WRITE(6,505)TT5 375 505 FORMAT(III, 'SUB-TIME='.F8.4.'SEC) 376 C 377 C TO WORK OUT THE TOTAL TIME SPENT IN THE 5 REGIONS 378 C 379 TIME=TT1+TT2+TT3+TT4+TT5 139 Listing of PROFILE at 1 1:37:26 on MAY 23. 1987 for CC i d = TITA 380 WRITE(6.600)TIME 38 1 600 FORMAT(///2X, 'TOTAL TIME SPENT IN 5 REGIONS =' .F8 . 4, ' SEC' ) 382 C 383 999 CONTINUE 384 C 385 9999 CONTINUE 386 STOP 387 END 388 389 C 390 C * 391 C SECTION 3) STORE ALL THE SUBROUTINES 392 C * 393 510 C 511 C 512 C * 513 C -514 C SUBROUTINE TEMP2 * 515 C * 516 517 C 518 C 519 SUBROUTINE TEMP2(TG.DIA.CP.DENG.KP,VIS.RR.DEN,CPP.KPP,HH.ACOL. 520 & HM.O,AS.ES.EA.T1,UMF.T2.DTIME2.DIS2.R2,UP2,TT2,HP2.BI0T2) 521 C 522 C 523 IMPLICIT REAL»8 (A-H.O-Z) 524 DIMENSION A(100),B(100),C(100),D(100) 525 DIMENSION 0TIME2(20).DIS2(20),R2(20).HP2(20).BI0T2(20) 526 DIMENSION T1(20.20).T2(20.20).UP2(20) 527 REAL KPP.NU.KP 528 C 529 c SPECIFY CONDITIONS OF GRID 530 c 531 N=10 532 DR=RR/9.D0 533 DD=HH/9.00 534 TT2=O.0D0 535 DTIME2(1)=O.ODO 536 c 537 c 538 c INITIALISE ALL R(I) -539 c 540 DO 20 I=1.N 54 1 20 R2(I)=(I-1)*DR 542 c 543 c 544 c INITIALISE ALL TEMPERATURES 545 c 546 DO 21 IK=1 ,10 547 T2(IK. 1 )=T1(IK. 1) 548 2 1 CONTINUE 549 c 550 c 551 c WORK OUT THE VERTICAL DISTANCE 552 c 553 DO 22 1=1.11 140 Listing of PROFILE at 1 1:37:26 on MAY 28. 1987 for CC id = TITA 554 22 01S 2( I)=DD *(I - 1 ) 555 C 556 C TO WORK OUT SPOUTING VELOCITY AT THE TOP OF THE SPOUT. USH 557 C 558 C 559 UA = UMF*( 1 .D0-(( 1 .DO-(HH/HM))* * 3.DO)) 560 OA=UA*(ACOL-AS) 561 OS=Q-QA 562 USH=QS/AS/ES 563 c 564 c 565 c TO SET UP TRIDIAGONAL EOUATIONS TO SOLVE THE 566 c TEMPERATURE HISTORY FOR A SINGLE PARTICLE 567 c 568 DO 23 0 = 2. 1 1 569 c 570 c 571 c TO WORK OUT THE UA AT EACH INTERVAL 572 c 573 IF (J .EO. 11) GOTO 24 574 UA=UMF*(1.D0-((1.DO-(DIS2(J)/HM))**3.D0)) 575 OA=UA*(ACOL-AS) 576 QS=Q-QA 577 US=OS/AS/ES 578 UP2(d)=( (0.3D0*0.2D0*USH)*(DIS2(d)/HH) )/(1.D0-0.2D0) 579 GOTO 25 580 24 UA=UMF 581 OA=UA*(ACOL-AS) 582 US=QS/AS/ES 583 UP2(J)=((0.3D0*0.2D0*USH)*(DIS2(J)/HH))/(1.D0-0.2D0) 584 25 RV=DABS(US-UP2(J)) 585 c 586 c TO CALCULATE HP FOR THE OIL SHALE IN THE SPOUTING REGION 587 c 588 E=0.400 589 RE=DIA*RV*DENG/VIS 590 PR=CP*VIS/KP 591 AA=2.D0/(1.D0-((1.DO-E)**(1.D0/3.D0))) 592 BB = 2.DO* E/3.DO 593 NU = AA+BB*(PR**( 1.00/3.DO))*(RE * *0.55D0) 594 HP=NU*KP/2.D0/RR 595 JJ = d- 1 596 HP2(Jd)=HP 597 BI0T2(dJ)=HP*RR/KPP 598 c 599 c 600 ALPHA=KPP/CPP/DEN 601 c 602 c TO WORK OUT THE DT 603 c 604 DTIME2(d)=0D/UP2(d) 605 TT2=TT2+DTIME2(J) 606 DT=DTIME2(d) 607 UP2(1)=O.ODO 608 c 609 c SET COEFFICIENTS OF MATRICS 610 c 6 1 1 c BOUNDARY CONDITION AT R=0 141 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC i d = TITA 6 12 C 6 13 B( 1) = -(6.DO*ALPHA/(DR*"2.DO) )-( 1 .DO/DT) 6 14 C(1 ) =6.DO*ALPHA/(DR**2.DO) 6 15 C 616 c BOUNDARY CONDITION AT R=N 617 C 6 18 A(N) = 2.DO*ALPHA/(DR * * 2.DO) 619 B(N) = (- 1.DO/DT)-(2.DO* A LPHA *HP/R2(N)/KPP) -620 > (2.DO*ALPHA/(DR**2.DO))-(2.DO*ALPHA*HP/DR/KPP) 62 1 C 622 C INITIALISE ALL VALUES OF A(I). B(I). ANO C(I) 623 c 624 DO 26 IK=2.9 625 A(IK) = (ALPHA/(DR * * 2.DO))-(ALPHA/R2(IK)/DR) 626 B(IK) = (-2.DO*ALPHA/(DR* *2.DO))-( 1.DO/OT) 627 26 C(IK)=(ALPHA/R2(IK)/OR)+(ALPHA/(DR* *2.DO)) 628 c 629 D(1) = -T2( 1 .J-1)/DT 630 DO 27 1=2.9 631 27 D(I)=-T2(I.J-1)/DT 632 0(N) = -(T2(N,«J-1)/DT) - ( 2 .DO*ALPHA *HP *TG/R2(N)/KPP)-633 > (2.D0*ALPHA*HP*TG/DR/KPP) 634 c 635 c CALL LIBRARY PROGRAMM TO SOLVE THE TRI-DIA EONS 636 c 637 CALL TRISLV(N,A.B.C.D.0.&99) 638 C 639 C 640 C STORE THE SOLUTIONS T2(I.d) 64 1 C 642 DO 28 11=1.N 643 T2(II.J)=D(II) 644 28 CONTINUE 645 C 646 23 CONTINUE 647 C 648 GOTO 299 649 99 WRITE(6.29) 650 29 F0RMAT(///2X.'ERROR MESSAGE') 651 299 CONTINUE 652 C 653 RETURN 654 END 655 C 656 C 657 658 C * 659 C SUBROUTINE TEMP3 * 660 C * 66 1 662 C 663 C 664 SUBROUTINE TEMP3(TG.DIA,DENG,KP,VIS.DENS.RR,DEN.CPP.KPP 665 & UP2.T2.H.T3.DTIME3.DIS3.R.UP3.TT3.HP3.BI0T3) 666 C 667 IMPLICIT REAL * 8 (A-H.O-Z) 668 DIMENSION A( 100),B( 100),C( 100) .D( 100) 669 DIMENSION BI0T3(20).DI S3(20 ) .DTIME3(20).HP3(20).R(20) 142 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CCid=TITA 670 DIMENSION T2(20.20).T3(20.20),UP2(20).UP3(20) 671 REAL KP.NU.KPP 672 C 673 C TO CALCULATE THE HEIGHT OF FOUNTAIN REGION. H. 674 C 675 UP3( 1 )=UP2( 10) 676 UP3(11)=O.ODO 677 E0=0.7D0 678 H=(E0**1.46D0)*(UP3( 1)**2.DO)*DENS/(DENS-DENG ) /2.DO/980.DO 679 C 680 C TO WORK OUT THE TEMPERATURE OF DIFFERENT PARTICLE SIZE 681 C 682 C 683 C SPECIFY CONDITIONS OF GRID 684 C 685 N= 10 686 DR=RR/9.D0 687 DD=H/9.D0 688 TT3=0.0D0 689 DTIME3(1)=0.0D0 690 C 691 c 692 c INITIALISE ALL R(I) 693 c 694 DO 30 1=1.N 695 30 R(I ) = (I-1 )»DR 696 c 697 c 698 c INTIALISE ALL TEMPERATURES 699 c 700 DO 31 11 = 1 . 