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Supercritical water oxidation of phenol and 2,4 dinitrophenol Perez, Ivette Vera 2002

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SUPERCRITICAL WATER OXIDATION OF PHENOL AND 2,4 DINITROPHENOL By IVETTE VERA PEREZ B.Sc, "Jose A. Echeverria" Higher Polytechnical Institute (ISPJAE) Havana, 1994 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 MECHANICAL ENGINEERING We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA November 2002 © Ivette Vera Perez, 2002 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 M eg -Ayn /ga - l ^h\%'r\€€f7^ The University of British Columbia Vancouver, Canada DE-6 (2/88) Abstract The destruction kinetics of two model compounds has been investigated in the University of British Columbia (UBC) Supercritical Water Oxidation (SCWO) pilot plant. High concentrations of phenol (2.7% and 4% by weight) were oxidized at pressures of 24 to 26 MPa, temperatures of 666 to 778 K , and 0 to 39% oxygen excess. Phenol and Total Organic Carbon (TOC) conversions varied from 92 to 99.98% and 75 to 99.77% respectively. The second group of wastes studied contained 2,4 dinitrophenol (DNP). Two different solutions that simulated an aromatic nitration facility's wash-water were investigated. The first one contained 2.4% by wt. 2,4 dinitrophenol with 2% by wt. ammonium sulphate and simulated the final wash waters from the nitration plant with no sulphates elimination. The second solution contained 2.27% by wt. as ammonium dinitrophenol, with no sulphates. For the first DNP waste, at process conditions of 25 MPa, 780 K and 37% oxygen excess, 99.9996% destruction efficiencies were obtained for 2,4 dinitrophenol, and 99.92% for TOC. Mono-nitrophenols were detected as intermediates, but not in the liquid effluent, where residuals of ammonium bicarbonate and sulphates were detected. No N O x or CO was present in the gaseous effluent streams. This solution resulted to be very corrosive to the system. The second solution was treated at 22.9 ±0 .1 MPa, 742-813 K and oxygen concentrations ranging from sub-stoichiometric to 69% excess. Destruction efficiencies for 2,4 dinitrophenol were 99.9996% in all cases (not detected). TOC destruction efficiencies ranged from 98.98 to 99.98%, while ammonia destruction ranged from 15 to 50%. Picric acid, mono-nitrophenols, ammonium carbonate and bicarbonate were detected as intermediates, but not in the liquid effluent. No CO or N O x was present in the effluent gas samples, except in cases with less than stoichiometric oxygen. ii Table of Contents Abstract ii Table of Contents iii List of Tables vi List of Figures vii Nomenclature ix Acknowledgements xi Chapter 1 Introduction ».« 1 1.1 Project objectives 1 1.2 Thesis Overview 2 Chapter 2 Supercritical Water Oxidation (SCWO) as a means to destroy phenolic wastes 3 2.1 Processes that produce phenolic wastes: The mononitrobenzene process 3 2.2 Commonly used methods in the treatment of phenolic wastes 4 2.2.1 SCWO process description 8 Chapter 3 Supercritical Water Oxidation of Phenol and 2,4 Dinitrophenol Wastes 10 3.1 Introduction '.: 10 3.2 Studies on phenol, nitrophenols and nitrogenous compounds 13 3.2.1 Phenol 13 3.2.2 Nitrogenous compounds 15 3.2.2.1 Nitrophenols 16 3.2.2.1.1 2,4 D N P 19 3.3 Experimental apparatus and methods : 20 3.3.1 Apparatus 20 3.3.2 Fluid temperature measurements 26 3.3.3 Sampling system 26 3.3.4 Analytical procedures 28 3.4 Calculations 29 3.4.1 Oxygen excess 29 3.4.2 Residence times 30 3.4.3 Yields and Conversions 32 3.4.4 Calculations for the comparison with other studies of the phenol experiments 33 3.4.5 Error analysis 36 3.4.5.1 Residence times 36 3.4.5.2 Yields and conversions 38 iii 3.5 Discussion of results 39 3.5.1 Phenol Experiments 39 3.5.1.1 Experimental conditions 39 3.5.1.2 Observations 40 3.5.1.3 Effect of temperature 44 3.5.1.4 Effect of Residence time 46 3.5.1.5 Effect of excess oxygen 49 3.5.1.6 Effect of phenol concentration .' 49 3.5.1.7 Comparison with other studies 50 3.5.2 2,4 D N P based wastes 53 3.5.2.1 Experimental conditions 53 3.5.2.2 2,4 Dinitrophenol, ammonium sulphate and excess ammonia 55 3.5.2.2.1 Observations 55 3.5.2.3 2,4 DNP and Ammonia 59 3.5.2.3.1 Observations 59 3.5.2.3.2 Effect of temperature 68 3.5.2.3.3 Effect of residence time 71 3.5.2.3.4 Effect of oxidant excess 76 3.6 Conclusions 78 Chapter 4 Corrosion observed in the UBC-Noram SCWO facility 80 4.1 Previous experience 80 4.2 Corrosion in the UBC-Noram pilot plant 82 4.3 Conclusions • 88 Chapter 5 Conclusions and Recommendations 89 5.1 Conclusions 89 5.2 Recommendations 91 References 92 Appendix A Oxygen flow meter calibration 96 Appendix B Gas flow meter calibration report I l l Appendix C Thermocouples location 114 Appendix D Sample coolers validation 116 Appendix E Stock preparation and solubility data. 2,4 DNP experiments 118 Appendix F Phenol experiments. Results and mass balances 120 Appendix G 2,4 DNP, ammonia and ammonium sulphate experiments 134 Appendix H 2,4 and ammonia experiments. Reports and mass balances 138 iv Appendix I Corrosion Appendix J Matlab programs and electronic files. List of Tables Table 2.1 Commonly used treatment technologies for phenolic wastes 4 Table 3.1 Conditions and global kinetic models for SCWO of Phenol 14 Table 3.2 Influent characteristics for DNT wastewater experiments. (Li et al.) 19 Table 3.3 Experimental conditions for DNP experiments at UBC/Noram pilot plant, 1999 20 Table 3.4 Experimental conditions for phenol destruction 40 Table 3.5 Conversions and yields for phenol experiments 42 Table.3.6 2,4 D N P experimental conditions 54 Table 3.7 2,4 DNP and ammonium sulphate experiments. Conversions and yields 57 Table 3.8 Stoichiometric table for Equation [28] 60 Table 3.9 Predicted gaseous molar flows 64 Table 3.10 Air contamination. BCRI results and balance predictions 66 Table 3.11 2,4DNP and ammonia experiments. Conversions and yields 67 Table A . 1 First set of calibrations. Data at 3900 and 4200 psi 107 Table A.2 Second set of calibrations. Data at 3600, 3900 and 4000 psi 108 Table A.3 Uncertainty in voltage 2,4 DNP and ammonium sulphate experiments 109 Table A.4 Uncertainty in mass flow 2,4 DNP and ammonium sulphate experiments 110 Table B . l Gas Flow measurements. Corrections table 113 Table C. 1 Thermocouples location in the SCWO pilot plant 114 Table E . l Solubility of 2,4 DNP solutions with temperature and p H 5 2 119 Table F. 1 Channel configuration. Phenol experiments 120 Table F.2 Temperatures for text files. Phenol experiments 121 Table G. 1 Channel configuration. 2,4 DNP, ammonium sulphate and ammonia 134 Table G.2 Temperatures for text files. 2,4 DNP, ammonium sulphate and ammonia 135 Table H. 1 Discrepancies in ammonia measurements 139 Table H.2 Channel configuration. 2,4 DNP and ammonia experiments 140 Table H.3 Temperatures for text files. 2,4 D N P and ammonia experiments 141 Table H.4 2,4 DNP and ammonia experiments. Molar balances 143 Table H.5 2,4 D N P and ammonia experiments. Predicted gas percentages from molar flows (not considering air contamination) 144 Table H.6 2,4 DNP and ammonia experiments. Air contamination 144 Table H.7 Uncertainties in oxygen flows. 2,4 D N P and ammonia experiment, runs 1, 3, and 5 169 Table L l Metals losses. 2,4 DNP, ammonia and ammonium sulphate experiments 170 Table J.l Matlab file 172 Table J.2 Excel files 173 Table J.3 Experiments data files 173 vi List of Figures Figure 2.1 Block diagram for SCWO of liquid streams 9 Figure 3.1 Primary reaction paths for SCWO of nitrophenols (Martino and Savage) 18 Figure 3.2 Schematic flow sheet of the UBC-Noram SCWO reactor 24 Figure 3.3 Pressure and oxygen flows. Samples only taken from the effluent 25 Figure 3.4 Pressure and oxygen flow. Samples taken from sampling ports and the effluent 25 Figure 3.5 Sample cooler for intermediate sampling port 27 Figure 3.6 Plot of residence time vs. system length at different conditions 31 Figure 3.7 Effect of temperature, feed concentration and oxygen excess on phenol DREs 45 Figure 3.8 Effect of temperature, feed concentration and oxygen excess on TOC DREs 45 Figure 3.9 Phenol experiments. Temperature profiles for 4% wt runs 46 Figure 3.10 Phenol experiments Temperature profiles for 2.7% wt runs 47 Figure 3.11 Phenol experiments. Conversions and yields for Runl (666K, 10% 0 2 excess) 47 Figure 3.12 Phenol experiments. Conversions and yields for Run 5 (681 K , 34% O2 excess) 48 Figure 3.13 Phenol experiments. Conversions and yields for Run 6 (690 K , 0% 0 2 excess) 48 Figure 3.14 Phenol experiments. Conversions and yields for Run 7 (703 K , 21% 0 2 excess) 49 Figure 3.15 Phenol experiments. Agreement study. Run 1 (666K, 10% 0 2 excess) 51 Figure 3.16 Phenol experiments. Agreement study. Run 5 (681 K , 34% 0 2 excess 51 Figure 3.17 Phenol experiments. Agreement study. Run 6 (690 K , 0% 0 2 excess) 52 Figure 3.18 Phenol experiments. Agreement study. Run 7 (703 K , 21% 0 2 excess) 52 Figure 3.19 2,4 D N P and ammonium sulphate. Conversions and yields (780 K , 199% 0 2 excess). 57 Figure 3.20 2,4 DNP and ammonium sulphate. Intermediates formation 58 Figure 3.21 Appearance change. (From left to right: Feed, PH2 out, RL-2, RL-6, effluent) 58 Figure 3.22 2,4 DNP and ammonia experiments. Temperature profiles runs l-2c 68 Figure 3.23 2,4 DNP and ammonia, temperature profiles runs 3-4b 69 Figure 3.24 2,4 DNP and ammonia. Temperature profiles runs 5-7 69 Figure 3.25 2,4 DNP and ammonia. Conversions and yields for Runl (813 K , 74.7% 0 2 excess) 73 Figure 3.26 2,4 DNP and ammonia. Intermediates, TOC and ammonia destruction, Run 1 73 Figure 3.27 2,4 DNP and ammonia. Conversions and yields for Run 3 (791 K , 73.3% 0 2 excess) 74 Figure 3.28 2,4 DNP and ammonia. Intermediates, TOC and ammonia destruction, Run 3 74 Figure 3.29 2,4 DNP and ammonia. Conversions and yields for Run 5 (769 K , 78.6% 0 2 excess) 75 Figure 3.30 2,4 DNP and ammonia. Intermediates, TOC and ammonia destruction, Run 5 75 Figure 3.31 2,4 DNP and ammonia. Effect of oxygen excess at 813 K 77 Figure 3.32 2,4 DNP and ammonia. Effect of oxygen excess at 791 K 77 Figure 3.33 2,4 DNP and ammonia. Effect of oxygen excess at 769 K 78 Figure 4.1 Corrosion as a function of temperature in preheater and heat exchanger 81 vii Figure 4.2 Tube failure due to corrosion in the first preheater (PH 1) 83 Figure 4.3 Temperature and thickness profiles, P H 1 85 Figure 4.4 Temperature and thickness profiles, R H X 85 Figure A . l Schematic of the oxygen set up for the first set of calibrations 98 Figure A.2 Schematic of the oxygen set up for the second set of calibrations 98 Figure A.3 First set of calibrations. Mass flow rate vs. voltage 104 Figure A.4 First set of calibrations. m2/density vs. voltage difference 104 Figure A.5 First set of calibrations. Transmitter reading vs. voltage difference 105 Figure A.6 Second set of calibrations. Mass flow rate vs. voltage 105 Figure A.7 Second set of calibrations. m2/density vs. voltage difference 106 Figure A.8 Second set of calibrations. Transmitter reading vs. voltage difference 106 Figure B . 1 Schematic of the calibration set up 112 Figure D. 1 Sampling ports (Cooling jacket not shown) 117 Figure F. 1 Phenol Experiments. Agreement study. Run 2 131 Figure F.2 Phenol Experiments. Agreement study. Run 3 132 Figure F.3 Phenol Experiments. Agreement study. Run 4 132 Figure F.4 Phenol Experiments. Agreement study. Run 8 133 Figure F.5 Phenol Experiments. Agreement study. Run 9 133 Figure 1.1 Optical microscope image. Preheater 1, corroded section 171 Figure 1.2 Optical microscope image. Preheater 1, corroded section, pits, : 171 vin Nomenclature Acronyms and symbols % Ea A [ ] C X P DRE DNP DNT L th x h M.W n N Ph PH 1 PH 2 P r K a, b, c RL-2 RL-6 RHX % Volume of indicated gas, or % wt. of indicated liquid Activation energy Area [m2] Concentration of indicated specie [mol/L] Concentration of indicated specie [mg/L] Conversion/yield of the indicated species Density [g/L] Destruction Removal Efficiency Dinitrophenol Dinitrotoluene Excess oxygen [%] Frequency factor Length [m] Mass flow rate of indicated specie [g/min] Mass fraction, or percent fraction Molar flow rate of indicated specie [mol/min] Molecular weight of indicated specie [g/mol] Number of moles, or number of measurements Number of segments Phenol Preheater 1 Preheater 2 Pressure Rate Rate constant Reaction orders to the indicated species Reactor length 2 Reactor length 6 Regenerative heat exchanger r Standard deviation SCWO Supercritical Water Oxidation T Temperature [K] TS Test section t Time TOC Total of Organic Carbon w Uncertainty of individual variables wR Uncertainty of measurement R Universal gas constant y Variables for which w is measured WAO Wet Air Oxidation BCRI British Columbia Research Institute Subscripts a Air ex. Excess 0 Initial in Inlet, feed, initial liquid Liquid feed into the system (water + waste) out Outlet, effluent oxygen Oxygen 1 Segment in the SCWO system, or specie stoich. Stoichiometric total Total vapor Vapour sat Saturation gas Gas Acknowledgements During this project, I was privileged to work with an exceptional group of wise, dedicated and experienced people. First and foremost, I would like to thank my supervisor, Dr. Steve Rogak, for his support, belief in my ability to see the project through, and for never accepting less than my best efforts. I would also like to express my gratitude to Dr. Richard Branion, who has been my mentor throughout this project and whose guidance has been vital in its completion. My sincerest appreciation to Dr. Clive Brereton, who always found time to give me advice and to Mohammad Khan, who helped me run all the experiments, even at the most inconvenient times A special note of thanks to Doug Yuen and the machine shop staff, without whom it would have been impossible to complete this work. Finally, I would like to thank my parents and grandparents, whose example and support has always been invaluable; and Mark, to whom this work is dedicated, for his love and encouragement. xi Chapter 1 Introduction 1.1 Project objectives Phenol derivatives, often part of industrial wastewaters, are priority pollutants. Supercritical Water Oxidation (SCWO) is a technology developed to treat phenolic wastes, but often, the chemical and physical data needed to design practical systems is lacking. The supercritical water oxidation research project at UBC currently focuses, among other things, on the destruction of high concentrations of ammonia red waters, specifically the waste waters from a nitrobenzene production plant whose main organic component is 2,4 dinitrophenol (2,4 DNP) ( C 6 H 3 O H ( N 0 2 ) 2 ) . Before exploring the elimination of 2,4 DNP wastes, it was necessary to validate the destruction capabilities of the plant with high concentrations of a simpler organic waste. Phenol represented an ideal component for the operational validation of the pilot plant. Low concentration trials had been reported in literature and phenol was catalogued as difficult to eliminate by SCWO. The objectives of this project were: 1. To validate the destruction capabilities of the UBC-Noram SCWO pilot plant with high concentrations of phenol; and 2. To complete and report destruction measurements of 2,4 DNP and ammonia wastewaters. 1 1.2 Thesis Overview This thesis is composed of five chapters. Following the overview in this section, Chapter 2 provides a brief introduction to phenolic waste streams, the different technologies available for their destruction, and the supercritical water oxidation process. Chapter 3 presents the study of two main groups of wastes: phenol, a simple organic compound, and a second group composed of 2,4 DNP solutions. These included a solution with sulphates and ammonia, and a solution with no sulphates, but containing ammonia. Chapter 4 looks at the corrosion problems faced when treating one of these wastes. Chapter 5 presents final conclusions, and recommendations for future work. Chapter 3 was written so that it could be submitted as a separate article for publication in a technical journal, with little modification, and as such, is intended to be a self-supporting document. 2 Chapter 2 Supercritical Water Oxidation (SCWO) as a means to destroy phenolic wastes 2.1 Processes that produce phenolic wastes: The mononitrobenzene process. Phenol, C6H5OH, is a colourless or white solid when pure. However, it is usually sold and used as a liquid solution. It is highly flammable, has a sickeningly sweet and irritating odour; and evaporates more slowly than water. Its primary use is in the production of phenolic resins, which are used in the plywood, construction, automotive, and appliance industries. Phenol is highly soluble in water, causing phenolic compounds to be common in a wide variety of industrial wastewaters. Along with substituted phenols, it is a suspected carcinogen, as well as very toxic to aquatic life. The main sources of phenolic wastewater are industries, such as solvent production, petrochemicals, coal gasification, pesticide manufacture, metallurgical and nitration processes. Mononitrobenzene (MNB) manufacturing is an example of a nitration process that produces nitrophenols as wash water effluents. Mononitrobenzene, the raw material of aniline, is widely used in the production of polyurethane, rubber chemicals, dyes, agrochemicals, and as a solvent in petroleum refining. Its production has increased substantially in the past years, and so have the waste streams that this process generates. For example, in 1960, 73,600 metric tonnes of M N B were produced in the United States alone. By 1986, the production had increased to 434, 900 metric tons.1 M N B is produced commercially by the exothermic nitration of benzene with nitric acid in the presence of a sulphuric acid catalyst at 110°C. The crude nitrobenzene is passed through washer-separators to remove residual acid and then distilled to remove benzene and 3 water. Commonly, the nitro-hydroxy-aromatic by-products such as dinitrophenol are extracted from the crude through counter-current washing,2 for which alkali chemicals are used, usually caustic soda or aqueous ammonia.1 This final wash water, called "red water" because of its colour, will be one of the subjects of study in this work. In some cases, certain inorganic compounds are kept out from the red water prior to its treatment. For example, sulphates would produce sulphur dioxide, or non-volatile salts, when treated by incineration and therefore needs to be kept out of disposal systems that use this technology. 2.2 Commonly used methods in the treatment of phenolic wastes Viable treatment alternatives for phenolic wastes follow different approaches, including biological, physical and chemical and thermal processes. Generally, the choice of treatment depends on local site conditions, volumes and concentration of the wastes, economic feasibility and operator's preferences. Table 2.1 shows a scheme of the most commonly used techniques. Table 2.1 Commonly used treatment technologies for phenolic wastes Type of treatment Technology Biological Anaerobic digestion Enzymatic detoxification Aerobic digestion (activated sludge) Physical and chemical Chemical oxidation Activated carbon adsorption Ultraviolet (UV) oxidation Thermal Incineration Wet air oxidation Supercritical water oxidation 4 Anaerobic digestion is a sequential, biologically destructive process in which organics are converted from complex to simpler molecules in the absence of free oxygen, and ultimately to carbon dioxide and methane.3 Phenolic wastes are among the organic chemicals listed as degradable by anaerobic digestion, however, biological removal efficiencies are not always high enough to meet discharge standards and require another secondary treatment method. Enzymes are complex proteins ubiquitous in nature. A biological method for removal of chlorophenols in drinking water and wastewater is enzymatic detoxification using the horseradish peroxidase enzyme. Adding this enzyme together with hydrogen peroxide to the waste solution causes enzymatic cross-linking of the substrate, thus forming insoluble polymers. These then precipitate out of solution and can be removed by filtration. However, the use of enzymes to detoxify chemical pollutants is often dismissed as technologically too challenging.3 In aerobic digestion by activated sludge, oxygen is used by a mixture of different types of micro-organisms as a source of energy for the breakdown of organic substances This system develops a microbiological community that converts organics into new non-toxic material, CO2 and water3. Noram Engineering and Constructors Ltd, has developed an aerobic activated sludge process: Vertreat. The Vertreat reactor is capable of treating diluted concentrations of 2,4 DNP, but it needs a sludge specially conditioned to treat this waste stream. Research looking into treating high concentrations of 2,4 DNP is still ongoing. Chemical oxidation processes applied to the destruction of organic, phenolic wastes include oxidizing agents like hydrogen peroxide, Fentons reagent, ozone, permanganate and peroxidisulphate, a very strong chemical oxidant.4 Some of the limitations of chemical 5 oxidation are that often, large quantities of oxidizing chemicals are needed, thus increasing the cost. Moreover, it is difficult to achieve strict discharge limits without further treatment.2'4 Activated carbon can be used to treat phenolic wastewaters3. Most carbon-adsorption systems use granular activated carbon in flow through column reactors. The adsorption process is reversible, but even when the activated carbon can be regenerated; the treatment remains very expensive and often develops excessive head loss as the result of suspended-solids accumulation or premature exhaustion of the carbon capacity.3 U V oxidation destroys organics by the addition of strong oxidizers (O3 and/or H2O2) and irradiation with U V light. It generates highly reactive hydroxyl radicals (OH *) that react with and destroy most organic chemical compounds. UV/O3 and UV/H2O2 processes have been proven effective in the treatment of phenol5. However, they are not considered cost competitive due to the high energy consumption of the U V lamps. Additionally, turbidity (e.g., cloudiness) of the water can cause interference in the process. Treatment limits range from 10 ppm to over 1000 ppm TOC. Incineration has been a widely used method of reducing the volume and hazard of organic hazardous wastes since the 1930s.4 In the past years, environmental regulators have turned their attention to the concentration of products of incomplete combustion (PICs) from incinerators and their associated risks to human health. Some incineration systems have additional technologies to control the PICs emissions to the required limits. Despite its capability to destroy phenolic wastes, incineration often suffers from poor public image due to potential N O x and SO x and other toxic emissions. In the case of wastewaters from the M N B process, incineration is only used in ammonia-washed effluents, as caustic soda 6 2 produces ash and slay which tend to foul the incinerator. Operation costs can be high due to the large amounts of heat needed to evaporate the water and to elevate the temperature of combustion products and air to the point of combustion. In wet air oxidation (WAO), waste materials in diluted aqueous solution or suspension are mixed with dissolved oxygen at relatively high temperatures (120 to 230°C) and pressures (490 to 21,000 KPa). Oxidation and hydrolysis reactions degrade the initial compound into a series of compounds of simpler structure. A major disadvantage, however, is that very often organic matter is not fully destroyed. Consequently, the effluent requires further treatment. In 1821 a French scientist, Baron Charles Cagniard de la Tour, showed experimentally that there is a critical temperature above which a single substance can only exist as a fluid and not as either a liquid or gas. Since then, the study of supercritical fluids has advanced considerably. Supercritical water oxidation (SCWO) is one of the principal developments. Due to its peculiar properties, water at supercritical conditions has been found to be an excellent medium for converting toxic organic substances into benign and environmentally acceptable products. Its density is approximately one order of magnitude less than at ambient conditions, which allows flow systems to operate at very small residence times. Viscosity drops quickly at the critical point, diffusivity increases, and mass transfer limitations become minimal. The static dielectric constant, which is a measure of the hydrogen bonding, is much lower above the critical point than it is at ambient conditions. This causes supercritical water to act like an organic solvent.6'7'8 By contrast, inorganic compounds turn insoluble under supercritical conditions. Supercritical water oxidation (SCWO) can be seen as an extension of wet air oxidation to more severe conditions. It was patented in the 1980s, but research and development is still ongoing. SCWO processes take place at pressures and temperatures above the critical point of water (374.2°C and 22.1 MPa). Since supercritical water is miscible in all proportions with oxygen, oxidation reaction rates will be limited by reaction kinetics rather than by mass transfer. SCWO can usually guarantee complete oxidation of organic compounds without the need for further treatment,4 a distinct advantage over W A O . Typical operation temperatures are in the range of 450 to 600°C, much lower than those of incineration processes and less likely to produce NOx in the gas effluent. 2.2.1 SCWO process description Figure 2.1 shows a simplified block diagram of a SCWO process for liquid streams. The aqueous organic waste is pressurized and heated above the critical point of water by means of electrical energy or through addition and oxidation of some other kind of fuel; an oxidizer is added to this mixture and, given an adequate reaction time, the organic carbon is converted to CO2 and the nitrogen species to N2. Distilled water is used during the warming up, cooling down and rinsing phases of the process. Even though there are several pilot plants and research facilities, there are not many commercial SCWO plants at the moment. In the late 1990s Eco Waste Technologies implemented and commercialized a process at a site near Austin, Texas. The waste treated there contains long-chain alcohols, glycols and amines, with TOC concentration typically higher than 50,000 mg/L. In April 2001, a SCWO municipal wastewater sludge processing plant started operating in Harlingen, Texas, treating 9.8 tons per day. 9 8 Waste Oxidant Water SCWO Reactor Electrical energy/ fuel Figure 2.1 Block diagram for SCWO of liquid streams Gases Cooling & Vapor-pressure liquid letdown separation Liquids The industrial scale-up of SCWO has been hindered by some practical problems, such as salts deposition, corrosion and high costs. Careful selection of the wastes that are to be treated by SCWO and of the reactors designs and materials can help reduce the significance of these negative factors. The next chapter focuses on the treatment of high concentrations of phenolic wastes in the UBC/Noram SCWO pilot plan, followed by a discussion of the system's corrosion from one of the tested wastes. 9 Chapter 3 Supercritical Water Oxidation of Phenol and 2,4 Dinitrophenol Wastes 3.1 Introduction Concentrated organic wastewaters are becoming increasingly difficult and costly to treat. To comply with strict disposal standards while maintaining economic viability, waste treatment technologies should be validated for their destruction capabilities under these conditions. Supercritical water oxidation has been proposed as a technology capable of destroying a very wide range of organic, hazardous wastes so that no further treatment is needed. The feasibility of SCWO as a waste destruction technology has been proven in numerous studies,10' u ' 1 2 ' 1 3 but not much information exists on the treatment of highly concentrated wastes at moderate oxidant excess; conditions that could be considered more desirable (or practical) in an industrial setting. Matsumura et a l . 1 4 reported the treatment of high concentrations of phenol in a lab-scale facility, finding good agreement between their decomposition conversions and those of the reported literature ' ' ' When bringing SCWO into a practical setting, several factors have to be considered: • The concentration of the waste to be treated, because the heat released from the oxidation reaction depends on this factor, which will determine both the size of the reactor and the self-sustainability of the process. • The size of the reactor, so as to obtain the highest destruction removal efficiencies (DRE) with the minimum volume possible, as the reactor accounts for a significant portion of the system cost (50%)19 10 • Oxidant excess, which should be enough to allow the destruction of the waste, but not too much, because it represents an important cost factor and un-reacted oxygen will be wasted. • The formation of partial oxidation products. Besides achieving high Destruction Removal Efficiencies (DREs), a high degree of TOC destruction is mandatory. • Operating temperature, which should be high enough to achieve the necessary DREs, but not higher. • The preheater size and preheating strategies, which ought be developed in order to avoid or minimize char formation, which will be more likely to occur with more concentrated wastes. • Nature of the waste: Some compounds are more likely to promote corrosion and/or fouling, two factors that will influence the operating cost of the facility and define the feasibility of treating a certain waste by SCWO. In summary, in order to have an economically efficient process, it would be advisable to aim for concentrated feeds with high heating values higher than 300 kJ/kg , which must be treated at moderate oxidant excess and temperatures, while maintaining the desired destruction efficiencies. Higher concentrations of the waste will mean a lower amount of electrical heat (or other kinds of energy) supplied to the system, with more energy being provided by the heat of reaction of the organic feed. Relatively low oxidant excess would reduce the reactor volume, as well as the operating costs for the oxidant system. Additionally, lower preheating and operation temperatures can be interpreted as lower electricity and/or auxiliary fuel costs and more durability of the materials, and hence, as lower operating costs. 11 In this work, the destruction of two groups of model wastes (phenol and 2,4-ammonium dinitrophenol (2,4 DNP)) was investigated. The experimental conditions simulated those of a practical process where the excess of oxidant and heats of reactions would be of great importance when accounting for operating costs. In the case of phenol, a widely investigated waste,14' 1 5 ' 1 6 ' 1 7 ' 1 8 ' 2 1 ' 2 2 ' 2 3 our main goals were: 1. Validate the destruction capabilities of our pilot plant, at practical conditions (high waste concentrations and moderate oxidant excess) 2. Observe the influence of temperature on the residence time and destruction efficiencies. ^ i A | r jy- i-7 1 o ryr\ 3. Examine the agreement of rate laws available in the literature ' (most commonly for experiments at low waste concentration and very high oxidant excesses) with our experimental results under different conditions. The second group of wastes modeled contained 2,4 DNP. Two different solutions were treated. The first one, (2.4% by wt. as 2,4 DNP and 2% by wt. as ammonium sulphate), simulated the wash water ("red water") from an aromatic nitration facility without an acid wash to remove the bulk of sulphate. The second solution simulated the wastewaters with 2.27% wt. (as 2,4 DNP), with no sulphates. For the treatment of these 2,4 DNP solutions, our main goals were: 1. To obtain experimental data on the destruction of a 2,4 DNP waste. 2. To investigate the feasibility of treating 2,4 DNP waste waters with high content of ammonium sulphate. 12 3. To observe the influence of temperature, residence time and oxygen excess on the destruction of 2,4 D N P and ammonia. 3.2 Studies on phenol, nitrophenols and nitrogenous compounds 3.2.1 Phenol SCWO of phenol has been extensively investigated, although most of the available literature covers low concentrations (< 0.1% wt.) and high oxidant excess. In all cases 1 4 ' 1 5 ' 1 6 ' 1 7 ' 1 8 ' 2 1 ' 2 2 ' 2 3 , the overall rate of reaction was determined as: Where A , Ea, R, T, t and [species] express the frequency factor, activation energy, gas constant, absolute temperature, time, and species concentrations in mole per litres, respectively. Ph, O, and H2O denote phenol, oxidant, and water, with a, b and c as their respective reaction orders. Experimental conditions and coefficients used for the predictions are shown in Table 3.1. There are significant differences in the reported rate laws despite similar experimental conditions. Many aspects like non-isothermal operation, differing geometry and material of the reactor, operating procedures, or different set of conditions, can lead to a disagreement in model predictions. 2 4 [1] 13 3.2.2 Nitrogenous compounds f)C rys r\~j Wastes may contain high levels of nitrogen species ' ' . This nitrogen can be in the forms of ammonia, nitrate/nitrite, or it can be part of the organic waste, as in the case of nitrophenols, which are separately referred to below. Ammonia oxidation is often the slowest reaction for the final decomposition of the nitrogenous waste into CO2, N 2 and H 2 0 2 8 ' 29, and for this reason a lot of attention has been given to it. Killilea et al. and Cocero et al. found that ammonia destruction increased with temperature and with the presence of organic compounds. According to their findings, SCWO systems favoured N 2 formation over N 2 0 , while no NOx was produced; this is corroborated by other authors31. Even though it is not favoured by SCWO, N 2 0 can be observed in the gas effluent. Operating at high temperatures in the range of 873 K can eliminate this effect 2 9 ' 3 0 Due to its slow rate of disappearance in 0 2 , the destruction of ammonia in different environments has been extensively studied. Luan et a l . 3 2 treated organic/ammonia mixtures and observed an enhanced reactivity when using hydrogen peroxide (H 2 0 2 ) as the oxidant. They also pointed out that a co-oxidant system using both nitrate and hydrogen peroxide was 33 more effective and guaranteed the destruction of organics and ammonia. Aymonier et al. observed the same when treating fenuron (C6H5-NH-CO-NH(CH 3) 2) by using H 2 0 2 as the oxidizing agent. The nitrogen atoms from the fenuron were first transformed into ammonia, nitrate ions (NO3") and nitrobenzene. NO3 and H 2 0 2 created a powerful oxidant system that allowed the complete degradation of the nitrogenous organic. Proesmans et al. showed that ammonium nitrate was an effective oxidizer for some organic compounds, with better conversions for higher feed TOC concentrations. This last point coincided with the findings of Killilea et a l . 3 0 Gidner et al . 3 1 treated wastewaters from amine manufacturing. They developed a method of adding nitric acid to the feed tank, in a stoichiometric ratio to the amount of total nitrogen contained in it, and using oxygen as the other oxidizing agent. They also developed a process of continuous injection of nitric acid in the reactor. Lee et a l . 3 4 corroborated that the coexistence of the nitro group and oxygen had a positive effect on reducing ammonia concentration in the treatment of organic wastes. There was the possibility that oxygen could be consumed for oxidizing the organic compound, and the nitro groups, in addition to the decomposition products from the nitrogenous organic, could oxidize the ammonia. Ding et a l . 3 5 have explored catalytic destruction of ammonia as a way to reduce the temperature needed for ammonia conversion. Using Mn02/Ce02 as a catalyst at 27.6 MPa and temperatures ranging from 410 to 470°C, the rate of ammonia conversion increased considerably as compared to that of non-catalytic oxidation. 3.2.2.1 Nitrophenols While there is no information available on the SCWO of dinitrophenols, the destruction of mono-nitro phenols has been discussed in literature. Martino and Savage 3 6 , 3 7 investigated the thermolysis (pyrolysis and/or hydrolysis) and oxidation of 2-, 3- and 4- nitrophenol. Both types of reactions revealed that N02-substituted phenols are very reactive in SCW. From the thermolysis reactions, phenol was proven to be the major aqueous-phase product, the order of reactivity being 2-nitrophenol > 4-nitrophenol > 3-nitrophenol. During 16 all these experiments, some of the reacted carbon was deposited in the reactor in the form of a solid residue. The contribution of thermolysis and oxidation as well as the yields of CO and C 0 2 was quantified. The nitrogenous species yields were not quantified. Oxidation also produced phenol as the major product, although the phenol yield during oxidation was not much higher than that of thermolysis. According to their findings, thermolysis accounted for up to 25% of the total amount of destruction for 3- and 4-nitrophenol, and was higher for 2-nitrophenol, implying that the SCWO of N02-substituted phenols would involve a significant purely thermal component, and that a great portion of the oxidation would be of the thermal reactions products, rather than the NO2- substituted phenols. Martino and Savage discovered two major primary paths for the SCWO process of the investigated nitrophenols: the first one leading to phenol, and the other one leading to ring-opening products and ultimately to CO and CO2, as shown in Figure 3.1 17 Figure 3.1 Primary reaction paths for SCWO of nitrophenols (Martino and Savage) 36 In 1993, L i et a l . 2 6 treated dinitrotoluene (DNT) process wastewaters. The major organic components in these wastewaters were: DNT, phenol, 4,6-dinitro-ortho-cresol, 2,4 dinitrophenol, 2-nitrophenol and 4-nitrophenol, as shown in Table 3.2. Tests were conducted in batch and continuous flow systems, under subcritical and supercritical conditions, and with two choices of oxidant (oxygen and hydrogen peroxide). Oxidant excess was in the order of 100%, and in some cases biological sludge was added to provide additional heat. No numerical data were reported on the destruction of any of the individual components. However, it was described that the destruction of the higher molecular weight organic compounds in the influent generally occurred rapidly, and that the lighter weight transformation compounds (such as acetic acid) required longer residence times, higher temperatures and/or catalysis. TOC removals at supercritical conditions were higher for both batch and continuous flow reactors than those at subcritical. 18 Table 3.2 Influent characteristics for DNT wastewater experiments. (Li et al.) Composition Concentration [mg/1] Waste without sludge solids Waste with 3% wt sludge solids Dinitrotoluene (DNT) 346 179.1 2-Nitrophenol 0.466 0.243 4-Nitrophenol 0.471 0.346 2,4 Dinitrophenol (DNP) 3.93 2.03 4,6-dinitro-ortho-cresol (DNOC) 15.18 7.84 Phenol 16.11 8.83 Acetate 2.1 40.04 Chloride 3.9 473.1 Nitrite 37.2 19.25 Nitrate 1224 631.8 Sulphate 1391 854.4 Total Organic Carbon (TOC) 1840 -Chemical Oxygen Demand (COD) - 38970 3.2.2.1.1 2,4 DNP Destruction kinetics for 2,4 DNP wastes have not been reported in literature, although experiments were conducted at the UBC-Noram pilot plant in 1999 3 8 . These tests treated a low concentration, synthetic solution of ammonium 2,4 dinitrophenolate at very high oxygen excesses, according to Table 3.3. Instabilities in the pilot plant where observed due to poor regulation of the system's pressure and oxygen flow fluctuations, at times resulting in poor or unstable conversions of the waste. Likewise, foaming in the effluent was observed due to poor performance of the gas-liquid separator. Nevertheless, the tests yielded encouraging 19 results: No CO or NOx was detected in the vent gas and both TOC and nitrophenols were below the detection limits (see Table 3.3). In the aqueous effluent with a pH of 8.0, ammonium bicarbonate was observed. Taking into consideration experience from the 1999 experimental runs, some changes in the system were made, which will be discussed in the following section. Table 3.3 Experimental conditions for DNP experiments at UBC/Noram pilot plant, 1999. Composition Feed concentration [mg/1] DRE [%] Operating parameters Oxygen excess [%] Pressure [MPa] Temperature in reactor [K] 2,4 DNP 11,188 99.99 601 25.5 800 Total ammonia (as NH3) 5,543 53.13 TOC 5,500 99.89 3.3 Experimental apparatus and methods 3.3.1 Apparatus The oxidation experiments were conducted in a pilot-scale plant, designed to treat a maximum waste flow of 2 L/min. The system, a simplified schematic of which is shown in Figure 3.2, consisted of a high-pressure pump, an oxygen vessel with a compressed air-driven oxygen compressor, and a tubular system, (Inconel 625, high pressure tubing, 0.622 cm ID and 0.952 cm OD (3/8")) formed by the following sections: 20 • Regenerative Heat Exchanger (l/2"x 3/8"counter flow tube in tube exchanger): 6.2 m in length • Preheater 1: 4.7 m in length • Preheater 2: 4.7 m in length • Test Section: 3.8 m in length • Reactor: 120 m in length • Process Cooler (5/8"x 3/8", counter flow tube in tube, SS316): 6.2 m in length, A l l hot sections of the system were insulated in 15.2 cm x 15.2 cm boxes of ceramic board (Kaowool). One polyethylene storage tank (550 L capacity) supplied distilled water to the system, which was used during system warm up. Another tank (250 L capacity) contained the waste mixture that was fed into the system once steady state was reached. A steam coil was used during the red water tests to keep the feed in solution. Liquids were pumped into the system by a high pressure, triplex, positive displacement, metering pump (GIANT P57), followed by a pulsation damper (Hydrodynamics Flowguard DS-10-NBR-A-1/2" NPT). The flow from the pump was controlled by a variable frequency drive (VFD, Reliance ISU21002). Steam tracing maintained the feed line at 60-70 °C during red water tests. A compressed-air-driven booster pressurized gaseous oxygen from a liquid oxygen tank (equipped with a vaporizer) up to 324 bar. The delivery pressure to the SCWO system was regulated at 270 bar, allowing the oxygen to flow by pressure difference between this delivery system and the SCWO unit (normally 250 bar). The oxygen flow was controlled by a metering valve and measured by a 1.14 mm orifice meter, which was connected to a differential pressure transmitter (FOXBORO ID P10). Uncertainty in the calibration of this 21 orifice meter depended on the oxygen pressure and voltage reading (See Appendix A for details and system calibration), but in practice always was of the order of 1.3 to 1.6%. The aqueous and oxygen mixture first passed through a regenerative heat exchanger. The cold, incoming fluid flowed through the tube side, and the hot fluid left through the shell side. After the heat exchanger, two separately controlled preheaters were used to continue heating the fluid until it reached the desired temperature. The test section and the reactor were similarly heated, and together with the preheaters and the regenerative heat exchanger formed a 150-meter long tubular system, in which oxidation reactions started as soon as conditions allowed it. After leaving the reactor, the process fluid flowed through the shell side of the regenerative heat exchanger, and then through the process cooler, which took the bulk temperature down to 40-50 °C. When leaving the system, the fluid passed through a gas-liquid separator. Then, the gaseous stream passed through a carbon bed filter that eliminated odours. Its flow rate was measured by a dry gas flow meter (AL 425 Canadian Meter Company Limited) (see Appendix B for flow meter calibrations). A 310 bar nitrogen tank and the main body of a backpressure regulator Tescom 54-2100 series (without the spring element) formed the backpressure regulation system. The nitrogen tank was set to the pressure desired in the SCWO system, allowing it to operate with a pressure oscillation of no more than 1 bar. This stability in the system pressure could be translated into stable oxygen flow and better control over the operating conditions. Figure 3.3 shows an example of pressure and oxygen vs. time during a real oxidation experiment. In this case, samples were taken only from the effluent. Consequently, there was 22 no chance of pressure fluctuations due to sudden changes in the system's flow rate, which could occur when the intermediate sampling ports were in use. According to this figure, the maximum variation in the system pressure was 0.029 MPa, causing a variation of 0.02 kg/h in terms of oxygen flow. Since the system generally operated at relatively low oxidant excess, an accurate oxidant flow control was of vital importance for the proper oxidation of the waste. However, Figure 3.4 shows a case in which there was a noticeable pressure (and subsequently oxygen flow) fluctuation. This was due to opening the intermediate sampling valves, which destabilized the system pressure. After finishing each experiment, the system was rinsed and cooled down with distilled water, then depressurized. 23 Q. —i m (3 ° <r-®4-C0 GO I—*-CO 3 O 13 1.2 1.1 "a 1 o c o 2> 0 . 9 O 0 . 8 0 . 7 2 ,4 D N P - b a s e d e x p e r i m e n t s . R u n #4b A v e r a g e P r e s s u r e P r e s s u r e O x y g e n f low A v e r a g e O x y g e n f low 0 . 2 0 . 4 0 . 6 0 . 8 1 E x p e r i m en t tim e [m in] 1.2 1 .4 1 .6 1 . 8 2 5 2 4 . 8 2 4 . 6 2 4 . 4 <Z> 2 4 . 2 <£ CD 3 2 4 TJ CD </> 2 3 . 8 S 2 3 . 6 2 3 . 4 2 3 . 2 2 3 TJ .0> Figure 3.3 Pressure and oxygen flows. Samples only taken from the effluent. 2,4 D N P - b a s e d e x p e r i m e n t s . R u n #3 1.7 S> 1.6 1.3 — v - W - f H - — r -Y/^:T"T-A i \ P r e s s u r e A v e r a g e P r e s s u r e W O x y g e n f low 10 15 20 E x p e r i m ent tim e [m in] 25 30 25 24.75 24.5 24 5 23.75 <» 23.25 35 23 Figure 3.4 Pressure and oxygen flow. Samples taken from sampling ports and the effluent 25 3.3.2 Fluid temperature measurements Bulk and surface temperatures were monitored during the experiments. A table describing the thermocouples distribution throughout the system is provided in Appendix C. Bulk and surface thermocouples were K-type, Inconel sheathed, and ungrounded. Their uncertainty was ± 5°C. 3.3.3 Sampling system In order to learn about the destruction of the wastes studied, it was necessary to take samples not only from the effluent port, but also from several intermediate locations. This allowed us to follow the course of the SCWO reaction process in terms of destruction efficiency and intermediate species. For this purpose, a new, water-cooled, jacketed sampling system was installed and validated. It is imperative that the samples be instantly quenched, because otherwise the analysis of results could be deceiving, yielding false conversions that did not really take place in the system, but in the sampling ports. Each sampling port, (Figure 3.5) was purged for more than two sampling port residence times before taking a sample (typically a sampling time of 2 minutes). Additionally, the sampling ports were rinsed with distilled water between each experimental run, to make sure that no organics remained in the sampling line. Random samples of the final rinse water were taken and analysed for TOC in order to confirm the absence of organics (see Appendix D for calculations of the necessary rinsing times for each sampling port and other details). After assuring that the sampling lines were completely clean, the next experimental run started, and 26 the organic waste was again fed into the system. A l l jackets were made with Swagelok reducing tees and lengths of copper tube. Reactor Hot fluid C o o l i n g -H 2 0 in ~ 1 1/min Thermocouple (T below critical in ~ 1.5 sec.) 2.5 cm Jacket .Cooling H 2 Q out To gas-liquid separator Sample -0.1 ml/sec Figure 3.5 Sample cooler for intermediate sampling port. 27 3.3.4 Analytical procedures Given that chemical analyses methods have an important effect in the accuracy of the results, a brief discussion is in order here. Nitrophenols (including phenol) were analyzed with a HP HPLC 1100, with a detection limit 0.5 mg/L and an accuracy of ±10%. TOC was analyzed by a Shimadzu TOC-500 Carbon analyzer, with a detection limit of 1 mg/L and an accuracy of 10%. Ammonia was analyzed by a colorimetric method, with a detection limit of 0.01 mg/L and an accuracy of ±13%. It is important to mention that samples containing ammonia should be analyzed immediately after being taken, or be acidified and properly stored. Otherwise, the results from the analyses yield falsely low ammonia concentrations, due to the ammonia volatilization. Not observing this caused differences with the ammonia measured in two different labs. The values used for all calculations in this work corresponded to those of the lab that observed the proper treatment of the samples (see appendix H). Gas analyses were done by GC with a thermal conductivity detector in a HP packed column gas chromatograph (GC), with an accuracy of ±10% and detection limits ranging from 0.1 to 0.5 % (by volume). Carbonates and bicarbonates were obtained by pH titration; the accuracy was of the order of 10%. Nitrates and nitrites were analyzed in a Dionex ion chromatograph, with a detection limit of 0.1 mg/L and an accuracy of ±10%. Finally, metals were obtained by an inductively coupled plasma (ICP) method, with detection limits ranging from 0.02 to 0.1 mg/L and accuracies from ±1.3 to 7.5%.The accuracies of the analytical methods were considered for the calculations of errors in the yields and conversion of the different compounds. 