10 701 T3(II. 1 )=T2(II.10) 702 31 CONTINUE 703 C 704 C 705 C WORK OUT THE VERTICL DISTANCE 706 c 707 DO 32 1=1.11 708 32 DIS3(I ) =DD*( I - 1 ) 709 C 710 C 711 C TO SET UP TRIDIAGONAL EOUATIONS TO SOLVE THE TEMPERATURE 7 12 C HISTORY FOR A SINGLE PARTICLE 713 C 714 DO 33 d = 2, 1 1 715 C 716 C 717 IF (J.EO. 1 1 ) GOTO 34 718 C 719 C TO WORK OUT THE VELOCITY OF PARTICLE AT EACH INTERVAL IN 720 C THE FOUNTAIN REGION 721 c 722 UP3(J) = ((UP3( 1 )* * 2.DO)-(2.D0*980.DO*DI S3(J)*(DENS-DENG)/DENS/ 723 > (E0*« 1 .46D0)))**0.5D0 724 c 725 c TO WORK OUT THE DELTA TIME 726 c 727 DTIME3(d)=DD/UP3(d-1) 143 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC i d = TITA 728 TT3=TT3+DTIME3(d) 729 DT=0TIME3(d) 730 C 731 34 CONTINUE 732 C 733 RV = DABS(U-UP3(d) ) 734 C 735 c TO CALCULATE HP FOR THE COAL PARTICLE IN FOUNTAIN REGION 736 c 737 RE=DIA*RV*DENG/VIS 738 NU=0.42D0+0.3500*(RE * *0.8DO) 739 HP=NU*KP/2.D0/RR 740 ALPHA=KPP/CPP/DEN 741 dd=d-1 742 HP3(dd)=HP 743 BI0T3(dd)=HP*RR/KPP 744 c 745 c SET COEFFICIENTS OF MATRICS 746 c 747 c BOUNDARY CONDITION AT R=0 748 c 749 B(1)=-(6.00*ALPHA/(DR**2.DO))-(1.DO/OT) 750 C(1)=6.DO*ALPHA/(DR**2.DO) 751 c 752 c 753 c BOUNDARY CONDITION AT R=N 754 c 755 A(N)=2.DO*ALPHA/(DR**2.00) 756 B(N)=(-1.DO/DT)-(2.DO*ALPHA*HP/R(N)/KPP)-757 > (2.DO*ALPHA/(DR**2.DO))-(2.DO*ALPHA*HP/DR/KPP) 758 c 759 c INITIALISE ALL VALUES OF A(I). B(I). C(I) 760 c 761 DO 35 IK=2.9 762 A(IK)=(ALPHA/(DR**2.DO))-(ALPHA/R(IK)/DR) 763 B(IK)=(-2.D0*ALPHA/(DR**2.D0))-(1.DO/DT) 764 C(IK)=(ALPHA/R(IK)/DR)+(ALPHA/(DR**2.DO)) 765 35 CONTINUE 766 C 767 D( 1) = -T3(1,d-1)/DT 768 C 769 DO 36 1=2,9 770 D(I)=-T3(I,d-1)/DT 77 1 36 CONTINUE 772 C 773 C 774 D(N) = -(T3(N,d-1)/DT)-(2.DO*ALPHA *HP *TG/R(N)/KPP)-775 > (2.D0*ALPHA*HP*TG/DR/KPP) 776 C 777 C 778 C CALL LIBRARY PROGRAM TO SOLVE THE TRI-DIA EOUATIONS 779 c 780 CALL TRISLV(N.A.B,C,D.0.&99) 781 c 782 c 783 c STORE THE SOLUTIONS T3(I.d) 784 c 785 DO 37 11 = 1 .N 1AA Listing of PROFILE at 1 1:37:26 on MAY 28. 1987 for CC i d = TITA 786 T3(II .J)=D(I I ) 787 37 CONTINUE 788 C 789 33 CONTINUE 790 C 791 C 792 GOTO 39 793 99 WRITE(6.38) 794 38 FORMAT(///2X.'ERROR MESSAGE') 795 C 796 39 RETURN 797 END 798 C 799 C 800 C QQ -j Q ********************** 802 C 803 C SUBROUTINE TEMP4 * 804 C 805 C » 806 C 807 C 808 SUBROUTINE TEMP4(TG,DENG.KP.VIS,DIA.DEN,CPP,KPP.DENS.H.EO.U. 809 & UP3.T3.T4.DTIME4,0IS4,R.UP4,TT4.HP4.BI0T4) 8 10 C 811 IMPLICIT REAL*8 (A-H.O-Z) 812 DIMENSION A(100).B(100).C(100).D(1OO) 813 DIMENSION BI0T4(20),DIS4(20),DTIME4(20).HP4(20).R(20) 814 DIMENSION T3(20.20).T4(20.20).UP3(20).UP4(20) 815 REAL NU.KP.KPP 816 C 817 C SPECIFY CONDITIONS OF OIL SHALE 818 C 819 RR=DIA/2.DO 820 DEN=2.0D821 KPP=1.25D-2/4.186DO 822 C 823 C SPECIFY CONDITION OF GRID 824 C 825 N=10 826 DR=RR/9.D0 827 DD=H/9.D828 TT4=0.0D0 829 DTIME4(1)=0.0D0 830 UP4(1)=0.0D0 831 C 832 C INITIALISE ALL R(I) 833 C 834 DO 40 1 = 1 ,N 835 40 R( I ) = (I-1)*DR 836 C 837 C 838 C INITIALISE ALL TEMPERATURES 839 C 840 DO 4 1 11=1,10 84 1 4 1 T4( 11, 1 )=T3(11.10) 842 C 843 C 145 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC1d=TITA 844 C WORK OUT THE VERTICAL DISTANCE 845 C 846 DO 4 2 1=1.11 847 42 DIS4(I )=DD*(1-1) 848 C 849 C 850 C TO SET UP TRIDIAGONAL EOUATIONS TO SOLVE THE TEMPERATURE 851 C HISTORY FOR A SINGLE PARTICLE 852 C 853 DO 43 d = 2. 1 1 854 C 855 C TO WORK OUT THE VELOCITY OF PARTICLE AT EACH INTERVAL 856 C OF THE FALLING REGION 857 C 857. .3 IF (d .EO. 11) GOTO 44 857. 6 c 858 UP4(J) = ((2.00*980.DO*(DENS-DENG )/OENS/(EO**1.4600))* 859 & (H-DIS4(11-d)))**0.5D0 859. 5 c 859. 7 44 UP4(11)=UP3( 1 ) 860 C 861 C 862 C TO WORK OUT THE DELTA TIME 863 C 864 0TIME4(d)=0D/UP4(d) 865 TT4=TT4+DTIME4(d) 866 OT=DTIME4(d ) 867 C 868 c 869 c TO CALCULATE HP FOR THE OIL SHALE IN THE FALLING REGION 870 c 871 RV=DABS(U-UP4(d)) 872 RE=DIA*RV*DENG/VIS 873 NU=0.42DO+0.35DO*(RE * *0.8D0) 874 HP=NU*KP/2.D0/RR 875 ALPHA=KPP/CPP/DEN 876 dd=d-1 877 HP4(dd)=HP 878 BI0T4(dd)=HP*RR/KPP 879 c 880 c SET COEFFICIENTS OF MATRICS 881 c 882 c BOUNDARY CONDITION AT R=0 883 c 884 B(1 ) = -(6.00*ALPHA/(DR**2.DO))-( 1 .DO/DT) 885 C(1)=6.DO*ALPHA/(OR**2.00) 886 c 887 c 888 c BOUNDARY CONDITION AT R=N 889 c 890 A(N)=2.DO*ALPHA/(DR * * 2.DO) 891 B(N)=(-1.DO/DT)-(2.DO*ALPHA*HP/R(N)/KPP)-892 & (2.DO*ALPHA/(DR**2.DO))-(2.DO*ALPHA'HP/DR/KPP) 893 c 894 c INITIALISE ALL VALUES OF A(I ) .B(I ) .C(I ) 895 c 896 DO 45 IK=2,9 897 A(IK ) = (ALPHA/(DR**2.D0) )-(ALPHA/R(IK)/DR) 146 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC i d= TITA 898 B(IK)=(-2.DO*ALPHA/(DR**2.DO))-(1.DO/DT) 899 C(IK ) = (ALPHA/R( IK)/DR)+(ALPHA/(DR**2.D0)) 900 45 CONTINUE 901 C 902 D( 1 ) = -T4( 1 .J-1)/DT 903 DO 46 1=2.9 904 0(I)=-T4(I.d-1)/DT 905 46 CONTINUE 906 C 907 C 908 D(N)=-(T4(N,d-1)/DT)-(2.DO*ALPHA*HP*TG/R(N)/KPP)-909 & (2.D0*ALPHA*HP*TG/DR/KPP) 910 C 91 1 C CALL LIBRARY PROGRAM TO SOLVE THE TRI-DIA EQUATIONS 912 C 913 CALL TRISLV(N,A.B.C,D.0.