28 3.4 Calculations 3.4.1 Oxygen excess The stoichiometric relation for the complete destruction of phenol is given by Equation [2]. The stoichiometric requirement for oxygen in g/min at a given concentration is provided by Equation [3] below, where Phin represents the feed concentration in wt. %, muquid m e liquid feed mass flow rate in g/min and M.Wphenoi and M.W02 the molecular weights in g/mol of phenol and oxygen respectively. The percentage in oxygen excess was calculated as shown in Equation [4]. C6H5OH{l) +702{g) -> 6C02(g) +3H20(l) [2] %Phin/100 mugM ^oxygen stoich.Ph = MWphenol ° 2 [ ] (th — th, 1 v oxygen oxygen stoich.' °2ex = 1 1 0 0 oxygen stoich. [4] The stoichiometric relation for complete oxidation of 2,4DNP is: C 6 H 3 O H ( N 0 2 ) 2 ( 1 ) + 4.5 0 2 ( g ) -> 6 C 0 2 (g)+ 1.5 N 2 (g)+ 3.5 H 2 0 ( 1 ) [5] In this equation, it is assumed that nitrogenous compounds were converted to N 2 (g), and not to nitrous oxide (N 2 0), as could also have been the case. The assumption was made based on the experience from the experiments conducted in 1999, in which practically no N 2 0 was detected. The stoichiometric oxygen requirement could be calculated similarly to equation [3]: %DNP. /100 m,:auid oxygen stoich D N P M W 02 L J DNP 29 Where DNPin was the feed concentration of 2,4 DNP in % wt., and M.WDNP was the molecular weight of 2,4 dinitrophenol. 3.4.2 Residence times The residence time dt in a differential length of reactor dL is given by Equation [7], where A represents the area of the tubular cross sections in m2, L the length of the system, p(T) the density in g/L at its corresponding temperature T (in K) and m a l the total feed mass flow rate, including both the waste-water mixture and the oxygen fed into the system. A dL • dt = - p(T) [7] mtotal When the elements of the system are divided into a number of segments N, the cumulative residence time through out the system, for every position can be represented as in Equation [8]. ri\i)-hi-\)A N*mtotal A l l residence time calculations were performed in Matlab by forward integration over a number of segments of the tubular system (see Appendix J). Each element of the system (preheaters, test section, reactor and regenerative heat exchanger) was divided into 100-300 segments of constant enthalpy increments, and the water properties were obtained by interpolation from a lookup table from the IAPWS-95 Scientific Formulation of Water Properties.39 The data files loaded into the Matlab program included the readings from the thermocouples at different locations throughout the system. With this data, the program was able to calculate the residence time at each specific location in the system. 30 The densities used for the calculations corresponded to those of water because no data were available for density of water-phenol-oxygen or water-dinitrophenols-oxygen mixtures. However, using water densities is a reasonable assumption, considering that the mass percentages of oxygen and organics in the feed were still very low compared with those of water. For example, for a water-4% by wt phenol feed flow rate of 0.78 L/min and an oxygen flow of 0.23 l/min at 269 bar, the total flow entering the system would be 1.01 L/min, of which 74.26% of the volume would correspond to water, 3% to phenol, and 23.5 % to oxygen. Figure 3.6 presents an example of the progress of the residence time throughout the system. The experiments conducted at higher temperatures generated lower residence times. The progress in time of the destruction of both phenol and 2,4 DNP will be shown in different plots in the following sections. R e s i d e n c e t i m e v s . P o s i t i o n . 4 % w t P h e n o l 50 8 40 c a> •o w 30 a> 0C 0#-P H 2 out 1 R L 2 / P H I in , T T T ] R L 1 0 . i R L 6 . . . . -' j* ' o • • '7 -v ' i ..-?•" i }v 1 1 ,| -o | '& R H X i i n • •«•• Run 1, 666K, 10% 02 Run 2, 685K, 34% 02 • •O- Run 3, 778K, 39% 02 • V - Run 4, 693K, 34% 02 60 80 100 P o s i t i o n [m] 120 140 Figure 3.6 Plot of residence time vs. system length at different conditions 31 3.4.3 Yields and Conversions Conversion X at some location was calculated from the concentration C at that location and the initial concentration Cin: C-C X = I N [9] C ^in For example, the TOC destruction efficiency was CTOC • ~ CTOC XTOC= ^ [10] cTocin The destruction of other compounds in the feed, (e.g. ammonia) was calculated in the same way. Yields of CO, C02, N 2 and N 2 0 were calculated as the molar flow rate of CO or C 0 2 at the sampled point divided by the TOC molar flow rate in the feed, and the molar flow rate of N 2 and N 2 0 divided by the molar flow rate of N in the feed, respectively. For example: X C 0 2 = - T ^ - [11] "TOCIN * N 2 = ^ - [12] 2 n N -1 1 in Gas compositions were normally given in percent, on a per volume basis. Therefore, their molar flow rates could be obtained by simply multiplying their corresponding percentage in the gas sample by the gas flow rate, in gmol/min, for example: %co2 . NC02 =~[^- ngas [13] 32 The molar flows of TOC or N in the .feed were given as their corresponding concentrations in the feed, in g/L multiplied by the total liquid feed flow rate in L/min and divided by their respective molecular weight. For example: = CTOCin ^liquid T/~\S-* • r -w-r-r L J C 3.4.4 Calculations for the comparison with other studies of the phenol experiments The global reaction rate for phenol destruction [1], with the kinetic parameters from Table 1, was used to compare other authors' predictions with our experimental results. Equation [1] was integrated in Matlab over each segment of the tubular system, using our own system's temperature profiles and residence times calculated as previously explained. In the program, (see Appendix J), the system was divided into a number of segments z, and the rate from Equation [1] was expressed in the following form: r n = -K.. .. [Phf [0]b [H2Of [15] (') 0-1) 0-1) 0-1) z O ' - i ) Where K was the rate law constant given by A exp and water concentration varied KRT , according to its density at each different point in the system. A l l elements concentrations were entered in mol/L. The initial phenol concentration [Ph]in at the system's pressure and temperature was defined as: [Ph]in=xPhinTTJ^ [16] MWPhenol 33 Where pj„ was the initial water density at the initial temperature and xPn ,•„ the phenol mass fraction at initial conditions: xPh = ——^nol [17] (^liquid + ^Oxygen ) w-phenoi ' ^uquid' a n d ^Oxygen w e r e the feed mass flows of phenol, liquid and oxygen, respectively. The phenol mass flow rate was a function of the feed concentration Ph,in in weight percent and the total liquid flow rate rhLi id: Ph-Wpheno^-^j- mliquid - t18] The initial water concentration in moles/L was represented by the relation of its initial density divided by the molecular weight of water: [H20]in = [19] MWH20 The initial oxygen concentration was a function of the initial concentration of phenol and the molar relation oxygen-phenol: mOxygen / [02], =[Ph]. /MW<>xygen [ 2 Q ] m mphenol/ /M'Wphenoi Phenol concentration during the experiment varied as: [Phlw^Ph^+dlPh]^ [21] d[Ph]Q) = r ( 0 [22] With d[Ph] being the differential changes in phenol concentration per system segment i , and time was the residence time per segment i and the oxygen concentration was assumed to vary according to the stoichiometric relation: 34 [23] This stoichiometric assumption is not accurate when carbon-containing products different from CO2 appear.16' 4 0 In such a case, the oxygen consumption would be different than that of the stoichiometric relation [2]. Nevertheless, the effective stoichiometric coefficients for the formation of carbon compounds will increase with conversion, to finally reach the stoichiometric value of Equation [2]. Since the effective stoichiometry for the incomplete oxidation of phenol is not known, the oxygen concentrations cannot be calculated by using this approach. This situation would leave us with two alternatives: 1. Use the stoichiometric relation to calculate the oxygen concentration (a reasonable assumption when working with global rates); or 2. Use very high excess oxygen during the experiments, to assume that its concentration is either constant or changes only by a small fraction. Since the main objective of this work was to investigate and validate the supercritical water oxidation destruction of organics at practical conditions it was decided to maintain a low oxygen excess and use the stoichiometric relationship to calculate oxygen concentrations. The phenol conversions in the system were calculated according to Equation [9] from the previous section. This procedure was followed for the authors referred to in Table 3 . 1 . 1 4 ' 1 5 ' 1 6 ' 1 7 ' 1 8 ' 2 1 ' 2 2 ' 2 3 The results obtained will be discussed in section 3.2.1 35 3.4.5 Error analysis Errors in controlling experimental conditions also have an effect on the overall accuracy of the experiments. The measurement of temperatures, pressures and liquid and oxygen feed flow rates directly affect the calculated residence times. The control of the gaseous stream flow rates and sample collection techniques, together with the analytical uncertainties, affect the reported conversions and yields. 3.4.5.1 Residence times The calculation of system pressure and oxygen flow uncertainties have been described in the experimental conditions sections, and in Appendixes A , F, G, and H . According to Equation [7], in section 3.4.2, residence time can be calculated as a function of the area of the tubular system, its length, the relation between the density of the fluid, and the total mass flow rate of the fluid: Equation [7] was used as the basis of the calculation of the residence time's uncertainties. It was considered that the uncertainties in the densities were mostly given by the uncertainties in the temperature, and to a lesser extent, by the uncertainties in the system's pressure. As explained in section 3.4.2, mtotai included the liquid and the oxygen mass flow rates that were fed into the system (riiiiquid and moxygen). The uncertainty in measuring the liquid flow rate was neglected, as it was considered very small (0.5 mL/min, for feed flow rates of approximately 0.8 L/min in all experiments) in comparison with those of the oxygen flow rates. Therefore, the factors influencing the residence time were the system's temperatures 36 and pressure (affecting the density) and the oxygen mass flow rate (affecting the total feed flow rate). Considering the residence time as a general function R=f(yi, yi, ... yn), its uncertainty (wR) was expressed by the Equation [24]41 below, where w i , w 2 , w n ] were the uncertainties of the individual equation variables, ylt y2, ... yn. Taking mlotal as yi and p(T, P) as y2, wj was taken as the uncertainty in the oxygen mass flow rates (section 3.4.2 and Appendix A), and w2 as the uncertainty in the density. -1I/2 wR dR >2 — + dR \2 w2 'dR * wn [24] The calculations of residence time uncertainties for each experiment were performed in Matlab (see Appendix J). The overall uncertainty in the density (vv2) was calculated in several steps. First, the uncertainty due to the accuracy in temperature was obtained, then the uncertainty due to the oscillation in pressures. For the temperature component, it was assumed that the temperature readings were accurate within ± 5 degrees, as already explained in section 3.3.2. The densities at T+5 and T-5 degrees were calculated for each temperature reading. The same was done for their correspondent unbiased standard deviation, according to Equation [25], where n was the number of measurements, 3 for each temperature reading T, (p(T), p(T+5) and p(T+5). yi and J2 were p(T+5) and p(T+5) respectively, and ym was the density at the temperature reading p(T). r = 1 " n — l , i=l nl/2 [25] 37 To calculate the uncertainty in the density due to the fluctuations in pressure (SP), the same procedure was followed, but in this case, the uncertainty in the pressure varied for each case (refer to Tables 3.4 and 3.6 in the experimental conditions section). The densities at P+(SP) and P-(dP) were calculated, as well as the corresponding unbiased standard deviation, by Equation [25]. It was observed that the uncertainties due to the changes in pressure were lower than those from the changes in temperature, with their values always being maximum at temperatures/pressures close to the critical point. This was to be expected due to the sudden change in the water density around the critical point. Finally, the total uncertainty in the density measurements (w2) was calculated as the sum of the uncertainties caused by the temperatures and the pressures. Equation [24] was then used to calculate the total uncertainty in the residence time. As it was observed with the densities, the uncertainty in the residence time was maximum at locations with temperatures around the critical point. 3.4.5.2 Yields and conversions Conversion of organics, TOC and ammonia were calculated as shown in equation [9] of section 3.4.3. Using this equation, equation [24] and the procedure explained before, the uncertainty in the conversions was calculated in Matlab (Appendix J). The uncertainty in the destruction of these compounds was given by the uncertainty in the corresponding analytical technique. For the case of the gas yields, they were represented according to Equations [11] to [14] of section 3.4.3. In one formula, the gas yields were expressed, for example, as Equation [26]: 38 MWT0C Following a procedure similar to the one described for the residence times, Equation [24] was used to obtain the uncertainties in the gas yields, taking yi as the volume percent in the gas sample (%), y2 as the gas flow rate, as the TOC or N concentration in the feed and y4 as the total liquid feed flow rate. In the same way, all calculations were performed in Matlab, and can be seen in Appendix J. As shown, gas yield uncertainties depended both on analytical measurements and on the system's accuracy when measuring the liquid and gaseous flow rates. The uncertainty of the liquid flow rate was 0.5 mL/min, as explained before, and it was not neglected in this case. The uncertainty in measuring the gaseous streams flow rates varied with the experiments and appears explained in each of the correspondent discussion of results section. 3.5 Discussion of results 3.5.1 Phenol Experiments 3.5.1.1 Experimental conditions High concentrations of phenol were treated, in all cases maintaining the oxygen excess at a relatively low level. Uncertainties in the system pressure and oxygen excess were obtained from the uncertainties in the voltages recorded by the data acquisition system, (see Appendix F for more details on these calculations). At the time of the tests, a different orifice meter from the one described in section 3.3.1 was used. In this case, no uncertainties in its calibration 39 equation were considered (see Appendix A for more information). The precision with which the feed flow rate was measured was within ± 5 ml/min. The purity of the phenol used was > 99% (ultra pure grade). The investigated conditions are shown in Table 3.4. Table 3.4 Experimental conditions for phenol destruction. Phenol cone. [%wt] #of Runs Run Feed flow rate [Vmin] Temperature in reactor [K] Absolute Pressure [MPa] Oxygen excess [%] 1 666 25.67+ 0.02 10+5 4 4 2 0.78+ o.oo5 685 25.78± o.i8 3 4 ± 8 3 778 25.48+ o.2i 39+8 4 693 25.69± 0.2 3 4 ± 5 5 681 25.67+ 0.45 34+34 6 690 25.54±o.87 -1 ± 8 0 2.7 5 7 0.8± 0.005 703 25.69+ o.4 21± 10 8 726 25.61+0.26 19±6 9 737 25.61+0.26 19±6 3.5.1.2 Observations Phenol, TOC and GC analyses were carried out to obtain the destruction efficiencies (conversions) and gas yields, as described in section 3.4.3. Gaseous flow rates were measured with an A L 425 Canadian Meter Company Limited volume flow meter (Appendix B), and it was considered to have an uncertainty of 5%. As stated before, our objectives during these experiments were not to perform a kinetic analysis to determine a rate constant, its associate Arrhenius parameters or the reactant's reaction orders. We focused our attention on proving the pilot plant performance with high 40 concentrations of a hard to destroy simple compound, with practical (moderately low) excesses of oxygen. Table 3.5 shows TOC and phenol conversions and gas yields for all different runs. Please refer to Appendix G for more details on each experimental run. Conversions and gas yields were calculated as explained in 3.4.3. 41 Table 3.5 Conversions and yields for phenol experiments Run Conditions T[K], Excess 0 2 [%] Sampling Point Distance from feed [m] X phenol X TOC CO yield C 0 2 yield Carbon Balance Feed concentration =4 %wt as Phenol 1 PH2in 11.8 - 0.328 - - -PH2 out 16.07 0.669 0.49 0.034 0.28 -666,10 RL-2 34.18 - 0.656 - - -RL-6 61.91 - 0.744 - - -Effluent 150.14 0.98 0.815 0.12 0.786 1.15 2 685, 34 Effluent 150.14 0.95 0.784 0.094 0.55 0.94 3 778, 39 Effluent 150.14 0.9998 0.9977 - - -4 693,6 Effluent 150.14 0.977 0.858 - - -Feed concentration = 2.7 %wt as Phenol PH2in 11.8 0.41 0.3 - - -PH2 out 16.07 0.565 0.47 0 0.108 -5 681,34 RL-2 34.18 0.65 0.59 - - -RL-6 61.91 0.79 0.65 - - -Effluent 150.14 0.97 0.79 0.082 0.402 0.74 PH2in 11.8 0.25 0.24 - - -PH2 out 16.07 0.4 0.24 0 0 -6 690, stoich. RL-2 34.18 0.61 0.43 - - -RL-6 61.91 0.75 0.61 - - -Effluent 150.14 0.94 0.75 0.169 0.801 1.32 PH2in 11.8 0.52 0.34 -PH2 out 16.07 0.61 0.48 0.027 0.201 -7 703, 21 RL-2 34.18 0.73 0.59 -RL-6 61.91 0.8 0.68 -Effluent 150.14 - 0.81 0.097 0.458 0.87 8 726,19 Effluent 150.14 0.98 0.94 - - -9 737,19 Effluent 150.14 0.993 0.89 0.032 0.614 0.78 42 As can be seen, there is a difference between the TOC and the phenol conversions. In every case, the TOC conversion is lower than that of phenol. This shows that in all cases organic species different from phenol remained in the aqueous effluent. It was not the objective of this work to identify such intermediate species. From the runs in which intermediate samples were taken, it was observed that by the end of the Preheater 2 (PH 2 out), a good amount of phenol had already been converted into intermediate species and a smaller portion had been converted into CO or C 0 2 . However, for most of the runs, final TOC conversions were considerably lower than phenol conversions. Considering how fast phenol started to break down into other species, it could be speculated that the new intermediates were less reactive and hence more difficult to eliminate. This is consistent with results obtained by both Kranjc and Levee 1 8 and Rice and Steeper42, who observed complete disappearance of intermediates long after phenol had been destroyed. Gopalan and Savage17 have presented a quantitative reaction model that showed that longer residence times and higher temperatures could favour the destruction of intermediates and the formation of C 0 2 . Relatively good carbon balances were achieved in the effluent streams, although they usually did not completely close. One possible reason for this could have been the formation of tarry materials (organic intermediates that could have been formed and were not destroyed), which remained in the system. This is likely to occur at high concentrations.14'17 In our system, small amounts of tar were observed in the back pressure regulator when opened for cleaning. Traces of CO were obtained in the gas effluent samples, indicating that the oxidation of CO was relatively slow. Nevertheless, the yield of CO was less than that of C 0 2 at all times. Moreover, the yield of CO was always lower than unconverted TOC. This observation 43 suggests that even though CO—>CC>2 is a relatively slow reaction, it is not a rate-determining step. Rather, the rate-determining step is the further destruction of one (or more) of the oxidation intermediates. This agrees with the results repeatedly obtained by L i et a l . 4 3 and Martino and Savage44' 4 0 , in which it was concluded that the main path for CO2 formation by -passed CO. A suggested path to CO2 was via decarboxylation of carboxylic acid intermediates, which are formed via ring-opening reactions. No consistent temperature-CO yield production trend was observed, but no gas samples were taken at the highest temperature (run 3, 778 K). Run 9 (464 K) produced the smallest amounts of CO, with a yield of 0.032 (1.26 g/min). 3.5.1.3 Effect of temperature Figures 3.7 and 3.8 show plots of phenol and TOC conversions versus temperatures for all runs at both concentrations treated. In general it was observed that higher temperatures yielded higher phenol and TOC conversions for both the 4% and 2.7 % runs. One possible reason for not having observed a consistent increase in the conversion with temperature could have been some remaining contamination in the sampling ports, which suggests that they should be allowed more rinsing time. Taking this experience as base for the following 2,4 DNP experiments, it was decided to rinse the whole system with water after each experimental run. The sampling ports were rinsed out for as long as 5 minutes, with occasional steam flushing, in order to remove any remaining organic contaminants 44 1.05 r Pheno l experiments. Pheno l destruct ion eff iciencies g 'to > o O R u n 1 1 0 % 0 2 R u n 5 34% 0 2 t R u n 4 3 4 % 0 2 i Q | 0.95 I-R u n 2 3 4 % 0 2 R u n 6 s t o i o h . % 0 2 R u n 9 1 9 % 0 2 R u n 3 3 9 % 0 2 R u n 8 1 9 % 0 2 Phenol 4% Phenol 2.7% 660 680 700 720 740 Temperature [K] 800 Figure 3.7 Effect of temperature, feed concentration and oxygen excess on phenol DREs 1.05 Pheno l experiments. T O C destruct ion eff iciencies 0.95 o o o O O l -0.9 0.85 0.8 0.75 0.7 R u n 3 3 9 % 0 2 R u n 8 1 9 % 0 2 R u n 9 1 9 % 0 2 | -Run 1 1 0 % 0 2 R u n 5 3 4 % 0 2 R u n 2 3 4 % 0 2 R u n 4 3 4 % 0 2 ^ R u n 7 2 1 % 0 2 R u n 6 s t o i c h . % 0 2 • TOC 4% V TOC 2.7% 660 680 700 720 740 Temperature [K] 760 780 800 Figure 3.8 Effect of temperature, feed concentration and oxygen excess on TOC DREs 45 3.5.1.4 Effect of Residence time Figures 3.9 and 3.10 show the temperature profiles vs. residence time for the 4 % wt. and 2.7 % wt. experiments, respectively. From left to right, the graph symbols correspond to the feed, PHI in, PH2 in, PH2 out, points on the test section, the reactor and the finally R H X out (effluent). Residence times for higher temperature runs were lower. This was caused by the decrease in the water density with the increase in temperature, which directly affected the residence time. Phenol and TOC conversions, as well as the C 0 2 yield for each individual run, increased with residence time. However, there were still traces of CO, even though the C 0 2 yield proved to increase. Figures 3.11 to 3.14 show the conversions and yields profiles for runs in which the effect of residence time was studied. Phenol conversions increased more rapidly than those of TOC, and still some organic intermediate were obtained in the effluent. C 0 2 production was faster than that of CO. 800 750 700 650 s? "600 t_ 3 2 550 CD | 500 I-450 400 -350 300#-Temperature Profi les. 4%wt Pheno l •O O GO PH2 out P H 1 in / \ A >X-:xy. -V•••» « T " Is-.**'' " " \ R L 6 R L 1 0 \ \ *~*T RL2 • • R H X in ••«•• Run 1, 666K, 10% 02 ••0- Run 2, 685K, 34% 02 ••©• Run 3, 778K, 39% 02 - V Run 4, 693K, 34% 02 RHX out (effluent) 0 10 20 30 40 50 Res idence Time [sec] 60 70 80 Figure 3.9 Phenol experiments. Temperature profiles for 4% wt runs 46 800 r 750 700 650 Temperature Profi les. 2.7%wt Pheno l PH2 ouu ...ttv::.'.'.'.'-v w $ ^ w v - - - ' ; > o >,«-oo * A R ^-S? — ' : ^ f f ' R L 6 R L 1 0 \ \ \ \ ^ R H X in £ 6 0 0 t 3 2 550 l CD | 500 | 450 Q • XT R H X out (effluent) 400 350 30011-•«•• Run 5, 681K, 34% 0 2 Run 6, 690K, stoich. 0 2 ••©• Run 7, 703K, 2 1 % 0 2 ••V Run 8, 726K, 19% 0 2 • O - Run 9, 737K, 19% 0 2 10 20 30 40 Res idence Time [sec] 5 0 6 0 70 Figure 3.10 Phenol experiments Temperature profiles for 2.7% wt runs Pheno l Exper iments. Convers ions and Yie lds Run #1 • Phenol conversion O TOC conversion > C O yield O C Q 2 yield e-CD •o c 0.8 CO 0-6 \ w c o CO g 0. c o O .ar" 25 0.2 . 10 20 30 40 50 Res idence Time [sec] 60 70 8 0 Figure 3.11 Phenol experiments. Conversions and yields for Run 1 (666K, 10% 0 2 excess) 47 co 0-8 T3 a) >. " D a 0.6 co g 'co cu > 0.4 c o O 0» 0 Pheno l Experiments. Convers ions and Yie lds Run #5 • Phenol conversion O TOC conversion > CO yield O CQ2 yield -ID 10 30 40 Res idence T ime [sec] 50 60 Figure 3.12 Phenol experiments. Conversions and yields for Run 5 (681 K, 34% 0 2 excess) Pheno l Exper iments. Convers ions and Y ie lds Run #6 • Phenol conversion 1 - O TOC conversion Otl^ ' -fe- ' 1 1 1 '— 0 10 20 30 40 50 60 Res idence T ime [sec] Figure 3.13 Phenol experiments. Conversions and yields for Run 6 (690 K, 0% 0 2 excess) Phenol Experiments. Conversions and Yields Run #7 co o-8 CP '>< ro 0.6 0) > 0.4 O o 0.2 • Phenol conversion O TOC conversion > C O yield O C 0 2 yield If ..m 0#^ 20 30 40 Residence Time [sec] 50 Figure 3.14 Phenol experiments. Conversions and yields for Run 7 (703 K, 21% 0 2 excess) 3.5.1.5 Effect of excess oxygen Figures 3.7 and 3.8 show that with stoichiometric amounts of oxygen, phenol and TOC conversions were the poorest, but for runs with higher than stoichiometric oxygen, there was no apparent effect. Not achieving high conversions at stoichiometric oxygen amounts agrees with the findings of Koo et al . 2 1 and Thornton and Savage16. However, both Koo et al and Thornton and Savage found that the conversions increased with increasing the oxygen excess. 3.5.1.6 Effect of phenol concentration As a general trend, phenol destruction was not affected much by the feed concentration, but TOC destruction tended to be lower at lower phenol concentrations. Consistent with most of the previous work on SCWO of phenol, H 1 5 ' 1 6 , 1 7 , 1 8 , 2 1 • 2 2 ' 2 3 there appears to be little dependence of phenol conversion on the feed concentration. In most 49 of the previous work, the global reaction orders with respect to phenol are close to unity. A 18 higher dependence of TOC concentration in the feed was observed by Krajnc and Levee, who obtained a second order relation with respect to TOC conversion in phenol experiments. 3.5.1.7 Comparison with other studies Even though it is known that global rate laws are mainly applicable for the operating conditions at which they were obtained, we decided to conduct a comparison study of the predictions of the existing rate laws at our experimental conditions. Most of the rate laws 1 A. 1 ^ 1 1 "7 18 01 9 0 used in this comparison study, whose kinetic parameters are shown in Table 3.1, describe the SCWO of phenol under low concentrations and high oxygen excess. 9^  Nevertheless, previous studies observed disagreements among these rate laws for differences in excess oxygen of 200 and 300 % excess, concentrations of 50 and 100 mg/L and temperatures between 673 and 693 K. This confirms that global rate laws are quite sensitive to changes in operating conditions. Figures 3.15 to 3.18 show the results obtained as a function of residence time for several runs by following the procedure described in section 3.4.4 (refer to Appendix F for other comparisons). From the graphs, it can be seen that there are some discrepancies in the predicted conversions at these conditions, although very good agreements were obtained with the rate laws proposed by Krajnc & Levee 1 8 and Gopalan and Savage17, and in some cases with Koo et al . 2 1 Some of the other global rate laws either over predicted or underestimated the phenol conversion, which, if used in the design of a SCWO reactor, would lead to either too small or too big devices, respectively. Other reasons for possible discrepancies could have been possible contamination of the sampling ports, only justifying the disagreement with the rate laws that over predicted the phenol conversions. Very fast pyrolysis reactions 50 that also occur during the heating are not accounted for when evaluating the proposed oxidation rates. This would have justified the disagreement with the rate laws that underestimated the phenol conversions. P h e n o l Exper imen ts . C o m p a r i s o n with other s tud ies R u n #1 R e s i d e n c e T ime (sec) Figure 3.15 Phenol experiments. Agreement study. Run 1 (666K, 10% 0 2 excess) P h e n o l Exper imen ts . C o m p a r i s o n with other s tud ies Run #5 i ~ i 1 1 10 20 30 40 50 60 R e s i d e n c e T ime (sec) Figure 3.16 Phenol experiments. Agreement study. Run 5 (681 K, 34% 0 2 excess) 51 P h e n o l Exper iments . C o m p a r i s o n with other s tud ies Run #6 11 -1 '— 1 1 1 i_ 25 30 35 40 45 50 R e s i d e n c e T ime (sec) Figure 3.17 Phenol experiments. Agreement study. Run 6 (690 K, 0% 0 2 excess) P h e n o l Exper iments . C o m p a r i s o n with other s tud ies R u n #7 25 30 35 40 45 R e s i d e n c e T ime (sec) Figure 3.18 Phenol experiments. Agreement study. Run 7 (703 K, 21% 0 2 excess) 52 3.5.2 2,4 DNP based wastes 3.5.2.1 Experimental conditions Since 2,4 DNP has reduced solubility at ambient temperature compared to the elevated temperature at which real red water is produced and processed, the waste to be fed to the SCWO reactor was heated by using a steam coil (See Figure 3.2). During the heating process, steam at close to atmospheric pressure heated the insulated waste tank through a 3/8" stainless steel coil. A tap-water-driven aspirator pump then took it out of the system. This kept the steam circulating and provided temperatures up to 90°C in the waste tank. The stock preparation procedures and solubility conditions are discussed in Appendix E. The feed temperatures were set based on the criteria shown in Table E . l of that appendix. The compositions and conditions explored are shown in Table 3.6. A total of 13 experimental runs were carried out, with 5 different temperatures and several oxygen excesses in most of them. This allowed for the study of both the influence of temperature and oxidant excess in the destruction of the waste. Uncertainties in the oxygen excess for runs 0, 1, 3 and 5 (in which intermediate samples were taken) were obtained from the uncertainties in the voltages recorded by the data acquisition system. For the other runs, in which pressures and voltages were considered to be more stable, oxygen excess uncertainties were taken from the uncertainties in the oxygen flow calibration equation (see Appendix A for the oxygen flow meter calibration, and Appendixes G and H for oxygen excess uncertainties in each run). 53 Table 3.6 2,4 DNP experimental conditions. Feed Composition [% wt] #of Runs Run # Feed Flow Rate [L/min] Temp, in reactor ' [K] Feed Temp. [K] Absolute Pressure [MPa] Oxygen excess [%] 2.4% wt. as 2,4 DNP 2.1% wt. as (NH 4) 2S0 4 1 0 0.78± 0.005 780 358 24.9 + °' 2 6 - 1.22 ™: r 6.67 % wt. as NH 3 1 330 „ „ A + 0 - 2 24.4 „ , - 0.5 2 813 330.6 24.48± 0.01 22.44± 1.62 2b 331 24.48± 0.01 0.36+ 1.57 2c 331.7 24.54+ 0.05 -28.93± 1.76 2.26 % wt. as 3 335.3 „ , A + o-2 24.4 - 0.41 2,4 DNP 0.23 % wt as NH 3 12 4 0.78± 0.005 791 336.8 24.39± 0.02 21.05± 1.61 4b 338 24.47+ 0.02 -1.9± 1.57 5 335.5 ~ . ~ + °-25 24 3 Z - 0.99 7 8 . 6 2 ! -6 769 332.1 24.36+ 0.01 16.08+ 1.59 6b 330.7 24.36± 0.01 -3.43± 1.57 6c 327.8 24.32± 0.03 -18.4+ 1.64 7 742 327.8 24.33+ 0.03 73.15+1.98 54 3.5.2.2 2,4 Dinitrophenol, ammonium sulphate and excess ammonia 3.5.2.2.1 Observations Table 3.7 shows the conversions of 2,4 DNP, ammonia and TOC conversions, gas yields, and carbonates, nitrates and sulphates obtained during the experiment (see Appendix G for mass balances). The mass balances for the different species were not completely closed, although in the case of carbon, the balance was much better than for nitrogen and sulphur. Destruction efficiencies, along with gas yields are shown in Figure 3.19 and conversion profiles and intermediate species formation are shown in Figure 3.20. The intermediate species observed were 2-nitrophenol and 4-nitrophenol, which were not detected in the final effluent, and neither was 2,4 DNP. Ammonia was found in the effluent, in the form of ammonium sulphate, ammonium carbonate and ammonium bicarbonate. No phenol was obtained at any stage as an intermediate. From both figures it can be observed that most of the 2,4 DNP breaks into mono-nitrophenols during the first 18 seconds. Then, the process continues mostly as the oxidation of 2- and 4-nitrophenol. In an attempt of a second, higher temperature run, the system became unstable. Pressure and oxygen flows fluctuated, making it impossible to reach steady state; consequently no samples could be taken. A large amount of char deposited in the preheaters, throughout the system and in the backpressure regulator. The char accumulated in the system was observed once it was opened for repair and inspection of damages caused by corrosion. This waste resulted in a highly corrosive environment for the system, provoking the later failure of the regenerative heat exchanger (RHX) and the first preheater (PH 1). High levels of metals-55 mostly nickel, chromium and cobalt- were found in the aqueous effluent (see Appendix H and I). This topic is more thoroughly addressed in Chapter 4. Since only one experiment was conducted with 2,4 DNP and ammonium sulphate, the effect of temperature was not studied. The system was operated at high temperatures, with an average of 780 K in the reactor. These temperatures proved to be enough to destroy the organic feed and achieve high TOC and ammonia conversions. Even though the 2,4 DNP concentration in the feed was expected to be 4%wt. (see Appendix E), only 2,4 %wt. was obtained. This suggested that 2,4 DNP in the feed tank did not reach the necessary temperature to completely dissolve in water (in which case the solubility data from Table E . l should be revised), and/or that the mixing was poor. Despite the observed instabilities, the feasibility of destroying the organic component of the waste was proven. The experiments provided useful insights in how to perform the subsequent experiments. Figure 3.21 shows a picture of the samples taken at different points in the system. From the change in colour the progress of the destruction of the feed can be observed. Slightly red in the beginning, the feed turns green-brown in the intermediate stages, and completely clear in the effluent stream. 56 Table 3.7 2,4 DNP and ammonium sulphate experiments. Conversions and yields PH2 in PH2 out RL-2 RL-6 Effluent Distance from the feed [m] 11.8 16.07 34.18 61.91 150.14 X 2,4 DNP 0.997 0.993 0.9999 0.99996 0.99996 X T O C 0.85 0.93 0.977 0.992 0.9992 X NH3 - - - - 0.9855 CO yield - 0.06 - - < 0.017 C 0 2 yield - 0.322 - - 0.54 N 2 0 yield - 0.002 - - < 0.0016 N 2 yield - 0.106 - - 0.21 Carbon mass balance [%] - - - - 86.59 Nitrogen mass balance [%] - - - - 41.26 Oxygen mass balance [%] - - - - 40.01 Sulphur mass balance [%] - - - - 25.52 2,4 D N P and Ammonium Sulphate. Convers ions and yields 0.8 32 cu c 0.6 o 'co k_ CD > | 0.4 0.2 1 x TOC o 2,4 DNP O CO yield V C02 yield * N2 yield > N20 yield Ammonia ee^  —© — 5 10 15 20 25 30 35 Res idence T ime [sec] 40 45 50 Figure 3.19 2,4 DNP and ammonium sulphate. Conversions and yields (780 K, 199% 0 2 excess) 57 2,4 D N P and Ammonium Sulphate. Concentrat ion profiles or - -10 4 )f 10 O ) E, c o 10' 10 c CD O C O O ra o 10 10 10 ' 10 ' Q 10 15 20 25 30 Res idence T ime [sec] 35 X TOO o 2,4 DNP V 2-nitrophenol 0 4-nitrophenol a ammonia 40 45 50 Figure 3.20 2,4 DNP and ammonium sulphate. Intermediates formation Figure 3.21 Appearance change. (From left to right: Feed, PH2 out, RL-2, RL-6, effluent) 58 3.5.2.3 2,4 DNP and Ammonia 3.5.2.3.1 Observations The temperature rise observed when the waste fed into the system began to release heat from combustion, was not very high, from 10 to 15 P C (see Electronic Files, "red water no sulphate.xls"). The possibility of treating higher concentration wastes could still be explored. During the experiments, the gas samples became contaminated with atmospheric air that had remained in the gas liquid separators of the sampling ports. Nitrogen, oxygen and carbon balances were made to try to estimate the effects of this contamination and to calculate the amount of atmospheric nitrogen and oxygen contained in the sample bags. The procedure used is explained next (see Appendix H for more details and a sample calculation for one of the experimental runs). After finishing the experiments, the effluent rinsing water was collected in a separate container, followed by an analysis of its TOC and ammonia contents. Given the results that TOC was < 20 mg/L and NH3 = 12 mg/L, we assumed that we could account for all of the carbon and nitrogen by material balances. Based on this assumption, the oxygen and nitrogen contents in the gas effluent could be calculated and any additional volumes from the contaminating air could be determined. The volumetric composition of air was assumed to be 79% nitrogen and 21% oxygen. As mentioned before, the feed contained both 2,4 DNP and ammonia. The total feed destruction equation included the oxidation of 2,4 DNP, (see Equation [5]) and the destruction of ammonia: [27] 59 Where z , is the ratio of ammonia and 2,4 D N P molar flows. NHj Equation [28] was used to obtain a stoichiometric table (Table 3.8) that was used to obtain a mole balance that considered the conversions of both 2,4 DNP and ammonia, with nex as the excess of oxygen moles fed into the system, and is XN H3 the ammonia conversion: C6H3OH(N02)2 + ZNH3NH3H4.5+nex)02 ^6C02 X% ADNP + 2 H 2 ° X 2 4 D N P + N 2 X 2 4 D N P X i\n3 ' " [28] + ZNH3^XNH3 ^ + Z N H 3 X N H 3 ^ ^ H n ^ Z ^ X ^ )02 Table 3.8 Stoichiometric table for Equation [28] Specie In [mol] Change [mol] Out [mol] C 6 H 3 O H ( N 0 2 ) 2 1 -X2,4DNP 1- X2,4DNP o2 4.5+riex -4.5 X2J4DNP"% ZNH3 XNH3 4.5+ nex" 4.5 X2J4DNP" % ZNH3 XNH3 co2 0 +6 X2;4DNP 6 X2)4DNP H 2 0 0 +2 X2,4DNP +3/2 ZNH3 XNH3 2 X2>4DNP +3/2 ZNH3 XNH3 N 2 0 + X2J4DNP + !/2 ZNH3 XNH3 X2,4DNP + '/2 ZNH3 XNH3 N H 3 ZNH3 " ZNH3 XNH3 ZNH3 (I" XNH3) Equations [29]-[33], obtained from the stoichiometric table, were used to predict the molar flows in the effluent and intermediate streams: H C ° 2 o u t 6 H2ADNP,in X2,4DNP h =h X +±h X N2out 2ADNP in 2ADNP 2 NH3jn NHj h =2h X +!•" X H20 out 2ADNPin 2ADNP 2 A W 3 • NH3 AW3 A7/3 V NH-i out in [29] [30] [31] [32] 60 % o m = h2ADNPin <4-5 + "ex ~ 2 A D N p ) - \ h m ^ (1 - X m 3 ) [33] The formation of CO2 and N 2 , however, depended on the conversion of other intermediate carbonic and nitrogenous compounds to C 0 2 and N 2 , respectively. The main carbon containing by-products found were organics (e.g. 2-nitrophenol, 4-nitrophenol and picric acid), CO, carbonates and bicarbonates. None of the previously mentioned organics were observed in the aqueous effluent in any of the experiments. Nitrogenous compounds were mostly nitrates, nitrites, ammonia and N 2 0 . Attempts to write equations for the formation of some such compounds are shown in Equations [34]-[37], where £ and C would represent arithmetic values to balance the oxygen moles in the equations. A detailed study of the formation of all intermediate species was beyond the scope of this thesis. C6H3OH(N02)2 + 4.5 + nex02 -> Organics (1 - X ) + CO + CO1' + HCO~ +C02+g 02 [34] CO + \02-^C02 Xco+±02(l-Xco) + CO(l-Xco) + C 02 [35] C02+H2O^H2C03 [ 3 6 ] N20 + ±02^>N2+02 [37] The ratios of C O / C 0 2 and N 2 0 / C 0 2 (referred to as C O / C 0 2 ( B CRI) and N 2 0 / C 0 2 (BCRI) respectively) in the contaminated samples were used to account for CO and N 2 0 . It was assumed that the values of their relative ratios did not change after accounting for the contaminating air. Equations [29] and [30] were respectively transformed into equations [38] and [41]; CO and N 2 0 flows were obtained according to Equations [39] and [40]: ^ ^2,4DNP,inX2,4DNP ™COT. " T O C ^ X T O C ^ R O O N NC02 , = : — " i 3 8 J Lout 1 + -C 0 2 (BCRI) 61 ncoout~nco2out S 2 ( B C R l ) ™ n =n OW r 4 oi NlOout C02ou, C 0 2 ( B C R I ) "~N2out ~"l,ADNP in^2ADNP + 2^ NH3in^ NH3 ~^N03 ~ "N02 ~"'N20 The pressure vapour at the ambient temperature during the experiments (26 °C) was used to find the percentage of water vapour in the gas samples: P H2Ovapor = mp26°C 100 = 3-32% [42] *atm Finally, the total molar gas flows were obtained as the sum of all gaseous components and water vapour (Equation [43]). Molar rates for all runs are shown in Table 3.9. h , = T n i [43] gas total Ai-* 1 L J During the experiments, gas flow rates were measured with a volume gas flow meter model Equimeter RC-M-415. Measurement of pure oxygen flows showed that the gas flow meter was reading values much lower than those that were being fed into the system. For example, according to the voltage reading and Equation [A.6] of Appendix A , the flow fed into the system was of h0l =0.758 mol/min. However, according to the reading from the vent gas flow meter, the flow rate was =0.554 mol/min, 73 % of the measured feed 02. For this reason, the predicted total molar flow rates from Table 3.9 were considered to be more reliable and were used in subsequent calculations. The fractions of air contamination in the samples (xa )were obtained as the best fit with the fractions of the O2, N2 and C 0 2 obtained in the contaminated analyses, as shown in Equations [44] to [46]: 62 V02 BCRI = 0.2lxa+(\-xa)- °2ou< I " , n x = Q.19xa+{\-xa)-^ N2BCRI 2JXi co2 =(l-*a)-"ca lout BCRI [44] [45] [46] The percentages of gaseous components, after accounting for air contamination were calculated as: % N2 0 2 = (fOO-N2 , - ^ ^ - + 0.79 xa 100 J o2 , 100 y°N2-%02-%H2OVAPOR) co2 1 ! W c Q o » f , nN2°out h c o 2 o u t h c o 2 o u t [47] [48] [49] CO C02 h c°2„ [50] N2Q N20 C02 h co2 [51] Table 3.10 shows the percentage of air contamination in the samples, the predicted composition after accounting for the air contamination, and the results of the gas analyses given by BCRI. The errors in the percentage of air contamination were obtained from the average deviation of the individual errors from O2, N2 and CO2 (see Appendix H). 63 As a general trend, the percentage of air increased from intermediates to effluent and from higher to lower oxygen excesses. A considerable portion of air from the gas-liquid separators was evacuated when taking intermediate samples, but not when sampling from the effluent. Furthermore, samples were commonly taken during a fixed period of time. Thus with low oxygen excess levels, or sub stoichiometric runs, there was less total gas flow from the system and so air contamination was higher. Table 3.9 Predicted gaseous molar flows Run Location C02 [mol/min] CO [mol/min] N 2 [mol/min] N 2 0 [mol/min] o2 [mol/min] Y^nt (With water vapour) [mol/min] 1 PHI 0.419 0.012 0.123 0.000 0.304 0.886 PH2 0.477 0.013 0.096 0.023 0.279 0.917 Effluent 0.530 0.000 0.087 0.036 0.281 0.966 2 Effluent 0.525 0.000 0.077 0.044 0.052 0.721 2b Effluent 0.519 0.000 0.081 0.035 0.000 0.656 2c Effluent 0.325 0.017 0.091 0.013 0.000 0.461 3 PHI 0.309 0.020 0.110 0.000 0.296 0.761 PH2 0.462 0.017 0.123 0.014 0.299 0.945 Effluent 0.532 0.000 0.075 0.048 0.275 0.961 4 Effluent 0.525 0.000 0.080 0.040 0.042 0.709 4b Effluent 0.517 0.000 0.081 0.033 0.000 0.653 5 PHI 0.318 0.026 0.109 0.000 0.317 0.795 PH2 0.369 0.063 0.108 0.009 0.303 0.880 Effluent 0.526 0.000 0.068 0.051 0.292 0.968 6 Effluent 0.524 0.000 0.076 0.041 0.017 0.680 6b Effluent 0.515 0.000 0.074 0.041 0.000 0.652 6c Effluent 0.499 0.008 0.080 0.030 0.000 0.638 7 Effluent 0.523 0.000 0.079 0.041 0.269 0.942 64 Aqueous feed analyses showed the presence of high amounts of carbonates/bicarbonates, which, according to our knowledge, should have not been part of the feed (see Appendix E, stock preparation). These levels of carbonates in the feed were suspected to be erroneous and were not included in the above balances (see Appendix H). In general, TOC, C O and N 2 0 yields in the effluent remained very low, whereas ammonia conversions were found to be very poor. Table 3.11 shows a summary of conversions and yields for every sampling location at each experimental run. Metals concentrations in all aqueous samples were very low (Appendix H), indicating that no corrosion occurred during the experiments. 65 99 5 o M /•—s -a CV ;? I to 5 z o CD ex CD ex T J ft >-i n ct § CD Cfl CP o 3 3 o »2 ex w CD ex o o 3 6? 3 o 3 O 3 & CD O o 3 d CD 3 O N d CD a o ON -P . OJ OJ Oh 4^. O o O S 00 NO Oh o , ON d CD 3 to O N o o to o N O NO OJ -o d CD a ON W d CD 3 4*. 4^ d CD 3 to 4^ to ui d CD 3 "Hi 3 d CD 3 • O ON ON O m 31 CD 3 4^ 4^ X to re-X 31 d CD 3 ON ON "Si d o 3 to 3 d CD 3 3 d CD 3 w 3 d CD 3 X "HI 3 d CD 3 3 d CD 3 m d CD 3 to d CD 3 "HI | l CD 3 T T T 3 d CD a O J N O - J ON to to OJ to UJ 4^ NO OJ I © oi NO <1 i--> OJ NO 00 00 to NO o o OJ to I oo OJ oo OJ OJ I  N O oo Uh O N OJ 4^ OJ ON OJ to Uh Uh OJ oo to Ip OJ N O to OJ 4*. to to ON I ON o to o N O N O O N I to ON -o 4^ © OJ to oo NO o o o o -p. o NO o o o o o o 4^ •o I o o o NO o o o o o o o O N O N o o o o o o Uh o OJ to o o OJ OJ © - 4 Uh NO to to Uh NO 4^ '—1 4^ ON OJ •o Ito u>> OJ on 00 I O N oo *» I to Uh N O to © oo N O to OJ I NO NO Uh Oh © Oh OJ to N O to oo o to to to Oh <1 Oh to I N O OJ 00 ON I to OJ 4^  Oh o ON 00 OJ 00 00 o 4^ Oh oo o NO 4* © N O to N O o NO I to oo Oh <1 o © o o 4^ N O OJ oo to o o © o 4^ to N O o I to bo ON to ON 4^. Oh 4^ to - O OJ , A o NO NO •o ON |to OJ 00 NO 4^ OJ 00 ** ON I O N OJ O 4^ OJ I ^ to OJ OJ -o N O -j oo Oh OJ oo OJ OJ - J to 4i. O N 00 ON OJ 4*. I O N o OJ 4*. OJ OJ oo ON I O N N O to to I w Oh N O OJ N O to Oh Oh Oh 4*. 