&99) 914 C 915 C STORE THE SOLUTIONS T4(I.J) 916 C 917 DO 47 11 = 1 .N 918 T4(II.J)=D(II) 919 47 CONTINUE 920 C 921 43 CONTINUE 922 C 923 C 924 GOTO 49 925 99 WRITE(6.48) 926 48 FORMAT(///2X,'ERROR MESSAGE') 927 C 928 49 RETURN 929 END 930 C 931 C 932 C 933 934 C * 935 C SUBROUTINE TEMP5 * 936 C * 937 938 C 939 C 940 SUBROUTINE TEMPS(TG,DIA.DENG,KP.VIS.RR .DEN.CPP.KPP,HH.EA,ES 94 1 & ACOL.AS.UMF,HM.UP5,DIS5,T4,UP4,T5.DTIME5.R.TT5.HP5.BI0T5) 942 c 943 IMPLICIT REAL*8 (A-H.O-Z) 944 DIMENSION A(100). B(100). C(100). D(100) 945 DIMENSION BI0T5(20),DIS5(20).DTIME5(20).HP5(20).R(20) 94G DIMENSION T4(20.20).T5(20.20).UP4(20).UP5(20) 947 REAL NU. KP, KPP 948 c 949 c 950 c SPECIFY CONDITIONS OF GRID 951 c 952 N= 10 953 0R=RR/9.D0 954 TT5=O.ODO 955 DTIME5(1)=0.0D0 147 Listing of PROFILE at 1 1:37:26 on MAY 28. I987 for CC i d = TITA 956 C 957 C 958 C INITIALISE ALL R(I) 959 C 960 00 50 I = 1.N 961 R( I ) = (I-1)*DR 962 50 CONTINUE 963 C 964 C 965 C INITIALISE ALL TEMPERATURE 966 C 967 00 51 IK=1 . 10 968 T5(IK, 1 )=T4(IK. 10) 969 5 1 CONTINUE 970 C 971 C WORK OUT THE VERTICAL DISTANCE 972 C 973 C 974 c TO SET UP TRIDIAGONAL EOUATIONS TO SOLVE THE TEMPERATURE 975 c HISTORY FOR A SINGLE PARTICLE 976 c 977 DO 52 J=2.8 978 c 979 c TO WORK OUT THE UA AT EACH INTERVAL 980 c 981 UP5(1)=UP4(10) 982 UA=UMF*(1.D0-((1.D0-(DIS5(0-1)/HM)**3.DO))) 983 OA=UA*(ACOL-AS) 984 RV=DABS(UA-UP5(d-1)) 985 c 986 c 987 c TO CALCULATE HP FOR THE OIL SHALE PARTICLE IN THE ANNULUS 988 c 989 RE=DIA*RV«OENG/VIS 990 NU=O.42DO+O.35D0«(RE**O.80O) 991 HP=NU*KP/2.D0/RR 992 dd=d-1 993 HP5(JJ)=HP 994 BI0T5(Jd)=HP*RR/KPP 995 c 996 ALPHA=KPP/CPP/DEN 997 c 998 c TO WORK OUT DT 999 c 1000 IF (J .EO. 8)G0T0 53 1001 DTIME5CJ)=(DIS5(d-1)-DIS5(d))/UP5(J-1) 1002 TT5=TT5+DTIME5(J) 1003 DT=0TIME5(iJ) 1004 53 CONTINUE 10O5 C 1006 C TO SET COEFFICIENTS OF MATRICS 10O7 C 1008 c BOUNDARY CONDITION AT R=0 1009 c 1010 B( 1) = -(6.D0*ALPHA/(DR'*2.00))-( 1.DO/DT) 101 1 C(1)=6.D0*ALPHA/(DR**2.D0) 1012 c 1013 c BOUNDARY CONDTION AT R=N 148 Listing of PROFILE at 11:37:26 on MAY 28. 1987 for CC1d=TITA 1014 C 1015 A(N)=2.DO*ALPHA/(DR**2.DO) 1016 B(N) = (- 1 .DO/DT)-(2.DO*ALPHA*HP/R(N)/KPP)-1017 & (2.D0*ALPHA/(DR**2.D0))-(2.DO*ALPHA•HP/DR/KPP) 1018 C 1019 C INITIALISE ALL VALUES OF A(I), B(I), AND C(I) 1020 C 1021 DO 54 IK=2.9 1022 A(IK)=(ALPHA/(DR**2.D0))-(ALPHA/R(IK)/DR) 1023 B(IK)=(-2.DO*ALPHA/(DR**2.DO))-(1.DO/DT) 1024 54 C(IK)=(ALPHA/R(IK)/DR)+(ALPHA/(DR**2.DO)) 1025 C 1026 D(1)=-T5(1.J-1)/DT 1027 DO 55 1=2,9 1028 55 D(I)=-T5(I.J-1)/DT 1029 0(N)=-(T5(N.d-1)/DT)-(2.D0*ALPHA*HP*TG/R(N)/KPP) 1030 & (2.D0*ALPHA*HP*TG/DR/KPP) 1031 C 1032 C 1033 C 1034 C CALL LIBRARY PROGRAMM TO SOLVE THE TRI-DIA EONS 1035 C 1036 CALL TRISLV(N,A,B.C.D,0,&99) 1037 C 1038 DO 56 11 = 1 ,N 1039 T5(II,J)=D(II) 1040 56 CONTINUE 1041 C 1042 52 CONTINUE 1043 C 1044 GOTO 58 1045 99 WRITE(6,57) 1046 57 F0RMAT(///2X.'ERROR MESSAGE') 1047 C 1048 58 RETURN 1049 END 149 C.2 Entrance 150 Listing of ENTRANCE at 13:07:28 on JUN 11, 1987 for CC i d = TIT A 1 2 C -3 C NAME: ENTRANCE 4 C * • 5 C THIS PROGRAM IS USED TO ESTIMATE THE TEMPERATURE PROFILE 6 C FOR A PARTICLE IN THE ENTRANCE SECTION OF THE SPOUTED BED * 7 8 9 C * 10 IMPLICIT REAL"8 (A-H.O-Z) 1 1 DIMENSION A(100),B(100),C(100) 12 DIMENSION D(100), DTIME(IOO). DIS(100) 13 DIMENSION R(100),T(100,100) 14 DIMENSION DP(3 ) .VELT(3),TEMPG(3) 15 REAL KP.NU 16 C 17 C 18 C READ DATA 19 c 20 DATA DP/0.30D0.0.15D0,0.075D0/ 21 DATA VELT/567.9666DO, 784.358DO.355.02D0/ 22 DATA TEMPG/723.0D0.773.0D0.823.0DO/ 23 c 24 c TO WORK OUT THE TEMP PROFILE FOR TWO DIFFERENT GAS TEMPERATURE 25 c 26 DO 777 JJ=1.3 27 28 c 29 c 30 c SPECIFY CONDITIONS OF SPOUTING GAS 31 c 32 TG=TEMPG(JJ) 33 KP=O.OOO15O80O 34 DENG=1.DO*(28.00*0.85D0 +44.00*0.15DO)/82.0500/TG 35 VIS=O.OOO330O 36 CP = (6.76D0+((0.606D-3)*TG)+((0. 13D-6)*(TG**2.DO)))/28.DO 37 c 38 c 39 c CONDITION OF SAND PARTICLE 40 c 4 1 DPS=0. 1 121 1D0 42 RRS=DPS/2.D0 43 DENS=2.68D0 44 c 45 c 46 c DATA ON THE REACTOR 47 c 48 DI=1.58D0 49 DC=12.8D0 50 HC=76.2DO 51 AC0L = 3. 1416D0*(DC**2.D0)/4.D0 52 HH=33.ODO 53 c 54 c 55 c DATA ON THE ENTRANCE REGION 56 c 57 DPIPE= 1 .58D0 58 HPIPE=17.8D0 151 Listing of ENTRANCE at 13:07:28 on JUN 1 1. 1987 for CC id = TITA 59 APIPE=3. 1416DO*(DPIPE**2.DO)/4.DC 60 C 61 C USE DO-LOOP TO ESTIMATE THE TEMPERATURE PROFILE 62 C FOR 3 01FFERENT SIZES 63 C 64 DO 999 M=1,3 65 DIA=DP(M) 66 UT=VELT(M) 67 C 68 C 69 C WRITE TITLE 70 c 71 WRITE(6.101)DP(M) 72 101 FORMAT(1H1,'IN THE ENTRANCE REGION FOR SIZE =' ,2X,F6. 4, 'CM' ) 73 WRITE(6. 1 1 1 )TG 74 111 FORMATf/7.1X.'THE TEMPERATURE OF THE GAS IS ', F6. 1 .' DEG K' ) 75 c 76 C 77 C SPECIFY CONDITIONS OF OIL SHALE PARTICLE 78 C 79 RR=DIA/2.D0 80 DEN=2.0D0 81 E=0.4D0 82 KPP=1.25D-2/4. 