00 o N O to OJ to to NO OJ OJ OJ as Oh o Oh - J © -o o o OJ o to I OJ Oh o OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to OJ to NO o OJ I  NO © •o OJ -o NO OJ OJ OJ ON o o N O OJ OJ 00 o Oh O N I N O to ON OJ i— o o 2s r o o & 5 3 To > o x • r o o & 5 3 CD O -o CX CO o 2 CD ex CD _ex_ Cd o s CD cx CD cx o s CD ex CD cx Cd o 2 CD cx CD C X Cd 2 o o 1—1 2 to o o 0 S - 5 & X S b O N O 1 — 1 I: OJ Table 3.11 2,4DNP and ammonia experiments. Conversions and yields Run Conditions T [K], Oxygen excess [%] Sampling point Distance from the feed [m] X 2.4DNP X TOC X NH3 CO yield* C 0 2 yield* N 2 0 yield* N 2 yield* 1 813,74.73 PHx in 6.9 0.961 0.832 0.566 0.026 0.87 0 0.54 PH 2 in 11.80 0.978 0.891 0.638 - - - -PH 2 out 16.07 0.993 0.934 0.435 0.027 0.95 0.13 0.34 RL-2 34.18 0.99996 - 0.5 - - - -RL-6 61.91 0.99996 0.9997 0.49 - - - -Effluent 150.14 0.99996 0.9998 0.495 0.002 1 0.11 0.45 2 813, 22.44 Effluent 150.14 0.99996 0.9998 0.455 0.002 1 0.14 0.41 2b 813,0.36 Effluent 150.14 0.99996 0.9998 0.37 0.001 1 0.07 0.45 2c 813, -28.93 Effluent 150.14 0.99996 0.9898 0.155 0.03 0.84 0.03 0.44 3 791,73.27 PHI 6.9 0.93 0.71 0.385 0.05 0.71 0 0.49 PH 2 in 11.80 0.981 0.875 0.36 - - - -PH 2 out 16.07 0.996 0.915 0.76 0.036 0.94 0.07 0.53 RL-2 34.18 0.99996 0.9949 0.81 - - - -RL-6 61.91 0.99996 0.9994 0.5 - - - -Effluent 150.14 0.99996 0.9998 0.495 0.002 1 0.12 0.44 4 791,21.05 Effluent 150.14 0.99996 0.9998 0.435 0.002 1 0.07 0.47 4b 791,-1.9 Effluent 150.14 0.99996 0.9994 0.34 0.001 1 0.03 0.48 5 769, 78.62 PHI 6.9 0.931 0.7414 0.36 0.062 0.69 0 0.48 PH 2 in 11.80 0.952 0.7888 0.43 - - - -PH 2 out 16.07 0.974 0.8532 0.42 0.155 0.76 0.03 0.47 RL-2 34.18 0.9999 0.9853 0.594 - - - -RL-6 61.91 0.99996 0.9976 0.48 - - - -Effluent 150.14 0.99996 0.9997 0.42 0.002 1 0.16 0.38 6 769, 16.08 Effluent 150.14 0.99996 0.9989 0.385 0.001 0.958 0.12 0.40 6b 769, -3.43 Effluent 150.14 0.99996 0.9994 0.35 0.001 0.959 0.12 0.39 6c 769,-18.4 Effluent 150.14 0.99996 0.9965 0.26 0.013 0.939 0.106 0.39 7 742, 73.15 Effluent 150.14 0.99996 0.9983 0.425 0.002 0.862 0.13 0.40 Note: All mass balances adjusted for accuracy 67 3.5.2.3.2 Effect of temperature Figures 3.21, 3.22 and 3.23 show the change in temperatures with residence time for all the experimental runs. It can be observed that steady state conditions were achieved during the experiments that were run at the same temperatures, but with different oxidant excess. Conditions very close to isothermal were achieved throughout almost all the 120 meters of reactor, from RL-2 to RL-17B. 900 850 800 , 750 2> 700 g_ 650 E CD H 600 550 500 450 Temperature profiles for 2,4 DNP-based runs 1 to 2c PH2 out PHI in , * / RL2 RL6 RL10 A l l f e e d t e m p e r a t u r e s 3 3 0 K RL 17B ^ R H X in - X - Run 1, 813 K, 74.73% 0 2 Run 2, 813 K, 22 .44% 0 2 - O - Run 2b, 813 K, 0.36% 0 2 -\7- Run 2c , 813 K, -28.93% 0 2 10 15 20 25 30 Residence Time [sec] RHX out (effluent) 35 40 Figure 3.22 2,4 DNP and ammonia experiments. Temperature profiles runs l-2c 68 850 800 750 Temperature profiles for 2,4 D N P - b a s e d runs 3 to 4b 700 c o CD k CJ Q. m 600 550 h 500 450 ^ ^ ^ J ^ f e - ^ 4 - B jfy ^ RL6 1^1 RL2 R L 1 7 B RL10 ^ RHX in PH2 out PHI in .„ All feed temperatures 337 K -T3 - Run 3, 791 K, 73.27% 0 2 I - Run 4, 791 K, 21.05% 0 2 -4fr • Run 4b, 791 K, -1.9% 0 2 R H X o u t ( e f f l u e n t ) 10 15 20 25 30 Res idence Time [sec] 35 40 45 Figure 3.23 2,4 DNP and ammonia, temperature profiles runs 3-4b Temperature profiles for 2,4 D N P - b a s e d runs 5 to 7 800 750 i 700 c n CD 650 600 550 V-500 450 . PH2out . ^ . - ^ - * - - & v * L 1 7 B RL2 RL10 o , R H X . n PHI i n ' ' . . ^ v \ \ v \ \ C- \ \ v . x \ * V \ ' / i' i '/ /;, V \ \ - //, Y\ * /'/ >'/ i','^^k\\ feed temperatures 330 K - A - Run 5, 769 K, 78.62% 0 2 <] Run 6,769 K, 16.08% 0 2 --[>- Run 6b, 769 K, -3.43% 0 2 i i - Run 6c, 769 K, -18.4% 0 2 Run 7, 742 K, 73.15% 0 2 « A \ R H X o u t ( e f f l u e n t ) 10 15 20 25 30 35 Res idence T ime [sec] 40 45 50 Figure 3.24 2,4 DNP and ammonia. Temperature profiles runs 5-7 69 Runs 1, 3, 5 and 7 represent experiments with high excess oxygen (approximately the same, between 73 and 78%) carried out at different temperatures (from 813 K to 742 K). The data in Table 3.11 show that the conversion of 2,4 DNP was not affected by lowering the temperature, always staying maximum. TOC conversions decreased slightly at the lower temperatures (769 K and 742 K), but always remained higher than 99%. This suggested that TOC destruction at temperatures lower than 742 K would have started to decrease. The ammonia destruction was always poor, but decreased slightly (within the error margins) at lower temperatures. The same was observed by Killilea et al.29, who obtained very poor conversions using oxygen as the oxidizing agent, even at temperatures above 823 K. No CO was observed in any of these runs and the C 0 2 yield slightly decreased at 742 K. N 2 0 yields tended to increase for lower temperatures, which was consistent with the findings of previous 28 29 31 researchers. ' ' Runs 2, 4 and 6 were carried out at moderate oxygen excess (16 to 22%) and followed the same trend as the runs with high oxygen excess. No NO or N0 2 were observed in the gaseous effluent in any of the cases. This agreed with the results obtained in the experiments mentioned in section 3.2.2.1.1 at UBC . Runs 2b and 6b corresponded to two different operation temperatures (813 K and 769 K respectively) at oxygen flows around the stoichiometric point. Similarly to the runs previously mentioned, 2,4 DNP destructions were maximum, and TOC conversion slightly decreased from 813 to 769 K. Ammonia conversions remained approximately constant (35 to 37%), but was lower than those of the previous runs. N 2 0 production increased at 769 K, and the C 0 2 slightly decreased. No CO was detected at these conditions. The influence of temperature at sub-stoichiometric levels was also investigated in runs 2c, 4b and 6c. Runs 2c and 6C were carried out at very sub-stoichiometric levels and 4b 70 slightly below the stoichiometric point. Even though 2,4 DNP was fully destroyed, TOC conversions decreased with decreasing the temperatures, but were always higher than 99%. N2O production increased, and small amounts of CO were observed in the effluent gas from run 2c. In this run phenol was detected as part of the aqueous effluent stream. In general, temperatures did not have a strong effect in the effluent concentrations of nitrates or nitrites. 3.5.2.3.3 Effect of residence time Figures 3.21 to 3.23, introduced in the previous section, (similar to the trends from Figures 3.8 and 3.9) show that the residence times for higher temperature runs were lower. Higher residence times were observed in sections of the system that were operated at lower temperatures, such as the preheaters and the regenerative heat exchanger. The influence of residence time in the destruction of this waste was studied at different temperatures in runs in which intermediate samples were taken (1, 3, 5). Figures 3.24 to 3.29 present plots of change in the conversions and yields, and of the formation of intermediates with residence time for runs 1,3, and 5. In general, 2,4 DNP was completely destroyed early in the process (before the first sampling port in the reactor (RL-2)), while the highest TOC conversions were achieved by the end of the reactor. The organic intermediates detected were picric acid, 2-nitrophenol and 4-nitrophenol. Picric acid was found in runs 3 and 5, which were carried out at 791 and 769 K respectively, but it was not found in run 1, which was conducted at 813 K. Interestingly, runs 3 and 5 showed that 2-nitrophenol disappeared, but reappeared in small amounts, to be finally destroyed. Yet, more experiments and a detailed study of the intermediates would be 71 needed in order to reach conclusions on the sequence of formation and disappearance of these species. Ammonium carbamate (NH2COO) and urea ((NH2)2CO) are some of the compounds that could have been formed during the oxidation process. However, no chemical analyses were performed in order to detect them. Phenol was not found as an intermediate at any stages, although it was part of the effluent stream of a very sub-stoichiometric run (run 2c, at -28.93% below the stoichiometric amount of oxygen). This was different from what has been observed by Martino and Savage'36'37 for the case of mono-nitrophenol oxidation in SCWO, where phenol was an important aqueous-phase product. For the SCWO of m- and p- nitrophenols, Martino and Savage36' 3 7 observed two major parallel primary paths: one leading to phenol and the other one to ring-opening products and ultimately to CO and CO2. In these experiments, it was observed that the decomposition of 2,4 DNP led to the formation of 2 - and 4- nitrophenols, but the pathway leading to phenol formation was not observed, except in the case of run 2c, at 813 K and very sub-stoichiometric oxygen flows. There exists the possibility, however, that phenol had been a very reactive intermediate and that it was completely destroyed between sampling ports. In general, the intermediate products measured from the destruction of 2,4 DNP were 2-nitrophenol, 4-nitrophenol and picric acid. In all cases, these intermediates were completely destroyed. Ammonia conversions were higher while there were large amounts of TOC in the system. The reduction in the TOC/NH3 with the destruction of the organics clearly affected the ammonia destruction. Probably some carbonic inorganic salts were formed, which remained stable at the conditions explored. It could also be possible that large amounts of CO had been competing with the ammonia for the oxygen. 72 0.8 •4 TOC _ • 2,4 DNP AS NH3 • N 2 0 yield C 0 2 yield • Nitrogen yield c o CD > c o O 0.4 0.2 2,4 D N P and Ammonia. Convers ions and yields. Run 1 o*— $ - * - - - i t 10 15 20 25 30 Res idence Time [sec] 35 _ _ J 40 Figure 3.25 2,4 DNP and ammonia. Conversions and yields for Runl (813 K, 74.7% 0 2 excess) 2,4 D N P and ammonia. Intermediates formation Run 1 10 3> 10 o CD 1 0 ' c CD o c o O io' O) o 10 10 a X X ft 6 v> ' l ^ I o 10 15 ' 2 0 " 25 30 Res idence Time [sec] O 2,4 DNP • TOC X NH3 Jfc 2-nitrophenol O 4-nitrophenol V Nitrates A Nitrites Q 35 Figure 3.26 2,4 DNP and ammonia. Intermediates, TOC and ammonia destruction, Run 1 73 •4 TOC - m 2,4 DNP m NH3 • N 2 0 yield A C 0 2 yield • Nitrogen yield 2 ' 4 D N P and Ammonia . Convers ion and yields. Run 3 r*- - r» -- I 15 20 25 30 R e s i d e n c e Time [sec] 35 40 Figure 3.27 2,4 DNP and ammonia. Conversions and yields for Run 3 (791 K, 73.3% 0 2 excess) 10 o i 10 c o | 102 c o o o O 1 0 ' O) o 10 10 2,4 D N P and ammonia . Intermediates formation Run 3 7M^t 10 15 20 25 30 Res idence Time [sec] o 2,4 DNP • TOC X NH3 > Picr ic acid * 2-nitrophenol 0 4-nitrophenol v Nitrates A Nitrites •---a 35 40 45 Figure 3.28 2,4 DNP and ammonia. Intermediates, TOC and ammonia destruction, Run 3 74 0.8 c o <D > C o O 0.4 0.2 4 TOC - • 2,4 DNP • NH3 • N 2 0 yield C 0 2 yield • Nitrogen yield 2 > 4 D N P and Ammonia . Convers ion and yie lds. Run 5 ''A- ' 1 10 15 20 25 30 Res idence Time [sec] 35 . - -5 40 Figure 3.29 2,4 DNP and ammonia. Conversions and yields for Run 5 (769 K, 78.6% 0 2 excess) 10 i* 2,4 D N P and ammonia . Intermediates formation Run 5 20 " 25 30 Res idence Time (sec) o 2,4 DNP • T O C X NH3 > Picr ic acid * 2-nitrophenol o 4-nitrophenol V Nitrates A Nitrites 35 40 45 Figure 3.30 2,4 DNP and ammonia. Intermediates, TOC and ammonia destruction, Run 5 75 3.5.2.3.4 Effect of oxidant excess The effect of changing the oxygen excess was explored at 813 K (runs 1, 2, 2b, and 2c), 791 K (runs 3, 4, 4b) and 769 K (runs 5, 6, 6b, 6c) and is shown in Figures 3.30 to 3.32 Generally the excess of oxygen did not have an effect on TOC and 2,4 DNP destruction, except when below stoichiometric, where TOC conversions and CO2 yields decreased. Higher oxygen excesses yielded better ammonia conversions, although destruction efficiencies never exceeded 50%, which suggested that indiscriminately increasing the oxygen excess would not be a suitable way to improve ammonia destruction. This agrees with Dell'Orco et al. 2 7, who found that in oxygen deficient environments, nitrates and nitrites were converted to ammonia by reaction with organic carbon. Nitrate concentrations in the aqueous effluent were always below 0.6 mg/L, but they were found to decrease with lowering the oxygen excess. Nitrites were most of the time below the detection limits (0.1 mg/L). In all cases, bicarbonate production increased with lower oxygen excess, whereas the N2O yields tended to slightly decrease for lower oxygen excesses. For example, from runs 1 to 2c, with the same reactor's temperatures but different oxygen excess, bicarbonate increased from 3480 mg/L in run 1 (74.73 % excess 0 2) to 5940 mg/L in run 2c (-28.93 % excess O2) (See Appendix H) Traces of CO in the gas and of phenol in the aqueous stream were only obtained at a very sub-stoichiometric oxygen level, for run 2c (-28.93 % below the stoichiometric point). 76 10 o CD O c o o O) O CT) O 2,4 D N P and ammonia exper iments. Effect of oxygen excess at 813 K g CO c o O CT) O 10 X NH3 X T O C N 2 0 yield nitrates [mg/L] nitrites [mg/L] C O yield (0 tor runs 1, 2, 2b) 74.73 + 2 1 - 2 -9.5 (RUN 1) ( R U N 2) 22.4+/-1.62 0.36+/-1.57 -28.93 76 oxygen excess [%] < R U N 2 b» < R U N 2c> Figure 3.31 2,4 DNP and ammonia. Effect of oxygen excess at 813 K 2,4 D N P and ammonia exper iments. Effect of oxygen excess at 791 K 10 g 2 CD o c o o O) o CD . CT) O g ' c o CD > c o o CT) o • X N H 3 X T O C • N 2 0 yield • Nitrates [mg/L] • nitrites [mg/L 10 73.27 + 1 4 (RUN 3) " 8 ' 5 3 oxygen excess [%] 21.05 (RUN 4) -1.9 +/-1.57 (RUN 4b) Figure 3.32 2,4 DNP and ammonia. Effect of oxygen excess at 791 K 77 2,4 D N P and ammonia exper iments. Effect of oxygen excess at 769 K 10 o cu CJ c o CJ cn o cn o ~£ o 'cn o 10 X NH3 X T O C N 2 0 yield nitrates [mg/L] nitrites [mg/L] C O yield (0 for runs 6, 6, 6b) 78.62 +29-6 -8.9 (RUN 5) (RUN 6) 16.08 3.43+'-1-57 -18.4 +/-1.64 . . . , +/-1.59 (RUN 6b) (RUN 6c) oxygen excess [%] Figure 3.33 2,4 DNP and ammonia. Effect of oxygen excess at 769 K 3.6 Conclusions The conclusions will be divided in two sections, corresponding to each group of tests: 1. Phenol • High concentrations of phenol were successfully destroyed at 25 MPa, 666 -778 K and oxygen excesses from 0 to 39%. TOC and phenol DREs were in the range of 0.75 to 0.9977 and 0.95 to 0.9998 respectively • As a general trend, higher DREs were obtained at higher temperatures, although not in all cases. More experiments would be needed in order to clarify this point. • Moderate - but higher than stoichiometric- excess oxygen was needed in order to achieve high phenol and TOC conversions (e.g. between 10 and 39 %). • The feed concentration did not have much effect in the phenol DREs. However, TOC conversions tended to be lower for lower feed concentrations. 78 Reaction kinetics taken from the literature were used to predict phenol decompositions. The best were observed with the rate laws proposed by Krajnc and Levee, Gopalan and Savage, and Koo et al. Wastes with 2.4 D N P a. 2,4 DNP, ammonium sulphate and ammonia The waste containing 2,4 DNP, ammonia and ammonium sulphate was highly corrosive to the system. High concentrations of 2,4 DNP were fully destroyed and TOC DREs were of 99.92%. Due to the unclosed nitrogen balance, no conclusions on the destruction of ammonia could be made. b. 2,4 DNP and ammonia High concentrations of 2,4DNP were fully destroyed, with TOC DREs of 0.9898 to 0.9998. Ammonia conversions, in contrast, were very poor, from 0.37 to 0.5. Maximum DREs of 2,4 DNP were obtained at temperatures as low as 742 K, with TOC conversions of 0.9983. NH3 conversions decreased slightly at the lower temperatures. Even at sub stoichiometric oxygen flows, 2,4 DNP destruction was 99.996 %. Ammonia conversions were only slightly increased with oxygen concentration. 2- and 4-nitrophenol, and in some cases picric acid, were the intermediates detected. Analysis of intermediate samples lead to the belief that the destruction of 2,4 DNP followed a primary path to mononitrophenols. Destruction of 2- and 4-nitrophenol, apparently, didn't follow a path to CO2 through phenol. 79 Chapter 4 Corrosion observed in the UBC-Noram SCWO facility 4.1 Previous experience As noted in chapter 2, corrosion is one of the main challenges in SCWO systems and as such, has been given a lot attention. It has been found that the corrosion in SCWO of many materials depends on the physical properties of water.45 As pointed out in section 2.1, at constant pressure, the density, dielectric constant and the ion product decrease drastically after the critical point. These properties affect the dissociation of the aggressive, corrosive species and the stability of the protective oxide layers in a way that makes corrosion most severe at high temperatures where the water density remains high.4 4 5 In general, corrosion rates tend to increase with temperature, reach a maximum, and decrease with further increase in temperature.4 However, the generalization that supercritical water is less corrosive is only valid for water at low density.45 Increasing the pressure at supercritical temperatures, for example, will increase the density, the dielectric constant and the ionic product, subsequently favouring corrosion. The initial increase of corrosion with temperature has been justified by the effect of temperature on the rate constant of the reactions responsible for corrosion.4 Figure 4.1 sketches the rate of corrosion at 25 MPa found by Mitton et al. 4 6 in different portions of their tubular system, which was comprised of a preheater, a reactor and a cool-down heat exchanger. In the preheater, corrosion increased in the region from high subcritical to critical temperatures. Low corrosion was observed in the outlet of the preheater or inlet of the cool-down heat exchanger, portions of the system that operated at supercritical conditions. A peak in corrosion was again observed in the cool-down heat exchanger, at high subcritical temperatures. Even though corrosion in the reactor was not explored, degradation was suspected to be insignificant compared to that of the preheater and cool-down heat 80 exchanger, which failed several times in a period of time, while the reactor continued to work without apparent problems. Preheater Rsacaor Cool-Down Heat Exchanger Figure 4.1 Corrosion as a function of temperature in preheater and heat exchanger. Kritzer and Dinjus 4 7 studied the corrosion of alloy 625 in high-temperature, high-pressure sulphate solutions. They found no corrosion in solutions containing H2SO4 and O2 at low temperatures (between 150 and 200 °C), but observed that at higher temperatures, high densities favoured corrosion. In contrast, corrosion decreased considerably in low-density regions. In the corroded sections, solid, black products were found, mainly consisting of chromium, molybdenum and niobium, and smaller amounts of nickel. Solutions of NaHSCU and 0 2 h a d been observed to display similar trends. No corrosion was detected in oxygenated Na2SC>4 solutions up to 350 °C, while deoxygenated H2SO4 caused severe corrosion at low temperatures (200 °C). However, these rates became lower at higher temperatures. Facing the problem of materials degradation in SCWO, a number of methods for reducing corrosion damages have been proposed, commonly addressing 3 different areas:4 8'4 81 • Corrosion resistant liners and coatings • Feed modification • Reactor design Titanium and platinum have been suggested because of their good corrosion resistance. However, they are expensive. Elements in the feed that cause aggressive corrosion can also be diluted and/or somehow extracted from the waste prior treatment by SCWO. Another way to handle corrosion has been the development of novel reactors. The most common designs are the transpiring wall reactor49 and down-flow vertical vessels.48 On the basis of Figure 4.1, for example, two approaches could be used to manage corrosion in a system like this: a) incorporate easily replaceable, inexpensive sections at the two locations most prone to corrosion46, or b) use more expensive, corrosion resistant materials in these sections. 4.2 Corrosion in the UBC-Noram pilot plant As noted in section 3.4.2.1, the 2,4 DNP and ammonium sulphate solution treated in our SCWO pilot plant was highly corrosive to the system. During the experiment, no failures occurred. However, during the start-up of the next tests with water, the first preheater failed, when temperatures reached only 300 °C. The failure occurred at 1.72 m from its inlet. On a later cold static pressure test at 517 bars, the inner tube from the regenerative heat exchanger (RHX) also burst. The RHX failed where the hot stream coming from the reactor (outer tube) impinged on it. Figure 4.2 shows the burst tube from the preheater 1. 82 Figure 4.2 Tube failure due to corrosion in the first preheater (PH 1) Only 58 litres of 2,4 DNP and ammonium sulphate solution were treated, under the conditions described in section 3.5.2.1. The metals analyses, for which results can be seen in Appendix G, yielded high concentrations of molybdenum, nickel, chromium and sulphur in the effluent, the latter most probably caused by sulphur salts deposited in the system. The metals analyses from the separate sampling ports showed that practically all of the molybdenum, nickel and chromium released from the system came from the port located in the inlet of the preheater 2 (PH 2 in). At the time the experiments were run, this port was the closest to the first preheater. Lower amounts of metals were detected in the samples from the other ports, but it was suspected that they had been carried by the flow to other points of the system and had remained there. Samples from the previous tests with phenol were analyzed looking for traces of metals, in order to clarify whether the corrosion had been gradual, or if it had occurred only during the 2,4 DNP and ammonium sulphate test. These analyses showed that no metal had been lost during the phenol experiments. However, corrosion from previous tests could not be ruled out. The total amount of metals lost in the system was calculated based on the analyses of the effluent stream, the composition of alloy 625 under normal (no corrosion) conditions, and the 83 fact that only 58 litres of solution had been treated (See Appendix I). The calculations indicate that a total of approximately 18 g of metals (Ni, Cr, and Mo) were lost during the test, enough to weaken the tubes and to cause them to fail. The analysis of the corroded tube is summarized below. Wall thickness measurements The thickness of the preheater 1 and regenerative heat exchanger's tube walls were measured with a thickness probe at locations where no corrosion was observed as well as in the corroded areas. Measurements were made every one inch at four different points of the tube's cross sectional area, separated by 90°. Figures 4.3 and 4.4 show the thickness and bulk temperature profiles in the corroded sections of PHI and RHX respectively. As pointed out in section 3.4.2, temperature profiles were calculated using only water properties. Since these experiments also contained high excess oxygen (198%), real bulk temperatures would be expected to be few degrees lower than those presented in these figures. The results in Figures 4.3 and 4.4 show a considerable decrease in the thickness in both the preheater 1 and the regenerative heat exchanger. Note that the areas most affected by corrosion were in the vicinity of the critical point for the experiment's pressure (24.9 MPa). Most of the metallic losses in the inner tube of the RHX came from its top, internal surface, on the impinging point of the hot fluid coming from the reactor. Thickness measurements were also taken in the test section to look for signs of corrosion. However, these tubes were found to be in good condition. 84 740 2.4DNP, ammonium sulphate and ammonia Temperature and thickness profile in PH1 Temperature Thickness (+ 90) Thickness (top) 1.8 2 2.2 Axial Position, PH 1 [m] 2.4 2.6 2.8 70 65 H60 55 50 o CD 45 » o 40 O Figure 4.3 Temperature and thickness profiles, P H 1. 900 850 800 O 750 re CD 700 E £ 5 650 CO 600 550 500 2,4 DNP, ammonium sulphate and ammonia experiments Temperature and thickness profile in RHX, inner tube 0.8 1 Axial Position [m] Figure 4.4 Temperature and thickness profiles, RHX 85 The next three tests have not yielded any definite conclusions yet, leaving some work to be done. Optical Microscope An optical microscope was used to visualize the main changes on the exposed surface of the samples of corroded and non-corroded sections of the tubes. The samples were chemically prepared (etched) by the Pulp and Paper Research Institute of Canada (PAPRICAN) and analyzed under an optical microscope, with resolution of up to 400X. The graphic images (see Appendix I for graphic results) showed major irregularities in the shape of the surfaces of the corroded sections. Scanning Electron Microscopy/ Energy Dispersive Spectroscopy (SEM/EDS) S E M and EDS were used to examine the cross section of the tubes, determine the features of the corroded surface, and obtain an elemental analysis of any adherent deposits. The S E M is one of the major tools in the failure analysis process. After initial visual examination of the specimen, the sequence of procedures for a S E M examination in a typical project might go as follows 5 0: • Failure area viewed at low magnification -secondary electrons show an overall picture of the area. • Magnification increased to about 300X- secondary electron view highlights details with excellent depth of field. • Magnification increased to 3000X- backscatter electrons used to examine grain structure. 86 • EDS system identifies the elements present and their percentages in the materials examined. The tests were conducted in the Metals and Materials Department at UBC. Their analysis is still in progress. Auger electron spectroscopy/ X-ray photoelectron spectroscopy (AES/XPS) AES/XPS were used to examine the longitudinal section of the tubes. Both techniques provide quantitative analysis of elements. XPS can also identify the chemical state of an element. For example, a metal can be differentiated from its oxide or carbide. AES, which uses an electron beam for excitation, can be used to produce an elemental map of the surface and analyze small features such as particles and corrosion pits. Both techniques can produce a depth profile that gives the distribution of elements in the surface layers. In this case, only one longitudinal sample from the failed part of the preheater 1 (PHI) was analyzed, looking for any enrichment or depletion in the alloy elements at the corroded surface and the chemical composition of any adherent deposit or corrosion products in the surface of the tube. Their analysis is still in progress. 8 7 4.3 Conclusions Even though this corrosion study is ongoing and no definite conclusions have been reached regarding the causes of such severe degradation in the system, some preliminary conclusions can be drawn: • The 2.4% by wt. 2,4 D N P waste containing 2.1% by wt. of ammonium sulphate and 6.67% by wt. of ammonia was clearly corrosive to the system. While the possibility of some prior corrosion should not be completely rejected, this solution obviously caused enough damage to provoke the failure of P H 1 and R H X . • The corrosion profiles in the system agree with the observations made by Kritzer and Dinjus4 5 and Mitton et a l . 4 6 that highest corrosion rates are observed at high temperature and high density points, that is in the high temperature subcritical area when operating the SCWO system at 25 MPa. • More research needs to be done with the 2,4 DNP-ammonium sulphate-ammonia waste, but this first experimental trial suggested that sulphates elimination/reduction would be needed in order to treat the waste by SCWO. Chapter 5 Conclusions and Recommendations 5.1 Conclusions Phenol experiments • High concentrations of phenol were successfully destroyed at 25 MPa, 666 -778 K and oxygen excesses from 0 to 39%. TOC and phenol DREs were in the range of 0.75 to 0.9977 and 0.95 to 0.9998 respectively • As a general trend, higher DREs were obtained at higher temperatures, although not in all cases. More experiments would be needed in order to clarify this point. • Moderate - but higher than stoichiometric- excess oxygen was needed in order to achieve high phenol and TOC conversions • The feed concentration did not have much effect in the phenol DREs. However, TOC conversions tended to be lower for lower feed concentrations. • Reaction kinetics taken from the literature was used to predict phenol decompositions. The best agreements were observed with the rate laws proposed by Krajnc and Levee, Gopalan and Savage, and Koo et al. Wastes with 2.4 DNP a. 2,4 DNP, ammonium sulphate and ammonia • The 2.4% by wt. 2,4 DNP waste containing 2.1% by wt. of ammonium sulphate and 6.67% by wt. of ammonia was clearly corrosive to the system. While the possibility of some prior corrosion should not be completely rejected, this solution obviously caused enough damage to provoke the failure of PH 1 and R H X . 89 The corrosion profiles in the system agree with the observations made by Kritzer and Dinjus 4 5 and Mitton et a l . 4 6 that highest corrosion rates are observed at high temperature and high density points, that is in the high temperature subcritical area when operating the SCWO system at 25 MPa. More research needs to be done with the 2,4 DNP-ammonium sulphate-ammonia waste, but this first experimental trial suggested that sulphates elimination/reduction would be needed in order to treat the waste by SCWO. High concentrations of 2,4 DNP were fully destroyed and TOC DREs were of 99.92%. Due to the unclosed nitrogen balance, no conclusions on the destruction of ammonia could be made at this point. b. 2,4 DNP and ammonia High concentrations of 2,4DNP were fully destroyed, with TOC DREs of 0.9898 to 0.9998. Ammonia conversions, in contrast, were very poor, from 0.37 to 0.5. Maximum DREs of 2,4 DNP were obtained at temperatures as low as 742 K , with TOC conversions of 0.9983. NH3 conversions decreased slightly at the lower temperatures. Even at sub stoichiometric oxygen flows, 2,4 DNP destruction was 99.996 %. Ammonia conversions were only slightly increased with oxygen concentration. 2- and 4-nitrophenol, and in some cases picric acid, were the intermediates detected. Analysis of intermediate samples lead to believe that the destruction of 2,4 DNP followed a primary path to mononitrophenols. Destruction of 2- and 4-nitrophenol, apparently, didn't follow a path to CO2 through phenol. 90 5.2 Recommendations Even though high concentrations of 2,4 DNP wastes can be fully destroyed by SCWO, using low oxygen excess and moderate temperatures, ammonia conversion during these experiments was very poor. According to other researchers28'31'33'34, using nitrates as co-oxidant agents can solve this problem. Another possibility is to treat feed streams with higher TOC concentration. The possibility of treating even higher feed concentrations of 2,4 DNP calls for a better way of keeping the feed in solution. This could be solved by containing the aqueous 2,4 DNP solution in a slightly pressurized container at a temperature below the saturation point, but high enough to keep the nitrophenols into solution. It is important that the gas samples are not contaminated with atmospheric air. In the future, gas samples from the effluent could be taken from the outlet of the effluent tank's gas-liquid separator. This would not require major changes to the system. For the case of the intermediate sampling ports, it would be necessary to make sure that all the air is evacuated from the vial before collecting the gaseous sample. Bench top experiments should be carried out to shed more light on the corrosion caused by the sulphate containing 2,4 DNP waste. This would lead to conclusions on the feasibility of treating nitration wastewaters with sulphates. The use of liners or corrosion-resistant materials in the parts of the reactor that are more prone to corrosion could be considered. 91 References http ://ci sat .isci ii .es/bt/atsdr/ profi 1 es/Nitroben.pdf Boyd, D. A, Gairns, S. A., Guenkel, A. A., US Patent 6288289, 2001, "Integrated Effluent Treatment for Nitroaromatic Manufacture". Freeman, H. M., 1989, Standard Handbook of Hazardous Waste Treatment and Disposal, US Environmental Protection Agency, McGraw Hill, New York, Chap. 9. Chang, H. O., 2001, Hazardous and Radioactive Waste Treatment Technologies Handbook, Idaho National Engineering and Environmental Lab, Idaho, USA, Chap. 5. 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Staszak, C.N., Malinowski, K.C., and Killilea, W. R., 1987, "The Pilot-Scale Demonstration of the Modar Oxidation Process for the Destruction of Hazardous Organic Waste Materials", Environ. Progress, 6, pp. 39-43. McBrayer, R.N., and Griffith, J.W., 1996, "Turn Off the Heat", Industrial Wastewater, July/August pp. 43-48. Matsumura, Y., Nunuora, T., Urase, T., and Yamamoto, K., 2000, " Supercritical Water Oxidation of High Concentrations of Phenol", J. Haz. Materials, 73(3), pp. 245-254. 92 Li, L., Chen, P., and Gloyna, E.F., 1994. , "Chemical Oxidation: Technology for the Nineties", Proceedings of the Third International Symposium, Chemical Oxidation: Technology for the Nineties, Eckenfelder, W, Bowers, A., and. Roth, J., Eds, Vanderbilt University, Nashville, TN. 1 6 Thornton, T.D., and Savage, P. E., 1992, "Kinetics of Phenol Oxidation in Supercritical Water", AIChE J.,38 pp. 321-327. 1 7 Gopalan, S., and Savage, P. E., 1995, "A Reaction Network Model for Phenol Oxidation in Supercritical Water", AIChE. J., 41, pp. 1864- 1873. 1 8 Krajnc, M., and Levee, J., 1996, "On the Kinetics of Phenol Oxidation in Supercritical Water", AIChE J., 42, pp. 1977-1984. 1 9 Eckert, C. A., Leman, G. M., and Yang, H. H., 1990, "Homogeneous Catalysis for Wet Oxidation: Design and Economic Feasibility of a Mobile Detoxification Unit", Haz. Mat. Control, 3(20). 2 0 Rogak, S. N., Khan, M. S., and Vera Perez, I., 2002, "Thermal Design of Supercritical Water Oxidation Reactors", Proceedings of IMECE2002 ASME International Mechanical Engineering Congress & Exposition, IMECE 2002-33853, New Orleans, USA. 2 1 Koo, M., Lee, W.K., and Lee, C.H., 1997, "New Reactor System for SCWO and its Application on Phenol Destruction", Chem. Eng. Sci. 52, pp. 1201-1214. 2 2 Oshima, Y., Hori, K , Toda, M., Chommanad, T., and Koda, S., 1998, "Phenol Oxidation Kinetics in Supercritical Water", J. Supercrit. Fluids, 13, pp. 241-246. 2 3 Portela J.R., Nebot E., and de la Ossa E.M., 2001, "Kinetic Comparison Between Subcritical and Supercritical Water Oxidation of Phenol", Chem. Eng. J, 81 (1-3) pp. 287-299. 2 4 Kolaczkowski, ST., Beltran, F.J., McLurgh, D.B, and Rivas, F.J., 1997, "Wet Air Oxidation of Phenol: Factors that may Influence Global Kinetics", Trans. IchemE, 75 (B) pp. 257-265. 2 5 Harradine, D. M., Buelow, S. I., DelU'Orco, R. B., Foy, B. R., and Robinson, J. M., 1993, "Oxidation Chemistry of Energetic Materials in Supercritical Water", Hazardous Waste and Hazardous Materials, 10(2), pp. 233-245. 2 6 Li, L., Gloyna, E.F., and Sawicki, I.E., 1993, "Treatability of DNT Process Wastewater by Supercritical Water Oxidation", Water Environment Research, 53(3), pp250-257. 2 7 Dell'Orco, P., Luan, L., Proesmans, P., and Wilmanns, E, 1995, "Reaction Chemistry of Nitrogen Species in Hydrothermal Systems: simple Reactions, Waste Simulants, and Actual Wastes", First International Workshop on Supercritical Water Oxidation, Florida, USA. 2 8 Proesmans, P.I., Luan, L., and Buelow, S., 1997, "Hydrothermal Oxidation of Organic Wastes Using Ammonium Nitrate", Ind. Eng, Chem. Res. 36 (5), pp. 1559-1566. 93 Cocero, M. J., Alonso, E., Torio, R., Vallelado, D. and Fdez-Polanco, F., 2000, "Supercritical Water Oxidation in a Pilot Plant of Nitrogenous Compounds: 2-propanol Mixtures in the Temperature Range 500-700 °C", Ind. Eng. Chem. 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H., 1997, "Hydrothermal Decomposition and Oxidation of p-Nitroaniline in Supercritical Water", Journal of Hazardous Materials, 56(3), pp. 247-256. 3 5 Ding, Z., Y., Li, L., Wade, D., and Gloyna, E.F., 1998, "Supercritical Water Oxidation of NH 3 Over a Mn0 2/Ce0 2 Catalyst", Ind. Eng. Chem. Res., 37(5), pp. 1707-1716. 3 6 Martino, C J , and Savage, P.E., 1997, "Thermal Decomposition of Substituted Phenols in Supercritical Water", Ind. Eng. Chem. Res., 36 (5), pp.1385-1390. 3 7 Martino, C J , and Savage, P.E., 1999, "Oxidation and Thermolysis of Methoxy-, Nitro-, and Hydroxy-Substituted Phenols in Supercritical Water", Ind. Eng. Chem. Res., 38 (5), pp. 1784-1791. 3 8 Boyd, D. A., Gairns, S. A., and Guenkel, A.A., U.S. Patent # 6,288,289,2001, "Integrated Effluent Treatment Process for Nitroaromatic manufacture". 3 9 Wagner, W. and Prufl, A. , 2002,"The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use", J . Phys. Chem. Ref. Data, 31(2), pp. 387-535. 4 0 Martino, C.J, and Savage, P.E., 1999, "Total Organic Carbon Disappearance Kinetics for the Supercritical Water Oxidation of Monosubstituted Phenols", Environ. Sci. Technol, 33(11), pp. 1911-1915. 4 1 Holman, J. P., 2001, Experimental Methods for Engineers, McGraw Hill, Boston, Chap. 3. 4 2 Rice, S. F., and Steeper, R. R., 1998, "Oxidation Rates of Common Organic Compounds in Supercritical Water", Journal of Hazardous Materials, 59(2-3), pp. 261-278. 94 Li , R., Thornton, T. D., and Savage, P. E., 1992, "Kinetics of C 0 2 Formation from the Oxidation of Phenols in Supercritical Water", Environ. Sci. Technol., 26(12), pp. 2388-2395. 4 4 Martino, C.J, and Savage, P.E., 1999, "Supercritical Water Oxidation Kinetics and Pathways for Ethylphenols, Hydroxyacetophenones, and Other Monosubstituted Phenols", Ind. Eng. Chem. Res., 38(5), pp. 1775-1783. 4 5 Kritzer, P., Boukis, N., and Dinjus, E., 1999, "Factors Controlling Corrosion in High-Temperature Aqueous Solutions: A Contribution of the Dissociation and Solubility Data influencing Corrosion Processes", The Journal of Supercritical Fluids, 15(3), pp. 205-227. 4 6 Mitton, D.B, Han, E. - H , Zhang, S. - H , Hautanen, K. E., and Latanision, R. M., 1997, "Degradation of Supercritical Water Oxidation Systems", ACS Symposium series 670. Supercritical Fluids Extraction and-Pollution Prevention, Amer. Chem. Soc, USA, Chap. 17, pp. 243-253. 4 7 Kritzer, P., Boukis, N., and Dinjus, E, 1998, "Corrosion of Alloy 625 in High-temperature, High-Pressure Sulphate Solutions", Corrosion, 54(9), pp. 689-698. 4 8 Mitton, D. B., Eliaz, N. , Cline, J. A., and Latanision, R. M., 2001, "An Overview of the Current Understanding of Corrosion in SCWO Systems for the Destruction of Hazardous Waste Products", Materials Technology, 16(1), pp. 44-53. 4 9 Mueggenburg, H. H , Rousar, D. C, and Young, M. F., US Patent 5,387,398, 1995, "Supercritical Water Oxidation Reactor with Wall Conduits for Boundary Flow Control". 5 0 www.engelmet.com , Engel Metallurgical Ltd., Minnesota, USA. 5 1 Younlove, B., 1982, Journal of Physical and Chemical Reference Data, Amer. Chem. Soc; New York, Vol. 11 (Supplement no.l). 5 2 Gibson, N., BCRI, personal communication. 95 Appendix A Oxygen flow meter calibration 1. Objectives: To calibrate the oxygen flow measurements with the new pressure transmitter (Foxboro IDP10) and an orifice meter 1.14 mm in diameter. This pressure transmitter was installed in order to improve the system's flow control. The previous one was used during the first experiments with phenol detailed in Chapter 3 of this work, and its calibration relation was the following: m = 4 . 1 6 * ( V - V 0 ) 1 / 2 [A.l] Where m was the oxygen mass flow in kg/h, V the voltage reading from the data acquisition system, and Vo the zero offset of the transmitter. 2. Experimental set up and test description The Foxboro transmitter and the orifice were used to measure the oxygen flow coming from the O2 booster and the differential pressure across the orifice. The output from the transmitter, which is read by the data acquisition system (channel 24), was 2 to 10 V , depending on the oxygen flow. A 24-volt power supply was used to feed the transmitter. The calibration of the pressure transmitter was performed on two occasions; on the first one it was observed that the temperatures on the high-pressure side of the system were not constant and that they tended to be higher after the booster became warmer from operating. Changes in the system were made for the second set of calibrations, and the previous pulsation damper was used as a container to absorb both pressure and temperature pulsations (please refer to Figures A . l and A.2 for the first and second system's layouts). The second 96 calibration was used for interpretation of all experiments and the first calibration is given here only for completeness. The pressure of the oxygen coming from the booster is set to the desired value by a pressure regulator, and then the fluid flows through the orifice meter (Figures A . l and A .2). Its temperature is measured by a thermocouple (THP) and registered by the SCWO data acquisition system, and the pressure is read by a pressure gauge. When oxygen flows through the orifice, the transmitter records the differential pressure, which on its screen is measured in inches of water, and in volts by the SCWO data acquisition system (channel 24 on the computer). The oxygen flow rate is controlled by a needle valve, and a bulb thermometer (TLP) measures its temperature at atmospheric pressure. A flow meter, model Equimeter RC-M-415, then measures the volumetric flow. A pressure indicator (DPI 601) is used to measure the pressure in the inlet of the flow meter (PLP). Oxygen properties were obtained from a Matlab lookup table generated from the Journal of Physical and Chemical Reference Data 5 1 . 97 Oxygen damper 3H Pressure Ti re^ubator Oxygen booster Oxygen tank Orifice meter Needle valve - X b r TLP PLP Q? Patm Flow meter Figure A . l Schematic of the oxygen set up for the first set of calibrations A Oxygen accumulator Oxygen booster Oxygen tank Pressure regulator — HP - X J Orifice eter Needle valve T L P PLP Q> Patm 4 —. Flow meter Figure A.2 Schematic of the oxygen set up for the second set of calibrations 3. Calculations From Bernoulli's Law: [A.2] And since the change in pressure (AP) is linear to the output voltage signal: ;„2 m = k'<y-v0) p [A.3] Where Vo is the zero offset in voltage (Vo= 1.999), V is the voltage read at each flow conditions, and k' is a factor that can be found by fitting the data to the correlation. First calibration test The transmitter was calibrated at 3900 psi and 4200 psi. Calibration data for both 3900 psi and 4200 psi can be seen in Table A . l , and in Figures A.3 , A.4 and A.5. At 3900 psi, the mass flow rate obtained as a function of the voltage difference was: Where: m : Mass flow rate in kg/h, p : Average density at 3900 psi and the temperatures that appear in Table A . l (341 kg/m3), V : Output voltage (V) Vo: Zero offset of the transmitter (V) At 4200 psi, the mass flow rate obtained was: m = 0.197 *pU2* <y-v0) 1/2 [A.4] 99 m = 0.214*p1'2 *(Y-V0) 1 /2 [A.5] Where the average density is p = 352.37 kg/m 3 As it was stated before, it was observed that the temperatures were quite unstable, and increasing, with time. This could have been one of the reasons for not having a single coefficient k' which was not dependent on the pressure. Second calibration test For this test, the pulsation damper (10 feet long by 2 inches in diameter, 316 SS) was used as an oxygen accumulator to absorb all the temperature and pressure fluctuations when the system was operating, changes can be observed by comparing Figures A . l and A.2. The procedure followed for the calculations was the same as the one explained above, and the calibration was performed for 3600, 3900 and 4200 psi. The calibration data at all pressures can be seen in Table A.2 and Figures A.6, A.7 and A.8. For all cases, the obtained relations were a function of the same coefficient k'. In this case m yielded the following result: rh = 0.23* p1'2 * ( V - V 0 ) 1 /2 [A.6] Where p was the average density for each pressure: P (36oo Psi)= 339.07 kg/m 3 P(3900Psi)= 364.34 kg/m 3 P(4oooPsi)= 372.94 kg/m 3 100 Error analysis The uncertainty in the oxygen mass flow rate was calculated on the basis of the uncertainties in the primary measurements. The uncertainties in the thermocouples and volume flow meter were neglected, being considered much smaller than that of the high-pressure side manometer, which directly influences the mass flow. The pressure gauge used had a precision of 50 psi, which introduced different densities uncertainties, depending on the pressure. This was because the density did not change linearly with the pressure. The calculation of any possible error in the density was performed for some of the pressures most commonly used, which were: 3800 ± 50 psi, 3900 ± 50 psi, and 4150 ± 50 psi. Densities at these pressures, and at their corresponding average temperatures on the high-pressure were obtained from the lookup table. The yielded errors were the following: P(3800 Psi)=355.49±1.2% P(3900 Psi)=364.64±1.26% P(4i50 Psi)=384.75±1.14% The contribution of the constant factor (0.23) to the error in the flow was also calculated. From Figure 7 it can be observed that the exact value of the constant oscillated from 0.228 to 0.232, 0.23 being the mean value. The unbiased standard deviation was calculated according to equation [A.7], 4 1 where n=3. n-l TT 1/2 [A.7] The result yielded T=0.002 and the uncertainty in the equation's constant was + 0.87%. 101 To obtain the contribution of the voltage to the oxygen flow rate equation, several cases of oxidation experiments were considered. During these experiments, the system pressure and oxygen flows were considered to be stable. No samples were taken from the intermediate ports; hence no external actions to upset the system's stability existed. The analysed runs were Run 2, 2b, 2c, 4, 4b, 6, 6b, 6c, and 7of the 2,4 dinitrophenol-based experiments. To calculate the voltages uncertainty, the average of the voltages reading of all the runs were taken, as well as their corresponding maximum and minimum deviations, in percent. The unbiased standard deviation was calculated according to equation [A.7], and the Chauvenet's criterion for rejecting a reading 4 1 was applied. This resulted in a voltage uncertainty of 0.04% (see Table A.3 for calculations). The uncertainty in the zero offset was assumed to be negligible. Finally, the expected uncertainty in the oxygen mass flow rate formula (which is a product function of the type R=yi a l * y 2 a 2 * . . . y n a n) can be expressed by general equation [A.8] 4 1 , or by the simplified case for product type functions [A.9]: wR dR_ w. + dR_ dy2 'Wo + . dR_ - | l / 2 [A.8] wR = R ( * V 1 /2 [A.9] Where wR is the uncertainty in the oxygen mass flow, and w, are the uncertainties in the independent variables. The values of the uncertainties depended on the pressures at which the oxygen system was operated, and the target voltages. Table A.4 shows their values for runs 2, 2b, 2c, 4, 4b, 6, 6b, 6c and 7 of the 2,4 DNP and ammonia experiments. 102 4. Conclusions The oxygen flowmeter Forboro IDP10 was calibrated, and mass flow rate relations were obtained. The second set of calibrations was considered to be more accurate, due to the uniformity in the temperatures on the high-pressure side, and the stability in the oxygen flow and pressure at all times. An error analyses was performed, yielding that the uncertainty on the equation's constant was ± 0.87%, the voltage's uncertainty was 0.04%and the error in the density depended on the pressure at which the oxygen system was being operated. For subsequent calibrations, the relation mass flow rate- voltage will be the following: [A.6], (considering the calculated uncertainties) m = 0.23*p1'2 *(V-V0)U1 103 9.000 8.000 7.000 € 6.000 CT) " 5.000 E 4.000 8 3.000 s 2.000 1.000 0.000 • 3900 psi • 4200 psi 1 2 3 4 5 Data Acquisition system output (CH24) [V] Figure A.3 First set of calibrations. Mass flow rate vs. voltage. 104 120 O 80 y =25.124x (4200) & y= 25.311x (3900) • 3900 • 4200 - - - - Linear (3900) Linear (4200) 1.5 2 2.5 3 3.5 4 V-VO [V] Figure A.5 First set of calibrations. Transmitter reading vs. voltage difference. U) 8.000 7.000 6.000 5.000 | 4.000 » 3.000 2.000 1.000 0.000 Tl 2.5 3 3.5 4 4.5 Data acquisition system output (CH24) [V] • 3600 psi • 3900 psi 4000 psi Figure A.6 Second set of calibrations. Mass flow rate vs. voltage. 