186DO 83 CPP=1 . 13DO/4.186DO 84 C 85 C 86 C TO WORK OUT HM BASED ON SAND PROPERTIES 87 C 88 GEMA= 1 . 89 HM=0.105D0*((DC/DPS)*"0.75D0)*((OC/DI)**O.40O) *DC/(DENS **1 .200) 90 WRITE(6,41)HM 91 41 FORMAT(//'HM=',F8.4,'CM') 92 c 93 C TO CALCULATE THE MINIMUM SPOUTING VELOCITY USING 94 c MARTHER GISHLER MODEL 95 C 96 UMS=(DPS/DC)*((DI/OC)**(1.DO/3.DO))*((2.D0*980 .DO*HH* 97 & (DENS-DENGJ/DENG) - *(1.DO/2.DO)) 98 U=1.1DO*UMS 99 Q=U*ACOL 100 VEL=0/APIPE 101 V=VEL-UT 102 RV=VEL-V 103 C 104 C 105 c TO CALCULATE HP FOR OIL SHALE PARTICLE 106 c 107 RE=DIA*RV*DENG/VIS 108 PR=CP*VIS/KP 109 AA=2.D0/(1.D0-((1.DO-E)**(1.DO/3.DO))) 1 10 BB = 2.DO* E/3.DO 1 1 1 C 1 12 c IN THE ENTRANCE REGION 113 c 1 14 NU=2.DO+0.6DO*(RE**0.5D0)*(PR**(1.DO/3.DO)) 1 15 HP=NU*KP/2.DO/RR 1 16 ALPHA=KPP/CPP/DEN 152 Listing of ENTRANCE at 13:07:28 on JUN 1 1. 1987 for CC i d = TITA 1 17 C 1 18 C 1 19 C SPECIFY CONDITIONS OF GRID 120 c 121 N=10 122 DR=RR/9.D0 123 DT=HPIPE/9.D0/V 124 c 125 c 126 c SET ALL DELTA TIME 127 c 128 DO 4 1 = 1 ,N 129 4 DTIME(I)=0T*(1-1) 130 c 131 c 132 c INITIALISE ALL R(I ) 133 c 134 DO 5 1 = 1 ,N 135 5 R(I) = (I-1 )*DR 136 c 137 c 138 c INITIALISE ALL TEMPERATURES 139 c 140 DO 10 1=1,N 141 10 T(I.1)=298.DO 142 c 143 c 144 c WORK OUT THE VERTICAL DISTANCE 145 c 146 DO 6 I = 1 , N 147 6 DIS(I)=V*DTIME(I) 148 c 149 c 150 c TO SET UP TRIDIAGONAL EQUATIONS TO SOLVE THE 151 c TEMPERATURE HISTORY FOR A SINGLE PARTICLE 152 c 153 DO 30 0=2.11 154 c 155 c 156 c SET COEFFICIENTS OF MATRICS 157 c 158 c BOUNDARY CONDITION AT R=0 159 c 160- B(1) = -(6.DO* ALPHA/(DR* * 2.DO))-(1.DO/DT) 161 C(1)=6.DO*ALPHA/(DR**2.DO) 162 c 163 c BOUNDARY CONDITION AT R=N 164 c 165 A(N)=2.DO*ALPHA/(DR**2.DO) 166 B(N) = (- 1 .DO/DT)-(2.DO*ALPHA*HP/R(N )/KP ) -167 > (2.DO*ALPHA/(DR**2.DO))-(2.DO*ALPHA*HP/DR/KP ) 168 c 169 c 170 c INITIALISE ALL VALUES OF A(I). B(I) AND C(I) 17 1 c 172 DO 20 IK=2.9 173 A(IK) = (ALPHA/(DR**2.DO) )-(ALPHA/R(IK)/DR ) 174 B(IK) = (-2.DO* ALPHA/(DR * * 2.DO ) ) -( 1 .DO/DT) 153 Listing of ENTRANCE at 13:07:28 on JUN 1 1. 1987 for CC i d = TITA 175 20 C ( IK ) = (ALPHA/R(IK)/DR)+(ALPHA/(DR**2.D0)) 176 C 177 D( 1 ) = -T( 1.J-1)/DT 178 00 40 1=2,9 179 40 D(I)=-T(I,J-1)/DT 180 D(N)=-(T(N.J-1)/DT)-(2.D0*ALPHA*HP*TG/R(N)/KP)-181 > (2.DO*ALPHA*HP*TG/DR/KP) 182 C 183 c 184 c CALL LIBRARY PROGRAM TO SOLVE THE TRI-DIA EONS 185 c 186 CALL TRISLV(N. A.B,CD.0.599) 187 c 188 c 189 c STORE THE SOLUTIONS T(I.d) 190 c 191 DO 50 11 = 1 .N 192 T(II.d)=D(II) 193 50 CONTINUE 194 c 195 30 CONTINUE 196 c GO TO 500 197 c 198 99 WRITE(6.103) 199 103 FORMAT(//.'SOLUTIONS ARE') 200 500 CONTINUE 201 c 202 c 203 c WRITE OUT THE SOLUTIONS OF T(I.d) 204 c 205 WRITE(6.301) 206 301 FORMAT(//'SEC,20X,'TEMPERATURE DEG K',28X,' CM ') 207 c 208 DO 200 KK= 1 , 10 209 J=11-KK 210 WRITE(6.300)DTIME(d).(T(I.J),I=1,10),DIS(d) 21 1 300 FORMAT(//1X.F5.4.2X. 10F6. 1.2X.F6.3 ) 212 c 213 200 CONTINUE 2 14 c 215 c 216 c WRITE OUT THE DELTA RADIUS FOR THE PARTICLE AT BOTTOM 217 c 218 WRITE(6,400)(R(I).1=1,10) 219 400 F0RMAT(//8X,10F6.3) 220 c 221 c 222 999 CONTINUE 223 c 224 777 CONTINUE 225 STOP 226 END 154 C.3 Calculate 155 Listing of CALCULATE at 14:22:12 on MAY 28. 1987 for CC1d=TITA t c ................. ........................................ 2 C 3 C NAME OF THIS PROGRAM: CALCULATE 4 C 5 C THIS PROGRAM IS USED TO CALCULATE THE DATA FOR ANALYSIS 6 C SECTION 1: TO CALCULATE OIL YIELD 7 C SECTION 2: TO CALCULATE SPENT SHALE YIELD 8 C SECTION 3: TO CALCULATE TOTAL GAS AND INDIVIDUAL GAS YIELDS 9 C 10 c *«***«*«-«««««««•««*«*«««*««»*«*****«•**«*•*«*-••***••******«* 1 1 c 12 REAL NF 13 C 14 C READ DATA 15 C 16 SN=5.371 17 CF=1801.5/80./60. 18 FEED= 19 WRITE(6.8)CF 20 8 FORMAT(2X, 'CF =' ,F7.4) 21 CFMA=CF 22 SG=0.158 23 WRITE(6.333)CF 24 333 FORMAT(2X,'CF',F7.4) 25 C 26 C *»«•*«••****•««*«*-*«*««--**«»*•*«**»•** 27 C * 28 C SECTION 1: TO CALCULATE OIL YIELD * 29 C30 C ****•**•*«»****«••«»•*«•»•««*««•«*«»*«« 31 C 32 C 33 OYIELD=(OIL/FEED)*100.0 34 WRITE(6. 11)0YI ELD 35 11 FORMAT(/,'OIL YIELD=' .F10.5) 36 C 37 C 38 C «•«•*-*•«*-«*«*•*-*•***••«*«***»*•*-««*••••*«*-39 C « 40 C SECTION 2: TO CALCULATE SPENT SHALE YIELD * 41 C * 42 C •**••••*«*««••*•*•--**•••««•«*«*«***«***«*»«-•* 43 C 44 SYIELD=(SPENT/FEED)*100.0 45 WRITE(6.22)SYIELD 46 22 FORMAT(/. 'SPENT SHALE YIELD=' .F 10.5 ) 47 C 48 C 49 C «**«**••*•-»»•••*««»••--«««*-«««««««•*«*«***«««*•«******«*-**• 50 C 51 C SECTION 3: TO CALCULATE TOTAL GAS AND INDIVIDUAL GAS YIELDS 52 C 53 C *«*«*-*«•***•*««»«-••«.-•••*««****«*«*****•**»»* 54 C 55 C READ VOLUME PERCENTAGE OF INDIVIDUAL FROM GAS CHROMOTOGRAPH 56 C 57 VH2=0.03324 58 VC02=1S.239O 156 Listing of CALCULATE at 14:22:12 on MAY 28. 1987 for CC i d = TITA 59 V02=0.0000 60 VN2=84.727 61 VCH4=0.00 62 VC0=0.0 63 C 64 C 65 WRITE(6. 