105 0.160 0.140 0.120 « 0.1CK o> i£ 0.080 o CM E DC 0.060 0.040 0.020 0.000 • • • A * — . . * W A ' A • - 4 " • 3600 psi i • 3900 psi • " — A 4000 psi 0 0.5 1 L 5 v-vO [V] i 1 2 2.5 3 Figure A.7 Second set of calibrations. m2/density vs. voltage difference. Figure A .8 Second set of calibrations. 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O O O O O O O O - . - . - . b b b b b r > s c o u c o ( 9 r * r o co co ro oi ° N I t j : ro o 1 CO - * — X cr = T cr = r o o » O S T o o o o o o o o o < - > © O O O O O O O O ' - — u i a i u i u i o i u i u i j i o i < ' I u c n o i j i t o u N i c o - ' 0 j o o o o o o o o o o o ' o o o o o o o o o o o - j o ro co o o o o o o o o o « ~ > ro O O O O O O O O O ' — . c n o i o i o i j i W j i A u i < I M O ) U W t D O ) K ( 0 0 ) ° j ro ro ro ro ro ro ro ro < *• r o r o r o r o r o r o r o r o < t u i j i c n j i j i j i M t . 0 t Table A.3 Uncertainty in voltage, 2,4 DNP and ammonium sulphate experiments R U N Deviation from the voltages [%] Deviation from the mean (y-y m ) DeviationA2 Deviation/USD (used to apply Chauvenet's criterion) New deviation DeviationA2 2 max 0.07335 -0.00222 4.948E-06 -6.017E-02 0.00522 2.7288E-05 min 0.07738 0.00180 3.256E-06 4.882E-02 0.00925 8.5612E-05 2b max 0.06356 -0.01202 1.445E-04 -3.252E-01 -0.00457 2.0922E-05 min 0.08848 0.01290 1.665E-04 3.490E-01 0.02035 4.1415E-04 2c max 0.07146 -0.00412 1.698E-05 -1.115E-01 0.00333 1.1074E-05 min 0.01761 -0.05797 3.361E-03 -1.568E+00 -0.05052 2.5527E-03 4 max 0.13178 0.05621 3.159E-03 1.521E+00 0.06366 4.0521E-03 min 0.15527 0.07969 6.350E-03 2.156E+00 0.08714 7.5927E-03 4b max 0.06872 -0.00686 4.709E-05 -1.856E-01 0.00059 3.4322E-07 min 0.00982 -0.06576 4.324E-03 -1.779E+00 -0.05831 3.4004E-03 6 max 0.05025 -0.02532 6.413E-04 -6.851E-01 -0.01788 3.1957E-04 min 0.04238 -0.03320 1.102E-03 -8.981E-01 -0.02575 6.6316E-04 6b max 0.01776 -0.05782 3.343E-03 -1.564E+00 -0.05037 2.5372E-03 min 0.06062 -0.01495 2.236E-04 -4.045E-01 -0.00750 5.6313E-05 6c max 0.06887 -0.00671 4.501E-05 -1.815E-01 0.00074 5.4687E-07 min 0.06928 -0.00630 3.966E-05 -1.704E-01 0.00115 1.3240E-06 7 max 0.09162 0.01604 2.574E-04 4.340E-01 0.02349 5.5182E-04 min 0.20220 0.12662 1.603E-02 3.425E+00 0 0 mean: 0.07558 U.S.D: 3.697E-02 New mean: 0.06813 USD: 3.7322E-02 Voltage uncertainty = V+- 0.04% 109 Table A.4 Uncertainty in mass flow. 2,4 DNP and ammonium sulphate experiments RUN 2 2b 2c 4 4b 6 6b 6c 7 Oxygen Flow [kg/h] 1.02 0.83 0.59 1.00 0.81 0.96 0.86 0.68 1.44 Stoichiometric oxygen [kg/h] 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 Voltage [V] 2.0566 2.039 2.0211 2.0554 2.0374 2.0512 2.0412 2.03 2.11 r r * Y T ' 2 T - I a, * w, wR = R* y — -m = 0.23*pV2*(V-Voy'2 al 1 1 1 1 1 1 1 1 1 yi 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 wl 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 a2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 y2 364.34 364.34 364.34 364.34 364.34 364.34 364.34 364.34 364.34 w2 4.58 4.58 4.58 4.58 4.58 4.58 4.58 4.58 4.58 a3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 y3 0.0536 0.036 0.0181 0.0524 0.0344 0.0482 0.0382 0.0238 0.1072 w3 (0.04% of V) 8.23E-04 8.16E-04 8.08E-04 8.22E-04 8.15E-04 8.20E-04 8.16E-04 8.11E-04 8.44E-04 Wf 0.0134 0.013 0.0146 0.0134 0.013 0.0132 0.013 0.0136 0.0164 Oxygen excess with average flow [%] 12.92 -7.45 -34.46 11.64 -9.53 7.06 -4.62 -24.74 59.68 Oxygen excess with average flow+Wf [%] 14.411 -6.004 -32.83 13.123 -8.084 8.5222 -3.173 -23.23 61.504 Oxygen excess uncertainty [%] 1.49 1.44 1.63 1.48 1.45 1.47 1.44 1.51 1.83 1 Appendix B Gas flow meter calibration report 1. Objectives: To calibrate the measurements obtained with the SCWO gas flow meter (AL 425 Canadian Meter Company Limited), by using an Equimeter RC-M-415 as a standard. 2. Setup: We located both flow meters in series; the standard preceding the SCWO one, (Figure B . l ) . The gas source consisted of a compressed air tank with a pressure regulator, which allowed us to change the air's outlet pressure, and the flow entering the flow meters. We assumed that there was no pressure drop inside the flow meters, which was corroborated by measuring the differential pressure between inlet and outlet of the device (less than 1 psi for all measurements). Additionally, it was assumed that there was no pressure drop between both flow meters. 3. Procedure: a) Set the pressure regulator to 10 psi, and check for leaks on both flow meters, and their connecting lines. => No leaks were detected b) Set the pressure regulator to different pressures and take measurements with both flow meters. The standard flow meter reads the measurement in clockwise cycles of 0.01 m 3 . The SCWO flow meter measured 1 cubic foot per revolution i l l c) Develop a corrections table for the SCWO flow meter, based on the measurements from the standard flow meter 4. Error analysis The precision of the instrument was of 5% or 0.05 ft3, taken from its minimum division divided by 2. 5. Conclusions The SCWO gas flow meter was calibrated against a standard flow meter => A correction chart was developed, which should be consulted whenever measurements with the object flow meters are taken. Pressure Regulator Atmospheric Dressufe Standard SCWO Flow meter Flow meter Compressed Air Figure B . l Schematic of the calibration setup 112 Table B . l Gas Flow measurements. Corrections table MEASURED FLOW MEASURED CORREC [FTft3/SEC] FLOW [L/SEC] FLOW [L/S (SCWO flow (SCWO flow (Standard meter) meter) meter) 0 .00353 0.1 0 .158 0 .00388 0.11 0 .162 0 .00424 0.12 0 .166 0 .00459 0 .13 0 .170 0 .00494 0.14 0 .175 0 .00530 0.15 0 .180 0 .00565 0.16 0 .186 0 .00600 0.17 0.191 0 .00636 0.18 0 .197 0.00671 0 .19 0 .204 0 .00706 0.2 0 .210 0 .00742 0.21 0 .217 0 .00777 0.22 0 .224 0 .00812 0 .23 0.231 0 .00847 0.24 0 .238 0 .00883 0.25 0 .246 0 .00918 0.26 0 .253 0 . 0 0 9 5 3 0.27 0.261 0 .00989 0.28 0 .269 0 .01024 0 .29 0 .277 0 .01059 0 .3 0 .285 0 .01095 0.31 0 .293 0 .01130 0.32 0.301 0 .01165 0 .33 0 .310 0.01201 0.34 0 .318 0 .01236 0.35 0 .326 0.01271 0.36 0 .335 0 .01306 0.37 0 .343 0 .01342 0.38 0.351 0 .01377 0 .39 0 .360 0 .01412 0.4 0 .368 0 .01448 0.41 0 .376 0 .01483 0.42 0 .385 0 .01518 0 .43 0 .393 0 .01554 0.44 0.401 0 .01589 0.45 0 .409 0 .01624 0 .46 0 .418 0 .01660 0 .47 0 .426 0 .01695 0 .48 0 .434 0 .01730 0.49 0 .442 0 .01766 0.5 0 .449 0.01801 0.51 0 .457 0 .01836 0.52 0 .465 0.01871 0.53 0 .473 0 .01907 0.54 0 .480 0 .01942 0 .55 0 .487 0 .01977 0 .56 0 .495 0 .02013 0.57 0 .502 0 .02048 0 .58 0 .509 0 . 0 2 0 8 3 0.59 0 .516 0 .02119 0.6 0 .523 MEASURED MEASURED CORRECT FLOW [FT«3/SEC] FLOW [L/SEC] FLOW [L/SEC] (SCWO flow (SCWO flow (Standard 1 meter) meter) meter) 0 .02154 0.61 0 .530 0 .02189 0.62 0 .537 0 .02225 0.63 0 .543 0 .02260 0.64 0 .550 0 . 0 2 2 9 5 0.65 0 .557 0 .02331 0.66 0 .563 0 . 0 2 3 6 6 0.67 0 .569 0 .02401 0.68 0 .575 0 .02436 0.69 0 .582 0 .02472 0.7 0 .588 0 .02507 0.71 0 .594 0 .02542 0.72 0 .599 0 .02578 0 .73 0 .605 0 . 0 2 6 1 3 0.74 0.611 0 .02648 0.75 0 .617 0 . 0 2 6 8 4 0.76 0 .623 0 .02719 0.77 0 .628 0 . 0 2 7 5 4 0.78 0.634 0 . 0 2 7 9 0 0.79 0 .639 0 . 0 2 8 2 5 0.8 0 .645 0 . 0 2 8 6 0 0.81 0 .650 0 . 0 2 8 9 5 0.82 0.656 0.02931 0.83 0.662 0 .02966 0.84 0 .667 0.03001 0.85 0 .673 0 .03037 0 .86 0 .678 0 .03072 0.87 0.684 0 .03107 0 .88 0 .690 0 .03143 0.89 0.696 0 . 0 3 1 7 8 0.9 0.701 0 . 0 3 2 1 3 0.91 0 .707 0 .03249 0.92 0.714 0 .03284 0 .93 0 .720 0 .03319 0.94 0.726 0 . 0 3 3 5 5 0.95 0 .733 0 .03390 0.96 0 .739 0 . 0 3 4 2 5 0.97 0 .746 0 .03460 0.98 0 .753 0 . 0 3 4 9 6 0.99 0 .760 0 .03531 1 0.768 0 . 0 3 5 6 6 1.01 0 .775 0 .03602 1.02 0 .783 0 .03637 1.03 0.792 0 .03672 1.04 0 .800 0 .03708 1.05 0 .809 0 . 0 3 7 4 3 1.06 0 .818 0 .03778 1.07 0 .828 0 .03814 1.08 0 .838 0 .03849 1.09 0 .848 0 .03884 1.1 0.858 Appendix C Thermocouples location with system's length The inlet of the cold side of the regenerative heat exchanger (RHX) has been taken as zero (the feed) and the outlet of its cold side as the effluent. Table C . l Thermocouples location in the SCWO pilot plant Thermocouple Type Location in the system Distance from feed [m] RHX in (cold side) 0.00 PH1 in Bulk Preheater 1 6.90 PH2 in Bulk Preheater 2 11.80 PH2 out Bulk Preheater 2 16.07 B2 Bulk Test Section 17.08 S10 Surface (bottom) Test Section 17.14 S4 Surface (bottom) Test Section 17.18 SB9 Surface (top) Test Section 17.23 S9 Surface (bottom) Test Section 17.33 SB8 Surface (top) Test Section 17.42 S8 Surface (bottom) Test Section 17.52 SB7 Surface (top) Test Section 17.60 S7 Surface (bottom) Test Section 17.69 SB6 Surface (top) Test Section 17.76 S6 Surface (bottom) Test Section 17.83 SB5 Surface (top) Test Section 17.89 S5 Surface (bottom) Test Section 17.92 SB4 Surface (top) Test Section 17.98 SB3 Surface (top) Test Section 18.11 S3 Surface (bottom) Test Section 18.19 SB2 Surface (top) Test Section 18.26 S2 Surface (bottom) Test Section 18.34 SB1 Surface (top) Test Section 18.41 S1 Surface (bottom) Test Section 18.48 B3 Bulk Test Section 18.55 S11 Surface (bottom) Test Section 18.66 S12 Surface (bottom) Test Section 18.82 S13 Surface (bottom) Test Section 19.00 S14 Surface (bottom) Test Section 19.18 S15 Surface (bottom) Test Section 19.30 S16 Surface (bottom) Test Section 19.38 S17 Surface (bottom) Test Section 19.52 S18 Surface (bottom) Test Section 19.65 S19 Surface (bottom) Test Section 19.79 S20 Surface [bottom) Test Section 19.95 114 Thermocouple Type Location in the system Distance from feed [m] B4 Bulk Test Section 20.44 R1B Surface Reactor 27.32 R1A Surface Reactor 33.54 RL2 Bulk Reactor 34.18 R2A Surface Reactor 34.21 R2B Surface Reactor 40.43 R3b Surface Reactor 41.04 R3a Surface Reactor 47.26 R4A Surface Reactor 47.90 R4B Surface Reactor 54.11 R5B Surface Reactor 54.76 R5A Surface Reactor 61.00 RL6 Bulk Reactor 61.91 R6A Surface Reactor 61.94 R6B Surface Reactor 68.16 R7B Surface Reactor 68.80 R7A Surface Reactor 75.02 R8A Surface Reactor 75.66 R8B Surface Reactor 81.88 R9B Surface Reactor 82.51 R9A Surface Reactor 88.73 RL10 Bulk Reactor 89.64 R10A Surface Reactor 89.67 R10B Surface Reactor 95.88 R11B Surface Reactor 96.52 R11A Surface Reactor 102.74 R12A Surface Reactor 103.40 R12B Surface Reactor 109.60 R13B Surface Reactor 110.21 R13A Surface Reactor 116.50 R14A Surface Reactor 117.10 R14B Surface Reactor 123.32 R15B Surface Reactor 123.96 R15A Surface Reactor 130.18 R16A Surface Reactor 130.81 R16B Surface Reactor 137.03 R17B Surface Reactor 137.64 RHX in (hot side) Surface RHX 143.71 RHX out (hot side) Surface RHX 150.14 115 Appendix D Sample coolers validation Temperature test for sample coolers To test how fast the samples were cooled we proceeded as following: • A 1/16" inconel thermocouple was inserted in the 14" sampling tube 2.5 cm downstream from the centre of the reactor's tube (see Figure 3.5 in Chapter 3). In the case of preheater 1 (PH 1), the selected thermocouple was 3/16" and the tube 3/8" (to avoid plugging of possible tarry material in this point) • The system was warmed up and the reactor's temperature elevated up to 500 °C • The cooling water valves were opened • The needle sampling valves were opened to allow a flow of approximately 0.1 mL/sec pass through them, and • The temperature measured by the thermocouples was registered by the data acquisition system. The registered temperatures were always in the range of 200-250 °C, so the quenching of the samples was considered to be good enough to prevent reaction from occurring in the sampling ports. Equation D . l was used to know how long it took the hot fluid to travel from its location in the reactor to the tip of the thermocouple. A was the total area of the tube, considering the inserted thermocouple, L was the length between the reactor and the tip of the thermocouple (always 2.5 cm), and m was the sample flow, approximately 0.1 mL/sec. The resulting time was 3.1 sec for P H 1 and 1.5 sec for the rest of the sampling ports (PH 2 in, P H 2 out, RL-2, RL-6, andRL-10). A*L m [D.l] Calculation of necessary rinsing times The same principle of Equation D . l was used to calculate the total necessary rinsing time for each sampling port, considering the total length of tube from the reactor to the sampling valve (see Figure D. 1). Both the portion of the sampling tubes containing the inserted thermocouple, and the free portions were considered. Equation D . l was then varied as: ^lotal ^portion with thermocouple ^portion without thermocouple [D.2] It resulted that the P H 1 had to be rinsed for at least 325 seconds (5.4 minutes) and the rest of the ports for at least 90 seconds (1.5 minutes) in order to evacuate at least one residence time. Reactor 2.5 cm Thermocouple 1/16", 3/16" To data acquisition system Sampling tubes, 1/4", 3/8" 1 m Sampling valve JXH To gas-liquid separator Figure D. 1 Sampling ports (Cooling jacket not shown) 117 Appendix E Preparation for 2,4 DNP, ammonium sulphate and ammonia The solubility of 2,4 DNP depends both on both the pH (fixed at around 9 for the wastes treated in this thesis) and the temperature of the solution. Table E . l shows temperature-solubility relations for 2,4 DNP at different pHs, in both ammonium sulphate and ammonium hydroxide solutions. This table was used a reference when setting the solubility temperatures for the feeds. The procedures followed to prepare both types of 2,4 DNP-based solutions were the following: 1. To prepare the 4% wt 2,4 DNP and 2% wt ammonium sulphate solution, the 200 L feed tank was filled with 100 litres of distilled water, then 4 kg of wet solid 2,4 dinitrophenol were added, Since the solubility of 2,4 DNP in ammonium sulphate solution is very low (see Table D. l ) ; 2,4 DNP was first dissolved in a high pH solution with ammonium hydroxide, and 3130 mL of 99% purity sulphuric acid was added afterwards to achieve the desired sulphates concentration and pH. After this, the tank was filled up with more distilled water to reach 200 L . To dissolve all the 2,4 DNP solids, the solution was heated up to 85 °C, by means of a steam coil, and stirred with a mechanical stirrer and by bubbling in low-pressure nitrogen. During the process, the person preparing the solution wore a self-contained breathing apparatus that allowed them to perform the job safely. When feed samples were taken from the feed tank, it was observed that not all the dinitrophenols had dissolved, and that only a 2.4% wt as 2,4 DNP solution was obtained. Additionally, the final concentration of ammonium sulphate was considerably lower than expected (only 0.39% wt), and the total ammonia concentration in the feed was much higher 118 than desired (6.67% wt). For this reason, the procedure to prepare the solution for the test without sulphates was changed, in order to try to dissolve the dinitrophenol in small batches. 2. The 2% DNP and ammonia solution was prepared as a set of 8 batches. The 2,4 dinitrophenol was purchased as 4, 1kg bottles of wet solid. 20L of deionised water was poured into a large stockpot equipped with a heating tape on the outside. As the water was heating, one half of a 2,4 DNP bottle was added. To this mixture was added 1200 ml of a 30% ammonia solution. Sufficient water was added to obtain an approximate volume of 25L. A n overhead mixer was used to agitate the solids at the bottom of the pot until dissolved. Typically, dissolution occurred between 40-45°C. Each batch of 25L was transferred to a plastic container for transportation. Once in the laboratory, the 8, 25 litre containers were poured into the feed tank. Table E . l Solubility of 2,4 DNP solutions with temperature and pH' pH of solution Solution Temperature [C] Solubility [% wt] 5 Ammonium sulphate 20 0.042 40 0.081 64 0.257 9 Ammonium hydroxide 20 0.12 51.7 0.61 75.3 1.11 11 Ammonium hydroxide 20 0.704 40 1.785 68 5.516 119 Appendix F Phenol experiments. Results and mass balances Channel configuration for the Data Acquisition System Table F. 1 Channel configuration. Phenol experiments Channel Port Position 1 PH2-in PH2-in 2 PH2-out PH2-out 3 E-2 B2 4 E - l l B3 5 E-25 B4 6 RL2-in RL2-in 7 RL6-in RL6-in 8 RLlO-in RLlO-in 9 E-5 S7 10 E - l l SB8 11 E-4 S10 12 E-22 S19 13 E-24 S20 14 E-23 SB20 15 Rl-B RIB 16 R3-B R3B 17 R8-A R8A 18 R15-A R15A 19 R15-B R15-B 20 R l l - A R l l - A 21 PIC 431 22 PT431 23 -24 o2 120 Temperatures entered in text files for Matlab programs Text files: runl.txt, run2.txt, run3.txt... and run9.txt Matlab files: ratelawsanalysis.m, convephenol.m, temprofiles2.m and temprofiles4.m Table F.2 Temperatures for text files. Phenol experiments Distance from the Registered feed [m] temperature Observations 0 Feed Ambient temperature 6.90 PHI in RHX out, (cold side) Calculated with MATLAB fllHEX.m) using TE 123 (obtained from Fortran program), and assuming no losses. 11.80 PH2 in Measured (CH 1) 16.07 PH2 out Measured (CH 2) 17.08 B2 Measured (CH3) 18.76 B3 Measured (CH4) 20.44 B4 Measured (CH5) 34.18 RL-2 Measured (CH6) 61.91 RL-6 Measured (CH7) 89.64 RL-10 Measured (CH8) 137.64 Reactor End Measured (CH 18) 143.71 RHX in (Hot side) Assumed = to Reactor's end 150.137 RHX out, TE 123 Calculated by Fortran program 121 PHENOL RUN 1 Date of test: Run 1.July11/01 Data Fi le jul11-1a.txt F e e d Phenol F e e d concentrat ion 4.036 %wt as Pheno l F e e d F low rate 0.780 l i tres/min 0 2 flow rate 5.026 kg/h 83.7667 g/min 1 0 % E x c e s s Stoichiometr ic 0 2 flow rate 4.57 kg/h 76.1667 g/min Vent G a s F low rate 75.51 l i tres/min at about 300K , 1 atm 3.0675 gmol /min Aqueous Stream Analysis S a m p l e Locat ion Feed Effluent PH2 in PH2 out RL2 in RL6 in Total Organ ic C a r b o n (ugC/g) 32000 21500 16300 11020 8180 5920.0 Pheno l (ug/g) 40357 13360 795.0 Gaseous Stream Analysis Abbreviation Sample Location S a m p l e Locat ion Effluent PH2out F e e d F e e d prior to test Oxygen (%) 36.87 75.35 Effluent Final effluent C a r b o n Monox ide (%) 8.26 2.3 P H 2 in Preheater 2 Inlet C a r b o n Diox ide (%) 53.33 19.03 P H 2 out Preheater 2 Outlet Hydrogen (%) 1.2 0 R L 2 in Reactor Sect ion 2 Inlet water vapor [%] (ambient temperature =2t 0.34 3.32 R L 6 in Reactor Sect ion 6 Inlet R L 1 0 _ i n Reactor Sect ion 10 Inlet g a s e o u s s t ream Vent gas (gas from gas-l iguid Mass Balance Hydrogen C a r b o n Oxygen Hydrogen Carbon Oxygen 1 12.011 15.9994 1 % of infl. % of infl. Component M.W. g/min g/min Feed T O C n/a in P h O H 0 0 0 Pheno l (C6H6O) 94.11 24 .105 5.352 100 .0% 6 .0% Oxygen (02) 32.00 0 83.767 0 .0% 94 .0% Total Influent 24.105 89.118 LIQUID EFFLUENT Total Ca rbon l ess T O C (assume C 0 3 ) not measu red T O C (assume C H x ) 12.011 4.618 0.000 19 .2% 0 Pheno l (C6H6O) 94.11 0.475 0.105 2 .0% 0 . 1 % Vent Gas Oxygen (02) 32.00 36 .1904 40 .6% C a r b o n Monox ide (CO) 28.01 3.0405 4 .0540 12.6% 4 . 5 % C a r b o n Diox ide ( C 0 2 ) 44.01 19.6309 52 .3490 81 .4% 58 .7% Hydrogen (H2) 2.016 0.0742 Total Effluents 0.074 27.764 92.699 Recovery (effluent/influent)x100 % 115 104 Destruction Efficiencies in(mg/l) out(mg/l) Conversion/ yield T O C 32000 5920.0 0.815 Pheno l 40357 795.0 0.98 C O yield 0 .121815822 C 0 2 yield 0 .786493678 122 PHENOL RUN 2 Date of test: D a t a Fi le F e e d F e e d concen t ra t i on F e e d F l o w rate 0 2 f low rate S to i ch iomet r i c 0 2 f low rate Ven t G a s F l o w rate Aqueous Stream Analysis R u n 2 J u l y 1 1 / 0 1 j u l H - 1 b.txt P h e n o l 4 .036 %wt a s P h e n o l 0 .780 l i t res/min 6 .130 kg /h 102 .1667 g /m in 4 .57 kg /h 7 3 . 1 0 l i t res/min at about 3 0 0 K , 1 a tm 2 . 9 6 9 6 g m o l / m i n 34 % E x c e s s S a m p l e Loca t i on Feed Effluent PH2 in PH2 out RL2 in RL6 in Tota l O r g a n i c C a r b o n (ugC/g ) 3 2 0 0 0 6 9 2 0 . 0 P h e n o l (ug/g) 4 0 3 5 7 2 0 4 2 . 0 Gaseous Stream Analysis S a m p l e Loca t i on G L S O x y g e n (%) 52 .22 C a r b o n M o n o x i d e (%) 6 .58 C a r b o n D iox ide (%) 3 8 . 5 7 H y d r o g e n (%) 0 .76 Abbreviation Sample Location F e e d F e e d prior to test Eff luent F ina l eff luent P H 2 _ i n P r e h e a t e r 2 Inlet P H 2 _ o u t P r e h e a t e r 2 Out le t R L 2 _ i n R e a c t o r S e c t i o n 2 Inlet R L 6 _ i n R e a c t o r S e c t i o n 6 Inlet R L 1 0 _ i n R e a c t o r S e c t i o n 10 Inlet g a s e o u s s t r e a m Ven t g a s (gas f rom gas- l i qu id separa to r ) Mass Balance H y d r o g e n C a r b o n O x y g e n H y d r o g e n C a r b o n O x y g e n 1 12.011 1 5 . 9 9 9 4 1 % of infl. % of infl. Component M . W . g /min g / m i n Feed T O C n/a in P h O H 0 0 0 P h e n o l ( C 6 H 6 0 ) 94.11 2 4 . 1 0 5 5 .352 1 0 0 . 0 % 5 . 0 % O x y g e n ( 0 2 ) 3 2 . 0 0 0 1 0 2 . 1 6 7 0 . 0 % 9 5 . 0 % Total Influent 24.105 107.518 LIQUID EFFLUENT To ta l C a r b o n l e s s T O C ( a s s u m e not m e a s u r e d T O C ( a s s u m e C H x ) 12.011 5 .398 0 .000 2 2 . 4 % 0 P h e n o l ( C 6 H 6 0 ) 94.11 1.220 0.271 5 . 1 % 0 . 3 % Vent Gas O x y g e n ( 0 2 ) 3 2 . 0 0 4 9 . 6 2 1 6 4 6 . 2 % C a r b o n M o n o x i d e ( C O ) 28.01 2 . 3 4 4 8 3 . 1 2 6 4 9 . 7 % 2 . 9 % C a r b o n D iox ide ( C 0 2 ) 44.01 13 .7446 3 6 . 6 5 2 2 5 7 . 0 % 3 4 . 1 % H y d r o g e n (H2) 2 . 0 1 6 0 .0455 Total Effluents 0.045 22.707 89.671 R e c o v e r y (ef f luent/ inf luent)x100 % 94 8 3 Destruction Efficiencies in(mg/l) out(mg/l) Conversion/yield T O C 3 2 0 0 0 6 9 2 0 . 0 0 .78 P h e n o l 4 0 3 5 7 2 0 4 2 . 0 0 .95 C O yie ld 0 . 0 9 3 9 4 2 5 7 3 C 0 2 y ie ld 0 . 5 5 0 6 6 3 3 8 2 PHENOL RUN 3 Date of test: Da ta Fi le F e e d F e e d concentrat ion F e e d F low rate 0 2 flow rate Stoichiometr ic 0 2 flow rate Vent G a s F low rate Aqueous Stream Analysis R u n 3.July11/01 jul11-2b.txt Pheno l 4.036 %wt as Pheno l 0.780 litres/min 6.360 kg/h 106 g/min 4.57 kg/h N O T M E A S U R E D litres/min at about 300K, 1 atm gmol/min R L 6 J N E 39 % E x c e s s S a m p l e Locat ion Feed Effluent PH2 in PH2 out RL2 in RL6 in Total Organ ic Ca rbon (ugC/g) 32000 73.0 Pheno l (ug/g) 40357 8.0 Gaseous Stream Analysis S a m p l e Locat ion G L S Oxygen (%) C a r b o n Monox ide (%) Carbon Dioxide (%) Hydrogen (%) Abbreviation F e e d Effluent PH2_ in PH2_ou t RL2_ in RL6_ in R L 1 0 in Sample Location F e e d prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Sect ion 2 Inlet Reactor Sect ion 6 Inlet Reactor Sect ion 10 Inlet I II— I U III I I v Q w l u l U C V L I O M l U l l l l t ^ l g a s e o u s s t ream Vent gas (gas from gas-l iquid separator) Mass Balance Hydrogen C a r b o n O x y g e n Hydrogen Carbon Oxygen 1 12.011 15.9994 1 % of infl. % of infl. Component M.W. g/min g/min Feed T O C n/a in P h O H 0 0 0 Pheno l ( C 6 H 6 0 ) 94.11 24 .105 5.352 100 .0% 4 . 8 % Oxygen (02) 32.00 0 106.000 0 .0% 9 5 . 2 % Total Influent 24.105 111.352 LIQUID EFFLUENT Total C a r b o n less T O C ( a s s u m e not m e a s u r e d T O C (assume C H x ) 12.011 0.057 0.000 0 .2% 0 Pheno l ( C 6 H 6 0 ) 94.11 0 .005 0.001 0 .0% 0 .0% Vent Gas Oxygen (02) 32.00 0.0000 0 .0% Carbon Monox ide (CO) 28.01 0 .0000 0.0000 0 .0% 0 .0% Carbon Dioxide ( C 0 2 ) 44.01 0 .0000 0 .0000 0 .0% 0 .0% Hydrogen (H2) 2.016 0.0000 Total Effluents 0.000 0.062 0.001 Recovery (effluent/influent)x100 % 0 0 Destruction Efficiencies in(mg/l) out(mg/l) Conversion/yield T O C 32000 73.0 0 .99771875 Pheno l 40357 • 8.0 0.9998 C O yield 0 C 0 2 yield 0 PHENOL RUN 4 Date of test: Data File F e e d F e e d concentrat ion F e e d F low rate 0 2 flow rate Stoichiometr ic 0 2 flow rate Vent G a s Flow rate Aqueous Stream Analysis Run 4.July11/01 jul11-2b.txt Phenol 4.036 %wt as Phenol 0.780 litres/min 6.130 kg/h 102.1667 g/min 4.57 kg/h N O T M E A S U R E D litres/min at about 300K, 1 atm gmol/min 34 % Ex c e s s Samp le Locat ion Feed Effluent PH2in PH2 out RL2 in RL6 in Total Organ ic C a r b o n (ugC/g) 32000 4540.0 Phenol (ug/g) 40357 932.0 Gaseous Stream Analysis Samp le Locat ion G L S Oxygen (%) 50.1 Carbon Monox ide (%) 8.09 Carbon Dioxide (%) 39.65 Hydrogen (%) 0.92 Abbreviation Sample Location Feed Effluent PH2_ in PH2_out RL2_in RL6_in RL10_ in gaseous st ream F e e d prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Sect ion 2 Inlet Reactor Sect ion 6 Inlet Reactor Sect ion 10 Inlet Vent gas (gas from gas-l iguid separator) Mass Balance Hydrogen Carbon Oxygen Hydrogen Carbon Oxygen 1 12.011 15.9994 1 % of infl. % of infl. Component M.W. g/min g/min Feed T O C n/a in P h O H 0 0 0 Phenol ( C 6 H 6 0 ) 94.11 24.105 5.352 100 .0% 5.0% Oxygen (02) 32.00 0 102.167 0 .0% 95 .0% Total Influent 24.105 107.518 LIQUID EFFLUENT Total Ca rbon less T O C (assume C not measured T O C (assume C H x ) 12.011 3.541 0.000 14.7% 0 Phenol ( C 6 H 6 0 ) 94.11 0.557 0.124 2 . 