1 ) 66 1 FORMAT(1H1.21X.'H2',7X,'C02',7X.'02'.8X.'N2'.8X, ,'CH4'. 67 & 8X, 'CO' ) 68 WRITE(6,2)VH2,VC02.V02,VN2.VCH4 . VCO 69 2 FORMAT(//.2X. 'VOL %' . 12X.6(F7.4,3X ) ) 70 c 71 C TO CORRECT FOR AIR LEAKED INTO THE SYSTEM 72 C 73 AIR = V02 + (V02*(0.79/0.21 ) ) 74 C0R=10O./(100.-AIR) 75 c 76 CVH=VH2*C0R 77 CVC02=VC02*C0R 78 CVN2=(VN2-(V02*(0.79/0.21)))*COR 79 CVCH4=VCH4*C0R 80 CVC0=VC0*C0R 81 C 82 C TO WRITE THE CORRECTED VOLUME PERCENTAGE OF INDIVIDUAL GAS 83 c 84 WRITE(6,IO)CVH.CVC02.CVN2.CVCH4.CVCO 85 10 FORMAT(/,2X. 'CORRECTED VOL %'.2X.2(F7.4,3X), 10X , ,3(F7.4.3X)) 86 c 87 c TO CALCULATE WEIGHT PERCENTAGE FOR INDIVIDUAL GAS 88 c 89 WH2=(2./82.07/293.)*CVH 90 WC02=(44./82.07/293.)*CVC02 91 WN2=(28./82.07/293.)-CVN2 92 WCH4=(16./82.07/293.)*CVCH4 93 WC0=(28./82.07/293.)•CVCO 94 TW=WH2+WC02+WN2+WCH4+WC0 95 c 96 c 97 HF=100."WH2/TW 98 C02F=10C.*WC02/TW 99 NF=100.*WN2/TW 100 CH4F=100.*WCH4/TW 101 COF=100.*WCO/TW 102 c 103 c TO WRITE THE WEIGHT PERCENTAGE OF INDIVIDUAL GAS 104 c 105 WRITE(6.20)HF,C02F.NF,CH4F,COF 106 20 FORMAT(/ , 2X , 'WEIGHT %' . 9X . 2 ( F7.4.3X ) . 10X.3(F7 . 4, 3X) ) 107 WRITE(6.30)TW 108 30 FORMAT(/ , 2X ,'TW='.F10.4) 109 c 1 10 c WEIGHT FRACTION OF NITROGEN 1 1 1 c 1 12 NF=(WN2+WC02)/TW 1 13 WRITE(6,7)NF 1 14 7 FORMAT(2X.F10.5) 1 15 TG=SN/NF 1 16 c 157 Listing of CALCULATE at 14:22:12 on MAY 28, 1987 for CC i d = TITA 1 17 C 1 18 C GAS PRODUCED DUE TO PYROLYSIS 1 19 C 120 PGAS=TG-SN 121 WRITE (6. 1 1 )TG.PGAS 122 1 1 FORMAT(2X.F10.5.5X,F10.5) 123 C 124 C GAS YIELD 125 C 126 YI ELD=100.*(TG-SN)/CFMA 127 C 128 WRITE(6,21)YIELD 129 21 F0RMAT(2X.'TOTAL YIELD OF GAS='.F7 .4) 130 C 131 C INDIVIDUAL GAS YIELD 132 C 133 YH=(TG/FEED)*(WH2/TW)*100. 134 YCH4=(TG/FEED)*(WCH4/TW)«100. 135 YC0=(TG/FEED)*(WC0/TW)*1O0. 136 C 137 C 138 C WRITE THE YIELD OF INDIVIDUAL GAS 139 C 140 WRITEC6.31)YH,YCH4,YC0 141 31 FORMAT (/,2X. 'YIELD 7,' , 1 1X . F7 . 4 . 32X , ,2(F7 142 C 143 C 144 RETURN 145 END 158 C.4 Model 159 Listing of MODEL at 12:26:52 on MAY 28. 1987 for CC i d = TITA , c  2 C 3 C NAME OF THIS PROGRAM: MODEL 4 C 5 C THIS PROGRAM USES UBC LIBRARY PROGRAM NL2SN0 TO SOLVE FOR 6 C THE PARAMETERS K3 & E3. INOROER TO OBTAIN THE RATE CONSTANT « 7 C FOR THE OIL TO GASES REACTION. * 8 C THE OTHER PARAMETERS KI. K2. E1. E2. FRACT1. FRACT2. AND 9 C KO ARE TAKEN FROM THE LITERATURES.10 C 12 C 13 C 14 IMPLICIT REAL*8 (A-H.K.O-Z) 15 INTEGER I.L.N.KK 16 COMMON/BLKA/FO(10).F1(10).F2(10).W(10).TEMP(10).SIZE ( 10) . 17 & FEED(10) .AEXPT( 10).ACAL(10),MUM( 10) 18 DIMENSION P(6). IV(66).V(5000). R(10) 19 EXTERNAL CALCR 20 C 21 C READ IN DATA 22 C 23 DO 1100 MM=1,6 24 READ(5,551)MUM(MM),FO(MM).F1(MM ) ,F2(MM).W(MM),TEMP (MM). 25 & SIZE(MM).FEED(MM).AEXPT(MM) 26 551 FORMAT(14,IX.F6.4,1X,F6.4,1X,F5.3. 1X.F6.1,1X.F5. 1, 1X.F4.2. 27 & 1X.F6. 1 . 1X.F6.2) 28 WRITE(6.66)TEMP(MM),AEXPT(MM).F0(MM).F1(MM) 29 66 FORMAT(1X,F10.4,2X.F1O.4,2X.F10.4.2X.F10.4) 30 1100 CONTINUE 31 C 32 C TO DEFINE THE N, M. P, IV AND V 33 C 34 N=6 35 M=2 36 P(1)=1.7D14 37 P(2)=2.D5 38 CALL DFALT (IV,V) 39 V(42)=1.00-25 40 IV(17)=1000 41 IV(18)=10042 C 43 C WRITE INITIAL GUESS VALUES 44 C 45 WRITE(6,666) (P(I), 1=1.2) 46 666 FORMAT('INITIAL GUESS=' . 1P2G16.8) 47 C 48 C TO CALL FOR LIBRARY PROGRAM NL2SN0 49 C 50 CALL NL2SN0(N.M.P.CALCR,IV,V,IPARM,RPARM,FPARM) 51 C 52 WRITE(6.120) IV(1) 53 120 F0RMAT('RETURN CODE ='. 110) 54 WRITE(6,140) (P(I), 1=1.2) 55 140 FORMAT('SOLUTION:', 1P2G16.8) 56 C 57 EE=2.718281728D0 58 RR=8.314D0 160 Listing of MODEL at 12:26:52 on MAY 28. 1987 for CC i d = TITA 59 K1=14.4DO 60 K2=2.025D10 61 E1=44560.D62 E2=177580.D0 63 T=4800.D0 64 65 C 66 C TO CALCULATE THE PREDICTED OIL YIELD VALUE BASED ON 67 C K3 AND E3 VALUES OBTAINED FROM THE NL2SN0 PROGRAM 68 C 69 DO 22 I= 1 ,N 70 TEMPA = TEMP(I) + 273.DO 71 T=4800.D0 72 KC 1=K1*EE**(-(E1/(RR*TEMPA))) 73 KC2=K2*EE**(-(E2/(RR*TEMPA))74 KC3=P(1)*EE**(-(P(2)/(RR*TEMPA))) 75 WF=(13.D0*454.D0)+(W(I)/2.DO) 76 FRACT2=0.62D0/0.9D0 77 A=FO(I)*0.11D0/WF 78 B=KC1 + (F 1 (I)/WF) + (F2( I)/WF) 79 C=0.9D0*KC1 80 D = (F 1 (I )/WF) + (F2(I)/WF)+KC2 81 C11=1.D0/B/D 82 C12=1 .D0/((D*-2)-(B*D)) 83 C13=1.D0/((B**2)-(B*D)84 CB=C*A*(C11+(C12*(EE**(-D*T)))+(C13*(EE**(-B*T)))) 85 V0L=O.0322DO*1.3D0 86 FN=0.000472DO*TEMPA/293.DO 87 TT=VOL/FN 88 PP=KC2*FRACT2*CB*WF/VOL 89 0=(FN/VOL)+KC3 90 CA=(PP/Q)*(1.00-(OEXP(-0*TT))) 91 OIL=(FN*PP/Q)*((T+((DEXP(-Q*T))/Q))-(1.DO/0)) 92 ACAL(I)=OIL 93 22 CONTINUE 94 C 95 C WRITE THE FINAL RESULTS 96 C 97 WRITE(6. 1111) 98 1111 FORMAT( 10X, 'TEMP' .9X.'TIME'.5X. 'OIL CALCULATED'.8X.'01L EXPT') 99 C 100 DO 40 KK= 1 .N 101 WRITE(6,515)TEMP(KK).T.ACAL(KK),AEXPT(KK) 102 515 F0RMAT(5X,F1O.4.4X.F10'.4,4X,F1O.4.8X,F1O.4) 103 40 CONTINUE 104 C 105 STOP 106 END 107 108 109 C. **««***»»-«•*««**«**-.* 1 10 c * 111 C SUBROUTINE: CALCR -1 12 C 114 C 115 C 116 SUBROUTINE CALCR(N.M.P,NF.R,IPARM.RPARM.FPARM ) 161 Listing of MODEL at 12:26:52 on MAY 28. 1987 for CC i d = TITA 1 17 C 1 18 IMPLICIT REAL *8 (A-H.K.O-Z) 1 19 DIMENSION P(M), R(N) 120 COMMON /BLKA/ F0( 10),F1(10),F2( 10),W( 10).TEMP( 10),SIZE! 10), 121 & FEED(10).AEXPT(10).ACAL(10),MUM(10) 122 C 123 C 124 EE=2.71828172800 125 RR=8.31400 126 K1=14.4D0 127 K2=2.025D10 128 E1=44560.DO 129 E2=177580.D0 130 T=4800.D0 131 132 C 133 C TO CALCULATE PREDICTED CK,CB ANO CA VALUES BASED ON GUESSED 134 C K3 AND E3 135 C 136 00 20 1=1.N 137 TEMPA=TEMP(I)+273.00 138 T=4800.D0 139 KC1=K1*EE**(-(E1/(RR*TEMPA))) 140 KC2=K2*EE**(-(E2/(RR*TEMPA))) 14 1 KC3 = P( 1 )*EE**(-(P(2)/(RR*TEMPA))) 142 WF=(13.00*454.DO)+(W(I)/2.DO) 143 FRACT2=0.62D0/0.9D0 144 A=FO(I)*0.11D0/WF 145 B=KC1 + (F1(I )/WF) + (F2(I)/WF) 146 C=0.9D0*KC1 147 D=(F1(I)/WF)+(F2(I)/WF)+KC2 148 C11=1.DO/B/D 149 C12=1.D0/((D**2)-(B*D)) 150 C13=1.D0/((B**2)-(B*D)) 151 CB=C*A*(C11+(C12*(EE**(-D*T)))+(C13*(EE**(-B*T)))) 152 VOL=0.0322DO*1.3D0 153 FN=0.000472D0*TEMPA/293.DO 154 TT=VOL/FN 155 PP=KC2*FRACT2*CB*WF/V0L 156 Q=(FN/V0L)+KC3 157 CA=(PP/0)*(1.D0-(DEXP(-0*TT))) 158 OIL=(FN*PP/0)*((T+((DEXP(-0*T))/0))-(1.DO/0)) 159 ACAL(I)=OIL 160 C 161 C •TO CALCULATE THE DIFFERENCE BETWEEN EXPERIMENTAL AND PREDICTED 162 C OIL YIELD VALUE 163 C 164 R(I)=ACAL(I ) -AEXPT(I ) 165 C 166 20 CONTINUE 167 RETURN 168 C 169 END 170 162 C.5 Jac 163 Listing of JAC at 12:27:06 on MAY 28. 1987 for CC1d=TITA 2 C 3 C NAME OF THIS PROGRAM: JAC * 4 C 5 C THIS PROGRAM USES UBC LIBRARY PROGRAM JACOBIAN TO SOLVE * 6 C FOR THE SET OF DIFFERENTIAL EQUATIONS TO CALCULATE KEROGEN. 7 C BITUMEN. AND OIL AS A FUNCTION OF TIME AT A GIVEN SET OF * 8 C OPERATING CONDITIONS.9 C * 10 C dW/dt = YDOT( 1 ) * 11 C dCK/dt = YD0T(2)12 C dC8/dt = YD0T(3)13 C dCA/dt = YD0T(4)14 C15 C 17 18 19 IMPLICIT REAL*8 (A-H.K.O-Z) 20 EXTERNAL FUNC.PD 21 C0MM0N/BLKA/FO( 10) . F1(10).F2( 10 ) . WW( 10).TEMP(10),SIZE(10). 22 & FEED(10),AEXPT(10).ACAL(10),MUM(10),WF(10).WT 23 C0MM0N/BLKB/KC1.KC2.KC3.FRACT1.FRACT2.FN.V,I 24 COMMON/GEAR9/HUSED,NQUSED.NSTEP.NFE.NJE 25 DIMENSION Y0(112),A(10) 26 C 27 C READ IN DATA. MM=N0 OF DATA READ IN 28 C 29 MM=3 30 DO 110 M=1.MM 31 READ(5,55)MUM(M),FO(M).F1(M).F2(M),WW(M).TEMP(M),SIZE(M). 32 & FEED(M),AEXPT(M) 33 55 FORMAT(14,1X.F6.4,1X,F6.4.1X,F5.3,1X,F6.1.1X,F5.1.1X,F4.2. 34 & 1X.F6.1,1X.F6.2) 35 WRITE(6,11)AEXPT(M),TEMP(M),F1(M),WW(M) 36 11 F0RMAT(2X,4(F10.4.2X)) 37 110 CONTINUE 38 C 39 C DEFINE ALL PARAMETERS AND BASIC INFORMATION 40 C 4 1 DO 1001 1=1.MM 42 EE=2.718281728DO 43 K1=10.4D0 44 K2=2.2850145 K3=1.7D14 46 E1=44560.00 47 E2=177580.D48 £3=244319.45 49 FRACT1=0.9 50 FRACT2=0.62DO/FRACT1 51 WF(I)=(13.00*454.DO)+(WW(I)/2.DO) 52 WT=WF(I) 53 V=0.O3220O*1.300 54 RR=8.314DO 55 C 56 C 57 T EMPA = TEMP( I )+273.DO 58 KC1=K1*0EXP(-(E1/(RR*TEMPA) ) ) 164 Listing of JAC at 12:27:06 on MAY 28. 1987 for CC i d = TITA 59 KC2=K2*DEXP(-(E 2/(RR * TEMPA))) 60 KC3 = K3 *0EXP(-(E3/(RR * TEMPA))) 61 FN=O.OOO472DO*TEMPA/293.0O 62 63 C 64 WRITE(6,66)KC1 .KC2.KC3 65 66 FORMAT(//,'KC1='.F10.8.3X,'KC2='.F10.8.3X.'KC3='.F10.8) 66 67 C 68 C SET VALUES FOR THE LIBRARY PROGRAM GEAR 69 C 70 N=4 71 H0=1.D-7 72 EPS=1.0-4 73 METH=2 74 MITER=2 75 MF=10*METH+MITER 76 ML = 3 77 MU=3 78 TOUT=100.00 79 INDEX=1 80 C 81 TO=O.DO 82 Y0(1)=13.DO 83 C 84 C INITIALISE THE VALUES OF YO AT TIME=0 85 C 86 DO 5 J=2.4 87 5 Y0(J)=O.ODO 88 C 89 C WRITE TITLE 90 c 91 WRITE(6,41) 92 41 FORMAT(5X,'TIME'.8X.'W'.12X,'CK'.12X,'CB',12X,'CA') 93 c 94 C CALL GEARB TO SOLVE PROBLEM 95 C 96 97 10 CALL GEARB(N,TO.HO,YO,TOUT,EPS.MF,INDEX,ML.MU,FUNC.PD . 6) 98 C 99 WRITE(6,20)T0UT.WT.YO(2),YO(3).YO(4) 100 20 FORMAT(2X,F8.2.4(3X,F10.5)) 101 102 IF(INDEX .EO. 0)GOTO 40 103 WRITE(6.30)INDEX 104 30 F0RMAT(//26X. 'ERROR RETURN WITH INDEX ='.I3) 105 GOTO 50 106 40 T0UT=T0UT+4OO.DO 107 IF(T0UT .GE. 490O.DO)G0T0 50 108 GOTO 10 109 50 WRITE(6.60)NSTEP 1 10 60 FORMAT(//2 1X.'PROBLEM COMPLETED IN',I 5. 'STEPS' ) 1 1 1 C 1 12 C CALCULATE OIL AT THE FINAL TIME 1 13 C 1 14 WRITE(6.69)YO(3).Y0(1) 1 15 69 FORMAT(2(F10.5.2X)) 1 16 C 165 Listing of JAC at 12:27:06 on MAY 28, 1987 for CC i d=T ITA 1 17 X=4800.D0 118 P=FRACT2*KC2*Y0< 3)'WT/V 1 19 Q=(FN/V)+KC3 120 OIL=(FN»P/Q)*((X+((0EXP(-Q«X))/Q))-( 1 .00/0) ) 121 ACAL(I )=0IL 122 WRITE(6,44)0IL 123 44 F0RMAT('OIL = ', F10.4) 124 C 125 1001 CONTINUE 126 DO 1 11=1,MM 127 WRITE(6. 1 1 1 1 )TEMP(II).ACAL( II ) 128 1111 F0RMAT(//,F6.2,2X.F7.2) 129 1 CONTINUE 130 STOP 131 END 132 133 134 C 135 C * 136 C SUBROUTINE FUNC * 137 C * 138 C 139 140 SUBROUTINE FUNC(N,T,Y,YDOT) 141 IMPLICIT REAL*8 (A-H.K.O-Z) 142 DIMENSION Y(4),YD0T(4) 143 C0MM0N/BLKA/F0(10).F1(10),F2(10).W(10),TEMP(10).SIZE(10). 144 & FEED(10).AEXPT(10).ACAL(10),MUM(10),WF(10),WT 145 C0MM0N/BLKB/KC1,KC2.KC3.FRACT1.FRACT2.FN.V,I 146 C 147 C 148 YD0T(1)=FO(I)-F1(I)-F2(I) 149 Y00T(2) = (FO(I )*0.11D0/WT)-(((F0(I)/WT)+KC1)*Y(2)) 150 YD0T(3)=(FRACT1*KC1*Y(2))-(((F0(I)/WT)+KC2)*Y(3)) 151 YD0T(4)=(FRACT2*KC2*Y(3)*WT/V)-(((FN/V)+KC3)*Y(4)) 152 RETURN 153 END 154 155 156 C ************************** 157 C * 158 C DUMMY SUBROUTINE PD 159 C * 160 C ************************** 161 162 SUBROUTINE PD(N.T.Y,P,NDIMPD,ML.MU) 163 IMPLICIT REAL*8 (A-H.K.O-Z) 164 DIMENSION Y(N),P(NDIMPD,N) 165 RETURN 166 END 166 C.6 Jac (Printout) Increasing KC1 :i = 5 x KC 1 KC2 =0.00337898 KC3=0. 00037883 TIME W CK CB CA 100. .00 6051 .OOOOO 0 .00021 0. .00038 2. .77130 500, .00 6051 .OOOOO 0 .00022 0, .00145 16, .72927 900. .00 6051 .OOOOO 0 .00022 0, .00173 20, .44090 1300. .00 6051 .OOOOO 0 .00022 0, .00179 21 .37767 1700. ,00 6051 .OOOOO 0, .00022 0. .00181 21 , .61381 2100. .00 6051 .ooooo 0 .00022 0. .00182 21 , .67278 2500. ,00 6051 .ooooo 0 .00022 0. .00182 21 , .68747 2900. ,00 6051 .ooooo 0 .00022 0, .00182 21 .69148 3300. ,00 6051 .00000 0 .00022 0. .00182 21 , .69184 3700. ,00 6051 .ooooo 0 .00022 0, .00182 21 .69180 4100. oo 6051 .ooooo 0 .00022 0. .00182 21 .69219 4500. ,00 605 1 .ooooo 0 .00022 0, .00182 21 .69247 KC1 = 10. x KC1 KC2=0.00337898 KC3=0.00037883 TIME W CK CB CA 100 .00 6051 .OOOOO 0 .00011 0 .00046 3 .49169 500 .OO 6051 .OOOOO 0 .00011 0 .00148 17 .03408 900 .00 6051 .OOOOO o .00011 0 .00173 20 . 534 15 1300, .00 6051 .OOOOO 0 .00011 0, .00180 21 , .41725 1700, .00 6051 .OOOOO 0, .00011 0, .00181 21 , .63994 2100. .00 6051 .OOOOO 0, .00011 o: .00182 21 , .69574 2500..00 6051 .OOOOO 0, .OOO11 0, .00182 21 , .70991 2900. ,00 6051 .ooooo 0. .00011 0. .00182 21 . .71281 3300. OO 6051 .ooooo o. .OOO11 0. ,00182 21 . ,71394 3700. 00 6051 .ooooo 0. ,00011 0. ,00182 21 . ,71461 4100. 00 6051 .ooooo 0. .00011 0. 00182 21 . 71447 4500. 00 605 1 , .ooooo o. ,00011 0. 00182 21 . 71394 KC1= 50 x KC1 KC2=0.00337898 KC3=0.00037883 TIME W CK CB CA 100 .00 6051 .OOOOO 0 .00002 0, .00052 4 .19059 500 .OO 6051 .OOOOO 0 .00002 0 .00149 17 .25547 900 .00 6051 .OOOOO 0 .00002 0, .00174 20, .60514 1300 .00 6051 .OOOOO 0 .00002 0 .00180 21 . 44784 1700, .00 6051 .OOOOO 0 .00002 0, .00182 21 , .66002 2100, .00 6051 .OOOOO 0 .00002 0. .00182 21 , .71425 2500, .OO 6051 .OOOOO o .00002 0, ,00182 21 , . 727 18 2900. .00 6051 .ooooo 0 .00002 0. .00182 21 . .73055 3300, .00 6051 .ooooo 0 .00002 0. ,00182 21 . .73167 3700. ,00 6051 .ooooo 0 .00002 0. ,00182 21 . ,73151 4 100. oo 605 1 .ooooo o .00002 0. 00182 21 . ,73124 4 500. 00 6051 .ooooo 0 .00002 0. 00182 21 . 73124 KC1= 100 x KC1 KC2=0.00337898 KC3=0.00037883 TIME W CK C8 CA 100 .00 6051 .00000 0 .00001 0, .00052 4 . 27888 500 .00 6051 .ooooo 0 .OOOO1 o .00149 17 . 28228 900, .00 6051 .ooooo 0 .00001 0, ,00174 20 .61495 1300, ,00 6051 .ooooo 0 .00001 0. ,00180 2 1 , ,45220 1700, ,00 6051 .ooooo 0 .00001 0. ,00182 21 . ,66309 2100. .00 6051 .ooooo 0 .00001 0, ,00182 2 1 . .71656 2500. 00 605 1 .ooooo 0 .OOOO1 0. ,00182 2 1 , ,72962 2900. 00 6051 .ooooo 0 .OOOO1 0, 00182 2 1 , ,73265 3300. 00 6051 .ooooo 0 .OOOO1 0. 00182 2 1 . ,73393 3700. 00 605 1 .ooooo 0 .OOOO1 0. 00182 2 1 . , 73416 4 100 . 00 605 1 .ooooo 0, .OOOO1 0. 00182 2 1 . ,73372 4 500. 00 605 1 .ooooo 0 .OOOO1 0. 00182 2 1 , 73339 Increasing KC2 KC1=0.01689492 KC2 = 5 X KC2 KC3=0.00037883 TIME W CK CB CA 100 .oo 605 1 .OOOOO 0 .00052 o .OOO10 3 . 40206 500 .00 6051 .OOOOO 0 .00105 0 .00034 19 .95759 900. .OO 6051 .OOOOO 0 .00110 0. .00036 21 .69000 1300. .00 6051 .OOOOO 0 .00110 0. .00037 21 .82659 1700. .00 6051 .OOOOO 0 .00110 0. .00037 2 1 .83867 2100. OO 605 1 .OOOOO 0 .00110 o. ,00037 21 .8376 1 2500. .00 6051 .OOOOO 0 .00110 0. ,00037 21 .83987 2900. OO 6051 .OOOOO 0 .00110 o. ,00037 21 , .83983 3300. OO 605 1 .OOOOO 0 .00110 0. 00037 21 , .84067 3700. 00 6051 .OOOOO 0 .00110 0. ,00037 21 . .84042 4 100. 00 6051 .OOOOO 0. .00110 o. ,00037 21 . .83975 4500. 00 6051 .OOOOO 0 .00110 0. 00037 21 . .83986 KC1=0.03378984 KC2= W_ X KC2 KC3=0.00037883 TIME W CK CB CA 100. .00 6051 .OOOOO 0 .00052 0, 00007 4 .87035 500. .OO 6051 .OOOOO 0. .00105 0. .OOO17 20 .42427 900. .00 6051 .OOOOO 0. .00110 0. .00018 21 .76849 1300. ,OC 605 1 .OOOOO 0. .00110 0. .OOO18 21 .87208 1700. .00 6051 .00000 0. .00110 0. .00018 21 , .88049 2100. ,00 6051 .OOOOO 0. .00110 o. ,OOO18 21 .88077 2500. ,00 6051 .00000 0, .00110 0. .00018 21 .88094 2900. ,00 6051 .OOOOO 0. .00110 0. ,OOO18 21 . .881 12 3300. oo 6051 .OOOOO 0. .00110 0. .00018 21 , .88088 3700. ,00 6051 .OOOOO 0. .00110 0. ,00018 21 .88068 4100. ,00 6051 .OOOOO 0. ,00110 0. .00018 21 , .88069 4500. 00 6051 .OOOOO 0. ,00110 0. ,00018 21 . .88081 KC1=0.16894918 KC2= 50 X KC2 KC3=0.00037883 TIME W CK CB CA 100 .00 6051 .OOOOO 0. .00052 0 . 00002 6 . 7853 1 500 .00 6051 .OOOOO 0. .00105 0 .00004 20 .68129 900. .OO 6051 .OOOOO 0. .00110 o. .00004 21 .81870 1300. .OO 6051 .OOOOO 0. .00110 0 .00004 21 .90688 1700. .00 6051 .OOOOO 0, .00110 0, .00004 21 .91321 2 100. OO 6051 .OOOOO 0. ,00110 0, .00004 2 1 .91394 2500, .00 6051 .OOOOO 0. ,00110 0, .00004 21 .91418 2900. do 605 1 .OOOOO 0. . 00110 0. .00004 21 .91357 3300. ,00 6051 .OOOOO 0. 001 10 0, .00004 21 .91348 3700. ,00 6051 .OOOOO 0. 001 10 0. .00004 21 .91379 4100. ,00 6051 .OOOOO 0. 001 10 0. .00004 21 . .91378 4500. ,00 6051 .OOOOO 0. 001 10 0, .00004 21 , .91366 KC1=0.33789836 KC2= 100 X KC2 KC3=0.00037883 TIME W — CK CB CA 100 .OO 605 1 .OOOOO 0. .00052 0, .OOOO1 7 .04378 500 .OO 6051 .OOOOO 0 .00105 0 .00002 20 .70764 900 .00 6051 .OOOOO 0 .00110 0, .00002 21 , .82087 1300 .00 605 1 .OOOOO 0 .00110 0 .00002 21 , .90879 1700 .00 605 1 .OOOOO 0. .00110 0 .00002 2 1 .91601 2100 .00 605 1 .OOOOO 0. .00110 0. .OOOO2 2 1 .91758 2500 .00 605 1 .OOOOO 0 .00110 0 .00002 21 , .91746 2900 .00 605 1 .OOOOO o .00110 0 .00002 2 1 , .91720 3300, ,00 6051 .OOOOO 0 .00110 0. .00002 21 , .91753 3700, ,00 605 1 .OOOOO 0 .00110 0 .OOOO2 2 1 , . 9 1772 4 100, ,00 6051 .OOOOO 0 .00110 0, .00002 2 1 .91764 4 500, .00 605 1 .OOOOO 0 .001 10 0 .OOOO2 2 1 .91760 169 Increasing KC3 :1=0.00337898 KC2=0. .00189415 KC3= 5 X KC3 TIME w CK CB CA 100 .00 6051 .OOOOO 0 .00052 0 .00014 0. .92593 500 .00 6051 .OOOOO 0 .00105 0 .00119 12. .67593 900. .00 6051 .00000 0 .00110 0 .00163 18 . ,23956 1300. .00 6051 .00000 0 .00110 0. .00176 19. ,84550 1700. .00 6051 .OOOOO 0 .00110 0. .00179 20. ,28006 2100, .00 6051 .OOOOO 0 .00110 0, .00180 20. ,38640 2500. .00 6051 .ooooo 0 .00110 0, .00180 20. ,41554 2900, .00 6051 .ooooo 0 .00110 0. .00180 20. ,42144 3300. .00 6051 .ooooo 0 .00110 0. ,00180 20. 42108 3700. OO 6051 .ooooo 0. .00110 0. .00180 20. ,42134 4100. .00 6051 .ooooo 0. .00110 0. ,00180 20. 42187 4500. .00 6051 .ooooo 0. .00110 0. .00180 20. 42171 KC1=0.00337898 KC2=0.00378831 KC3= 10 X KC3 TIME w CK 'CB CA 100, .00 6051 .OOOOO 0. .00052 0. .00014 0. .89680 500, .00 6051 .OOOOO o. .00105 0. . 00119 1 1 . .96279 900 .00 6051 .00000 0. .00110 0. ,00163 17, .16337 1300, .00 6051 .OOOOO o. .00110 0. .00176 18 . .661 19 1700 .00 6051 .OOOOO 0, .001 10 0. .00179 19 .06403 2100, .00 6051 .OOOOO 0, .001 10 0. , 00180 19, .16432 2500 .00 6051 .00000 0, .00110 0. .00180 19 , . 19162 2900, .00 6051 .00000 0. .00110 0. .0018O 19, . 19713 3300. .00 6051 .ooooo 0, .00110 0. .00180 19, .19735 3700, .oo 6051 .ooooo 0, .00110 o. .00180 19, . 19782 4100. .oo 6051 .ooooo 0, .00110 0. ,00180 19. .19849 4500, .00 6051 .ooooo 0, .00110 0, .00180 19, .19836 KC1=0.00337898 KC2=0.O1894153 KC3= 50 X KC3 TIME W CK CB CA 100 .00 6051 .OOOOO 0 .00052 0, .00014 0 .71225 500, .00 6051 .OOOOO 0 .00105 0, ,001 19 8 .24347 900, .OO 6051 .OOOOO 0 .OO110 0. .00163 1 1 .6528 1 1300. .00 6051 .OOOOO 0, .00110 0. ,00176 12 , .63242 1700, .00 6051 .OOOOO 0, .OO110 0, .00179 12 .88867 2100. .00 6051 .OOOOO 0, .00110 0. ,OO180 12, .95430 2500 .00 6051 .ooooo 0, .00110 0. .00180 12 .97087 2900, .00 6051 .ooooo 0. .00110 0. ,00180 12, .97498 3300 .OO 6051 .ooooo o. .00110 o. .00180 12 .97647 3700. .00 6051 .ooooo 0, .00110 0, ,00180 12 .97676 4 100. .00 6051 .ooooo 0. .001 IO 0. , 00180 12 .97664 4500, .00 6051 .ooooo 0, .00110 0, ,00180 12 , .97668 KC1=0.00337898 KC2 =0.03788306 KC3= 100 X KC3 TIME W CK CB CA 100, .00 6051 .OOOOO 0 .00052 0 , 00014 0 .56242 500, .00 6051 .OOOOO 0 .00105 0. ,00119 5, .93075 900, ,00 6051 .OOOOO 0 .00110 0, .00163 8 . .31349 1300. .00 6051 .OOOOO 0 .00110 0. ,00176 8 , . 99782 1700, .00 605 1 .OOOOO 0 .00110 0, 00179 9 . 17796 2 100. .00 605 1 .OOOOO 0 .00110 0, ,00180 9 . 22189 2500, OO 605 1 .OOOOO 0. .00110 0, 00180 9 . 23268 2900. .00 605 1 .OOOOO 0 .OO110 0, ,00180 9 . . 23522 3300. 00 6051 .OOOOO 0. .00110 0. 00180 9 . , 23585 3700, ,00 605 1 .OOOOO 0 .001 10 0. 0O18O 9 , ,23601 4 100. 00 6051 .OOOOO 0. .001 10 0, 00180 9 . 23602 4500, .00 6051 .OOOOO 0 .00110 0, ,00180 9 , , 23601 

Cite

Citation Scheme:

    

Usage Statistics

Country Views Downloads
United States 6 0
China 5 0
Russia 5 0
Japan 3 0
United Kingdom 2 0
Australia 1 0
Canada 1 1
City Views Downloads
Beijing 5 0
Ashburn 3 0
Penza 3 0
Tokyo 3 0
Unknown 3 1
Mountain View 2 0
Belfast 2 0
Calgary 1 1
Dallas 1 0

{[{ mDataHeader[type] }]} {[{ month[type] }]} {[{ tData[type] }]}
Download Stats

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0058776/manifest

Comment

Related Items

Admin Tools

To re-ingest this item use button below, on average re-ingesting will take 5 minutes per item.

Reingest

To clear this item from the cache, please use the button below;

Clear Item cache