3 % 0 . 1 % Vent Gas Oxygen (02) 32.00 0.0000 0 .0% Carbon Monox ide (CO) 28.01 0.0000 0.0000 0 .0% 0.0% Carbon Dioxide ( C 0 2 ) 44.01 0.0000 0.0000 0 .0% 0.0% Hydrogen (H2) 2.016 0.0000 Total Effluents 0.000 4.098 0.124 Recovery (effluent/influent)x100 % 17 0 Destruction Efficiencies in(mg/l) out(mg/l) Conversion T O C 32000 4540.0 0.86 Phenol 40357 932.0 0.98 C O yield 0 C 0 2 yield 0 PHENOL RUN 5 Date of test: Data Fi le F e e d F e e d concentrat ion F e e d F low rate 0 2 flow rate Stoichiometr ic 0 2 flow rate Vent G a s F low rate Aqueous Stream Analysis Run 5.July19/01 jul19-1a.txt Phenol 2 .700 %wt as Pheno l 0.780 litres/min 4.180 kg/h 69 .66667 g/min 3.13 kg/h 52 .16667 31.63 litres/min at about 3 0 0 K , 1 atm 1.2849 gmol/min 34 % E x c e s s S a m p l e Locat ion Feed Effluent PH2in PH2 out RL2 in RL6 in Total Organ ic C a r b o n (ugC/g) 21550 15100 11440 8860 7480 4430.0 Phenol (ug/g) 27127 16026 11798 9372 5737 704.0 Gaseous Stream Analysis Abbreviation Sample Location S a m p l e Locat ion G L S F e e d F e e d prior to test Oxygen (%) 46.27 88.24 Effluent Final effluent Ca rbon Monox ide (%) 8.91 0 P H 2 _ i n Preheater 2 Inlet Ca rbon Dioxide (%) 43.85 11.76 PH2_ou t Preheater 2 Outlet Hydrogen (%) 0.97 0 R L 2 _ i n Reactor Sect ion 2 Inlet R L 6 _ i n Reactor Sect ion 6 Inlet RL10_ in Reactor Sect ion 10 Inlet g a s e o u s st ream Vent gas (gas from gas-l iquid separator) Mass Balance Hydrogen C a r b o n Oxygen Hydrogen Carbon Oxygen 1 12.011 15.9994 1 % of infl. % of infl. Component M . W . g/min g/min Feed T O C n/a in P h O H 0 0 0 Phenol (C6H6O) 94.11 16.203 3.597 100 .0% 4 . 9 % Oxygen (02) 32.00 0 69.667 0 .0% 9 5 . 1 % Total Influent 16.203 73.264 LIQUID EFFLUENT Total Ca rbon less T O C (assume C 0 3 ) not measured T O C (assume C H x ) 12.011 3 .455 0.000 2 1 . 3 % 0 Phenol ( C 6 H 6 0 ) 94.11 0.420 0.093 2 .6% 0 . 1 % Vent Gas Oxygen (02) 32.00 19.0246 2 6 . 0 % Carbon Monox ide (CO) 28.01 1.3739 1.8318 8 .5% 2 . 5 % Carbon Dioxide ( C 0 2 ) 44.01 6 .7613 18.0302 4 1 . 7 % 2 4 . 6 % Hydrogen (H2) 2.016 0.0251 Total Effluents 0.025 12.011 38.980 Recovery (effluent/influent)x100 % 7 4 53 Destruction Efficiencies in(mg/l) out(mg/l) Conversion T O C 21550 4430.0 0.79 Phenol 27127 704.0 0.97 C O yield 0.081733252 C 0 2 yield 0.402245019 PHENOL RUN 6 Date of test: D a t a F i le F e e d F e e d concent ra t ion F e e d F l o w rate 0 2 f low rate S to i ch iomet r i c 0 2 f low rate Ven t G a s F l o w rate Aqueous Stream Analysis R u n 6.Ju ly19/01 jul19-1b.txt P h e n o l 2 .700 %wt a s P h e n o l 0 .780 l i t res/min 3 .100 kg/h 5 1 . 6 6 6 6 7 g/min 3 .13 kg/h 71 .90 l i t res/min at about 3 0 0 K , 1 a tm 2 .9209 gmo l /m in -1 % E x c e s s S a m p l e Loca t ion Feed Effluent PH2 in PH2 out RL2 in RL6 in Tota l O r g a n i c C a r b o n (ugC/g) 2 1 5 5 0 16310 13230 12280 8 4 8 0 5420 .0 P h e n o l (ug/g) 2 7 1 2 7 2 0 4 3 4 16270 10505 6 6 5 5 1531.0 Gaseous Stream Analysis S a m p l e Loca t ion G L S O x y g e n (%) 52 .66 C a r b o n M o n o x i d e (%) 8 .15 C a r b o n D iox ide (%) 38 .42 H y d r o g e n (%) 0.77 Abbreviation Sample Location F e e d Eff luent P H 2 _ i n P H 2 _ o u t R L 2 _ i n R L 6 _ i n R L 1 0 _ i n g a s e o u s s t r e a m F e e d prior to test F ina l eff luent P rehea te r 2 Inlet P rehea te r 2 Out let R e a c t o r Sec t i on 2 Inlet R e a c t o r Sec t i on 6 Inlet R e a c t o r Sec t i on 10 Inlet Ven t g a s (gas f rom gas- l iqu id separator ) Mass Balance H y d r o g e n C a r b o n O x y g e n Hyd rogen C a r b o n O x y g e n 1 12.011 15 .9994 1 % of infl. % of infl. Component M . W . g /min g/min Feed T O C n/a in P h O H 0 0 0 P h e n o l ( C 6 H 6 0 ) 94.11 16 .203 3.597 1 0 0 . 0 % 6 . 5 % O x y g e n ( 0 2 ) 32 .00 0 51 .667 0 . 0 % 9 3 . 5 % Total Influent 16.203 55.264 LIQUID EFFLUENT To ta l C a r b o n l ess T O C ( a s s u m e C( not m e a s u r e d T O C ( a s s u m e C H x ) 12.011 4 .228 0 .000 2 6 . 1 % 0 P h e n o l ( C 6 H 6 0 ) 94.11 0 .914 0 .203 5 . 6 % 0 . 4 % Vent Gas O x y g e n ( 0 2 ) 32 .00 49 .2182 8 9 . 1 % C a r b o n M o n o x i d e ( C O ) 28.01 2 . 8 5 6 6 3 .8088 1 7 . 6 % 6 . 9 % C a r b o n D iox ide ( C 0 2 ) 44.01 13 .4664 35 .9103 8 3 . 1 % 6 5 . 0 % H y d r o g e n (H2) 2 .016 0 .0453 Total Effluents 0.045 21.465 89.140 R e c o v e r y (eff luent/ inf luent)x100 % 132 161 Destruction Efficiencies in(mg/l) out(mg/l) Conversion T O C 2 1 5 5 0 5 4 2 0 . 0 0 .75 P h e n o l 2 7 1 2 7 1531 .0 0 .94 C O y ie ld 0 . 1 6 9 9 4 4 9 9 7 C 0 2 y ie ld 0 . 8 0 1 1 3 9 4 8 4 PHENOL RUN 7 Date of test : D a t a Fi le F e e d F e e d concen t ra t i on F e e d F l o w rate 0 2 f low rate S to i ch i ome t r i c 0 2 f low rate V e n t G a s F l o w rate Aqueous Stream Analysis R u n 7 .Ju ly25 /01 j u l 25 -2a P h e n o l 2 . 7 0 0 %wt a s P h e n o l 0 . 7 8 0 l i t res /min 3 .780 kg /h 63 g /min 3 .13 kg /h 36.61 l i t res/min at about 3 0 0 K , 1 a t m 1.4872 g m o l / m i n 21 % E x c e s s S a m p l e L o c a t i o n Feed Effluent PH2 in PH2 out RL2 in RL6 in To ta l O r g a n i c C a r b o n (ugC/g ) 2 1 7 0 0 1 5 1 0 0 11200 8 9 6 0 7 0 1 0 4 1 2 0 . 0 P h e n o l (ug/g) 2 7 4 3 6 1 3 1 3 3 10766 7 4 8 8 5 3 8 3 2 7 5 0 . 0 Gaseous Stream Analysis Abbreviation Sample Location S a m p l e L o c a t i o n G L S F e e d F e e d pr ior to test O x y g e n (%) 4 6 . 5 3 7 7 . 9 5 Eff luent F ina l eff luent C a r b o n M o n o x i d e (%) 9 .16 2 . 5 8 P H 2 _ i n P r e h e a t e r 2 Inlet C a r b o n D iox ide (%) 43 .4 19.08 P H 2 out P r e h e a t e r 2 Out le t H y d r o g e n (%) 0.91 0 .38 R L 2 in R e a c t o r S e c t i o n 2 Inlet R L 6 _ i n R e a c t o r S e c t i o n 6 Inlet R L 1 0 _ i n R e a c t o r S e c t i o n 10 Inlet g a s e o u s s t r e a m Ven t g a s (gas f rom gas- l i qu id separa tor ) Mass Balance H y d r o g e n C a r b o n O x y g e n H y d r o g e n C a r b o n O x y g e n 1 12.011 1 5 . 9 9 9 4 1 % of infl. % of infl. Component M . W . g /m in g /m in Feed T O C n/a in P h O H 0 0 0 P h e n o l (C6H6O) 94.11 16 .387 3 . 6 3 8 1 0 0 . 0 % 5 . 5 % O x y g e n ( 0 2 ) 3 2 . 0 0 0 6 3 . 0 0 0 0 . 0 % 9 4 . 5 % Total Influent 16.387 66.638 LIQUID EFFLUENT To ta l C a r b o n l e s s T O C ( a s s u m e C not m e a s u r e d T O C ( a s s u m e C H x ) 12.011 3 .214 0 . 0 0 0 19.6% 0 P h e n o l ( C 6 H 6 0 ) 94.11 1.643 0 . 3 6 5 1 0 . 0 % 0 . 5 % Vent Gas O x y g e n ( 0 2 ) 3 2 . 0 0 2 2 . 1 4 3 6 3 3 . 2 % C a r b o n M o n o x i d e ( C O ) 28.01 1.6348 2 . 1 7 9 7 1 0 . 0 % 3 . 3 % C a r b o n D iox ide ( C 0 2 ) 44.01 7 .7456 2 0 . 6 5 4 8 4 7 . 3 % 3 1 . 0 % H y d r o g e n (H2) 2 . 0 1 6 0 .0273 Total Effluents 0.027 14.237 45.343 R e c o v e r y (ef f luent/ inf luent)x100 % 87 6 8 Destruction Efficiencies in(mg/l) out(mg/l) Conversion T O C 2 1 7 0 0 4 1 2 0 . 0 0.81 P h e n o l 2 7 4 3 6 1.00 C O yie ld 0 . 0 9 6 5 8 3 8 7 6 C 0 2 y ie ld 0 . 4 5 7 6 1 3 5 6 PHENOL RUN 8 Date of test: Data Fi le F e e d F e e d concentrat ion F e e d F low rate 0 2 flow rate Stoichiometr ic 0 2 flow rate Vent G a s Flow rate Aqueous Stream Analysis R u n 8.July25/01 jul25-2b Pheno l 2 .700 %wt as Pheno l 0 .780 l i tres/min 3.740 kg/h 62 .33333 g/min 3.13 kg/h 30.74 litres/min at about 300K , 1 atm 1.2488 gmol /min 19 % E x c e s s S a m p l e Locat ion Feed Effluent PH2in PH2 out RL2 in RL6 in Total Organ ic Ca rbon (ugC/g) 21700 1240.0 Pheno l (ug/g) 27436 672.0 Gaseous Stream Analysis S a m p l e Location G L S Oxygen (%) Carbon Monox ide (%) Carbon Dioxide (%) Hydrogen (%) Abbreviation F e e d Effluent PH2_ in PH2_ou t RL2_ in RL6_ in R L 1 0 in Sample Location F e e d prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Sect ion 2 Inlet Reactor Sect ion 6 Inlet Reactor Sect ion 10 Inlet g a s e o u s st ream Vent gas (gas from gas-l iquid separator) Mass Balance Hydrogen C a r b o n Oxygen Hydrogen Carbon Oxygen 1 12.011 15.9994 1 % of infl. % of infl. Component M . W . g/min g/min Feed T O C n/a in P h O H 0 0 0 Pheno l ( C 6 H 6 0 ) 94.11 16.387 3.638 100 .0% 5 .5% Oxygen (02) 32.00 0 62.333 0 .0% 9 4 . 5 % Total Influent 16.387 65.972 LIQUID EFFLUENT Total Ca rbon less T O C (assume C 0 3 ) not measu red T O C (assume C H x ) 12.011 0.967 0.000 5 .9% 0 Phenol ( C 6 H 6 0 ) 94.11 0.401 0.089 2 .4% 0 . 1 % Vent Gas Oxygen (02) 32.00 0.0000 0 .0% Carbon Monox ide (CO) 28.01 0.0000 0.0000 0 .0% 0 .0% Carbon Dioxide ( C 0 2 ) 44.01 0.0000 0.0000 0 .0% 0 .0% Hydrogen (H2) 2.016 0.0000 Total Effluents 0.000 1.369 0.089 Recovery (effluent/influent)x100 % 8 0 Destruction Efficiencies in(mg/l) out(mg/l) Conversion T O C 21700 1240.0 0.94 Pheno l 27436 672.0 0.98 C O yield n.m C 0 2 yield n.m PHENOL RUN 9 Date of test: Data File F e e d F e e d concentrat ion F e e d F low rate 0 2 flow rate Stoichiometr ic 0 2 f low rate Vent G a s F low rate Aqueous Stream Analysis Run 9Ju ly25 /01 ju l25-2b Pheno l 2.700 %wt as Pheno l 0.780 litres/min 3.740 kg/h 62 .33333 g/min 3.13 kg/h 30.74 litres/min at about 300K , 1 atm 1.2488 gmol /min 19 % E x c e s s S a m p l e Locat ion Feed Effluent PH2 in PH2 out RL2 in RL6 in Total Organ ic Ca rbon (ugC/g) 21700 2290.0 Phenol (ug/g) 27436 179.0 Gaseous Stream Analysis S a m p l e Locat ion G L S Oxygen (%) 27.07 Carbon Monox ide (%) 3.63 Carbon Dioxide (%) 68.85 Hydrogen (%) 0.45 Sample Location Abbreviation F e e d Effluent P H 2 J n PH2_ou t RL2_ in RL6_ in R L 1 0 J n Sample Location F e e d prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Sect ion 2 Inlet Reactor Sect ion 6 Inlet Reactor Sect ion 10 Inlet n i_ iu_ in ncdo iu i ocouu i i I U unci g a s e o u s st ream Vent gas (gas from gas- l iquid separator) Mass Balance Hydrogen C a r b o n Oxygen Hydrogen Carbon Oxygen 1 12.011 15.9994 1 % of infl. % of infl. Component M . W . g/min g/min Feed T O C n/a in P h O H 0 0 0 Pheno l (C6H6O) 94.11 16.387 3.638 100 .0% 5 .5% Oxygen (02) 32.00 0 62 .333 0 .0% 9 4 . 5 % Total Influent 16.387 65.972 LIQUID EFFLUENT Total C a r b o n less T O C (assume C 0 3 ) not measu red T O C (assume C H x ) 12.011 1.786 0.000 10 .9% 0 Pheno l ( C 6 H 6 0 ) 94.11 0.107 0.024 0 .7% 0 .0% Vent Gas Oxygen (02) 32.00 10.8170 16 .4% Carbon Monox ide (CO) 28.01 0.5440 0.7253 3 . 3 % 1.1% Carbon Dioxide ( C 0 2 ) 44.01 10.3174 27.5131 6 3 . 0 % 4 1 . 7 % Hydrogen (H2) 2.016 0.0113 Total Effluents 0.011 12.755 39.079 Recovery (effluent/influent)x100 % 78 59 Destruction Efficiencies in(mg/l) out(mg/l) Conversion T O C 21700 2290.0 0.89 Pheno l 2 7 4 3 6 179.0 0.99 C O yield 0 .032138079 C 0 2 yield 0 .609561086 Deviations in oxygen excesses per runs Parameter Run 1 2 3 I 4 I 5 6 7 8 I 9 0 2 flow IV1 Average 3.46 4.17 4.33 4.17 3.02 2.62 2.81 2.81 2.81 Max 3.61 4.45 4.59 4.34 4.20 3.75 3.24 2.91 2.91 Min 3.33 3.92 4.07 3.99 2.57 1.96 2.68 2.75 2.75 0 2 f low rko/hl Average 5.04 6.13 6.36 6.13 4.20 3.11 3.74 3.74 3.74 Max 5.29 6.51 6.70 6.36 6.18 5.60 4.63 3.97 3.97 Min 4.82 5.77 5.98 5.86 3.14 0.59 3.43 3.60 3.60 0 2 excess f%l Average 10 34 39 34 34 -1 21 19 19 Max 15.85 42.49 46.53 39.22 97.31 78.93 48.03 26.98 26.98 Min 5.46 26.25 30.89 28.31 0.29 -81.25 9.59 14.87 14.87 0 2 e x c e s s (deviation from the mean) [%1 Max 5.52 8.36 7.41 5.10 63.07 79.69 28.68 7.65 7.65 Min -4.87 -7.87 -8.22 -5.82 -33.95 -80.49 -9.76 -4.46 -4.46 V2 e x c e s s , average deviation [%] * In t(-i£i f i e n r\f rnnr> 5 8 8 5 34* 80 10* 6 6 Other comparisons with other studies (runs 2.3.4. 8.9) P h e n o l E x p e r i m e n t s . C o m p a r i s o n w i t h o t h e r s t u d i e s R u n #2 R e s i d e n c e T i m e ( s e c ) Figure F. 1 Phenol Experiments. Agreement study. Run 2 131 Phenol Experiments. Comparison with other studies Run #3 20 25 30 35 40^ Residence Time (sec) Figure F.2 Phenol Experiments. Agreement study. Run 3 Phenol Experiments. Comparison with other studies Run #4 Residence Time (sec) Figure F.3 Phenol Experiments. Agreement study. Run 4 132 P h e n o l E x p e r i m e n t s . C o m p a r i s o n with other s t u d i e s R u n #8 Figure F.4 Phenol Experiments. Agreement study. Run 8 Figure F.5 Phenol Experiments. Agreement study. Run 9 Appendix G 2,4 DNP, ammonia and ammonium sulphate experiments Channel configuration for the Data Acquisition System Table G . l Channel configuration. 2,4 DNP, ammonium sulphate and ammonia Channel Port Position 1 PH2-in PH2-in 2 PH2-out PH2-out 3 E-2 B2 4 E - l l B3 5 E-25 B4 6 RL2-in RL2-in 7 RL6-in RL6-in 8 RLlO-in RLlO-in 9 E-19 S2 10 E-14 SB2 11 E-17 S4 12 E-18 SB4 13 E-5 S7 14 E-4 SB7 15 E-23 S20 16 R3-B R3B 17 R8-A R8A 18 R15-A R15A 19 Feed tank Feed tank 20 R l l - A R l l - A 21 PIC 431 22 PT431 23 -24 o2 Temperatures entered in text files for Matlab programs Text files: wastel.txt, Matlab files: dnpwastel.m Table G.2 Temperatures for text files. 2,4 DNP; ammonium sulphate and ammonia Distance from the feed [m] Registered temperature Observations 0 Feed Measured, CH 19 6.9 PHI in RHX out, (cold side) Calculated by in Matlab, assuming no losses 11.8 PH2 in Measured, CH 1 16.07 PH2 out Measured, CH 2 17.08 B2 Measured, CH 3 18.76 B3 Measured, CH 4 20.44 B4 Measured, CH 5 34.18 RL-2 Measured, CH 6 61.91 RL-6 Measured, CH 7 89.64 RL-10 Measured, CH 8 130.18 Reactor End Measured (close to the end), CHI 8 143.71 RHX in (hot side) Temperature loss was of approximately 8 °C * 150.137 RHX out,TE 123 Measured (TE 123) Calculation of temperature loss from the end of the reactor to R H X 1. Enthalpy loss (Ah) in another non-heated portion of the reactor (RL-10 to RL-11A) was calculated. Knowing the temperatures at RL-10 (848 K) and RL-11A ( 8 3 9 K), the heat loss ( j w a s represented as in equation G . l , with L as the distance between the two. (13.1 m). Ah was calculated from the water properties table , yielding that Ah=-2.4808 e4 J/kg i = Ah G.l L 2. Knowing the temperature close to the end of the reactor (831 K) and the distance from this point to the beginning of the R X H (also 13.1 m), the heat loss q2 was obtained as: 831 K i 2 = 8 4 8 ~ T ^ Z = ~ 2 - 4 2 8 1 e 4 J l k g 3. Finally, the temperature in the inlet of the RHX was obtained from the heat lost in the portion from the end of the reactor, yielding that T R Hx, in = 8 2 3 K. 135 2.4 DNP. Ammonia and Ammonium Sulphate Run 0 Date of test: Data file Feed Feed concentration Feed total ammonia Feed ammonium sulphate Feed Flow rate 02 flow rate Stoichiometric 02 flow rate Vent Gas Flow rate November 26th/01 nov2601.txt, nov26b01.txt Ammonium 2,4 Dinitrophenolate 2.400 wt% as Dinitrophenol 6.670 wt%asNH3 2.108 wt% as (NH4)2S04 0.800 litres/min 2.820 kg/h 47 g/min 0.95 kg/h 26.10 litres/min at about 300K, 1 atm 1.0603 gmol/min 197 % Excess Sample Location Feed Effluent PH2in PH2out RL2 In RL6 in Total Ammonia (as N) (pqN/q) 55800 810 Total Ammonia (pqN/q) 67757.1429 983.571429 Total Carbon (gqC/q) Total Orqanic Carbon (pqC/q) 9425 1410 644 218 8.0 Total Sulfate as (as S) (pqN/q) 5110 1304.0 Total Sulfate as S04 (pqN/q) 15330 3912 ratio NH3/T0C (mole/mole) 5.07464949 PH 8.9 7.4 2,4-Dinitrophenol (pq/q) 24088 81.2 16.5 1.6 0.7 1.0 2-Nitrophenol (pq/q) 0 84.4 70.5 40 0 1.0 4-Nitrophenol (pq/q) 0 196 146 51.2 2.2 1.0 Phenol (pq/q) 0 0 0 O 0 1.0 Nitrate (N03) (as N) (pq/q) 0.03 0.3 Nitrate (N03) (pq/q) 0.13285714 1.32857143 Nitrite (N02) (as N)(pq/q) 0.06 2.04 Nitrite (N02) (pq/q) 0.19714286 6.70285714 Carbonate(C03) 0 12600 Bicarbonate(HC03) 0 1810 Metals Calcium (pq/q) <2 8 11 2 * 4 1 Cobalt <0.05 13 8.3 3.8 13.2 0.23 Chromium (pq/q) <05 2640 891 437 836 4.71 Copper (pq/q) <0.1 219 137 57.6 186 5.5 Iron (pq/q) <0.2 1020 351 134 1190 <2 Potassium (pq/q) <5 <20 <6 <3 <4 <5 Molybdenum (pq/q) <1 1400 800 344 1120 231 Sodium (pq/q) 1.4 - - - - 2.2 Nickel (pq/q) <05 9520 4710 2230 . 5350 81.1 Zinc <2 105 54.7 38 87.3 3.1 Gaseous Stream Analysis Sample Location PH2out EFFLUENT Oxyqen (%) 45.4 8.2 Nitroqen (%) 32 63.4 Nitrous Oxide N20(%) 0.6 <5 Nitoqen dioxide (N02)(%) nd nd Carbon Monoxide (%) 3.6 <1 Carbon Dioxide (%) 19.1 32.1 Hydrogen (%) 0.6 <1 Abbreviation Feed Effluent PH2_in PH2_out RL2_in RL6_in RL10 in Sample Location Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Reactor Section 10 Inlet Vent gas (gas from gas-liquid separator) PH2 gaseous stream PH2 out gaseous stream Vent gas (gas from gas-liquid separator) effluent effluent 136 2.4 DNP. Ammonia and Ammonium Sulphate Run 0 Mass Balance Nitrogen Carbon Oxygen Sulfur Nitrogen Carbon Oxygen sulfur 14.0067 12.011 15.9994 32.06 % of infl. % ot infl. % of infl. % of infl. Component M.W. q/min q/min q/min q/min Feed Total Ammonia (as NH3) 17.031 44.640 93.8% Total Carbon less TOC n/a in 2.4dnp TOC n/a in 2.4dnp Total Sulfate as S04 (ugN/g) 96 8.1756934 4.088 12.9% 100.0% 0.0% 2,4-Dinitrophenol (C6H4N205) 184.11 2.932 7.543 8.373 6.2% 100.0% 13.2% 2-Nitrophenol (C6H5NCO) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 4-Nitrophenol (C6H5NOS) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% Phenol (C6H60) 94.11 0.000 0.000 0.0% 0.0% Nitrate (N03) 61.99 0.000 0.000 0.0% 0.0% Nitrite (N02) 45.99 0.000 0.001 0.0% 0.0010% Carbonate (C03) 60.00 0.00000 0.00000 0.0% 0.0% Bicarbonate (HC03) 61.00 0 0.00000 0.0% 0.0% Oxygen (02) 32.00 47.000 74.0% Total Influent 47.572 7.543 63.550 4.088 Liquid Effluent Total Ammonia (as NH3) 17.031 0.648 1.4% Total Carbon less TOC (assume C03) 60.009 not measured TOC (assume CHx) 12.011 0.006 0.1% Total Sulfate as S04 (uqN/q) 96.00 2.086 1.043 2,4-Dinitrophenol (OSH4N205) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2-Nitrophenol (C6H5N03) 139.11 0.000 0.000 0.001 0.0% 0.0% 0.0% 4-Nitrophenol (C6H5N03) 139.11 0.000 0.000 0.001 0.0% 0.0% 0.0% Phenol (C6H60) 94.11 0.000 0.001 0.001 0.0% 0.0% 0.0% Nitrate (N03) 61.99 0.00024 0.001 0.0% 0.0% Nitrite (N02) 45.99 0.00163 0.00373 0.0% 0.0% Carbonate (C03) 60.00 2.01785 8.06370 0.0% 12.7% Bicarbonate (HC03) 61.00 0.28987 1.15836 1.8% Vent Gas Oxygen (02) 32.00 2.7821 4.4% Nitroqen (N2) 28.01 18.8312 39.6% 0.0% Nitrous Oxide (N20) 44.01 0.1485 0.1696 0.3% 0.3% Carbon Monoxide (CO) 28.01 0.1274 0.1696 1.7% 0.3% Carbon Dioxide (C02) 44.01 4.0880 10.8569 54.2% 17.1% Hydroqen (H2) 2.016 0.0% Total Effluents 19.630 6.531 25.293 1.043 Recovery (effluent/intluent)x100 % 41.26 86.59 39.80 25.52 Destruction Efficiencies % Comments Dinitrophenol 99.996% None detected in effluent Total Ammonia 98.55% Residual present as NH4HC03 in effluent TOC 99.92% CO yield 0.01687458 C02 yield 0.54167396 N20 0.00083132 N2 yield 0.10541105 Oxygen excess uncertainty Parameter 02 flow [VI Averaqe 2.40 Max 2.46 Min 2.35 02 flow fkq/hl Averaqe 2.82 Max 3.03 Min 2.66 02 excess [%] Averaqe 197 Max 218.86 Min 179.51 02 excess (deviation from the mean) [%1 Max 21.65 Min -17.90 137 Appendix H 2,4 and ammonia experiments. Reports and mass balances Discrepancies in ammonia analyses Duplicates of samples were taken to measure ammonia in two different laboratories: BC Research Institute and UBC Civil engineering Environmental Lab. The BCRI laboratory gave consistently lower results. The reason for this is that the samples were not analyzed immediately, and were not properly prepared (acidified) before refrigerated. Unfortunately, the feed samples were only analyzed in the BCRI laboratory, (obviously yielding results that were lower than expected). The feed concentration was given by the amount of ammonia solution fed into the system, 2,000 mg/L (see Appendix E), under the assumption of perfect mixing. Table H . l shows the results given by BCRI and by UBC. 138 Table H. l Discrepancies in ammonia measurements Laboratory UBC BCRI Description Ammonia Ammonia mgN/L mgN/L Bucket 12 -feed 1851.33 Run 1 PH1 868 505.00 Run 1 PH2 in 723 602 • Run 1 PH2 out 1130 927 Run 1 RL-2 1000 602 Run 1 RL-6 1020 927 Run 1 Effluent 1010 736 Run 2 1090 804 Run 2b 1260 1098 Run 2c 1690 1234 Run 3 PH1 1230 1065 Run 3 PH2 In 479 384 Run 3 PH2 out 1280 885 Run 3 RL-2 380 286 Run 3 RL-6 989 750 Run 3 Effluent 1010 810 Run 4 Effluent 1130 933 Run 4b Effluent 1320 936 Run 5 PH 1 1280 1095 Run 5 PH 2 in 1140 996 Run 5 PH 2 out 1160 963 Run 5 RL-2 812 678 Run 5 RL-6 1090 723 Run 5 R L 6 2nd 1040 687 Run 5 Effluent 1160 600 Run 6 Effluent 1230 873 Run 6b Effluent 1300 1050 Run 6c Effluent 1480 1380 Run 7 1150 606 139 Channel configuration for the Data Acquisition System Table H.2 Channel configuration. 2,4 DNP and ammonia experiments Channel Port Position 1 PHI in PHI in 2 PH2-in PH2-in 3 PH2-out PH2-out 4 E-2 B2 5 E - l l B3 6 E-25 B4 7 RL2-in RL2-in 8 RL6-in RL6-in 9 TER-10 TER-10 10 E-19 PHI (weak point)* 11 E-14 S7 12 E-17 S20 13 R2-B R2-B 14 R3-A R3-A 15 R6-A R6-A 16 R l l - A R l l - A 17 R13-A R13-A 18 R17-A R17-A 19 R H X in R H X in 20 Feed tank Feed tank 21 - -22 PT431 23 - -24 o2 *Close to the corrosion failure from the 2,4 DNP, ammonium sulphate and ammonia experiments. The burst part of the tube was replaced, along with the thinnest portion. However, the thickness in this point was slightly less than that of a non-corroded 3/8" tube 140 Temperatures entered in text files for Matlab programs Text files: waste2.txt Matlab files: dnpwaste2.m Table H.3 Temperatures for text files. 2,4 DNP and ammonia experiments Distance from the feed [m] Registered temperature Observations 0.00 Feed Measured, CH 20 6.90 PHlin Measured, CH 1 11.80 PH2IN Measured, CH 2 16.07 PH2 OUT Measured, CH 3 17.08 TS IN Measured, CH 4 18.76 TS MED Measured, CH 5 20.44 TS OUT Measured, CH 6 34.18 RL-2 Measured, CH 7 40.40 R2-B Measured, CH 13 47.26 R3-A Measured, CH 14 61.91 R6-A Measured, CH 15 110.21 R13-B Measured, CH 17 137.64 R17-B Measured, CH 18 143.71 RHX in Measured, CH 19 150.14 RHX out Measured, TE 123 Sample calculation for accounting for air contamination (from section 3.5.2.3.1) Run 2c. effluent I n : ^2 ADNP = 0 - ° 9 6 mol/min(See Equation [14]) h 0 l =0.307 mol/min h =0.111 mol/min(See Equation [14]) nT0C = 0.576 mol/min (See Equation [14]) Out: X 2 , 4 DNP =0.99996 (~ 1) X N H 3 =0.155 141 XTOC = 0-9898 N2O/CO2 (BCRI) =0.041 CO/CO2 (BCRI) =0.051 C , I Q U I D =0.228 mol/min (CO3) Solving: Equation [38]: hCOn =0.325 moll'min Zout Equation [39]: h =0.017 mo//min Equation [40]: h =0.0135 mol/mm Equation [41]: hN =0.091 mo//min -'our Equation [33]: h0 =-0.195 rao//min = 0 out Equation [43]: h , =0.461 mol /min ^ gas total Equations [44], [45], [46], trial and error: xa = 0.64 (see Appendix H) Equation [47]: % =71.87 Equation [48]: % 0 L =13.86 Equation [49]: % C Q ^ =10.03 Equation [50]: % C Q =0.51 Equation [51]: % =0.42 i n —] T5T~ 3 = m 6c Effluent 6b Effluent 6 Effluent Effluent X to O £ PH 1 in & TTT~ 3 c= CD 3 4 Effluent Effluent Ui a to o c PH 1 in 2c Effluent to a" w~ c re 3 2 Effluent Effluent 1 PH2out PH 1 in Run Location 0.425 0.26 0.35 0.385 0.42 0.42 0.36 0.34 0.435 0.495 0.76 0.385 0.155 0.37 0.455 0.495 0.435 0.566 a x Ui - - - - - 0.974 0.931 - 0.996 0.930 - - - 0.993 I960 X 2.4DNP 0.998 0.997 0.999 0.999 - 0.853 0.741 0.999 -0.915 0.710 0.990 - - - 0.934 0.832 H O X n 0.748 0.354 0.448 0.500 0.772 0.772 0.772 0.422 0.521 0.749 0.749 0.749 0.307 0.434 0.529 0.755 0.755 0.755 3 ^ 9 I5' * 3.296 J 0.166 0.708 3.546 3.546 3.546 -0.105 0.925 3.302 3.302 3.302 I -1.299 0.019 1.012 3.367 3.367 3.367 X 9 0.051 0.067 0.060 0.051 0.050 0.045 0.044 0.059 0.051 0.044 0.046 0.039 0.228 0.057 0.051 0.045 0.044 0.026 C03  liquid [moVmin]* 0.000 0.017 0.000 0.000 0.000 0.170 0.081 0.000 0.000 0.000 0.037 0.066 0.051 0.000 0.000 0.000 0.028 0.029 S o 0.523 0.499 0.515 0.524 0.526 0.369 0.318 0.517 0.525 0.532 0.462 0.309 0.325 0.519 0.525 0.530 0.477 0.419 C02  gas [mol/min] 0.000 0.008 0.000 0.000 0.000 0.063 0.026 0.000 0.000 0.000 0.017 0.020 0.017 0.000 0.000 0.000 0.013 0.012 CO gas [mol/min] 0.078 0.061 0.080 0.079 0.098 0.023 0.000 0.064 0.076 0.090 0.030 0.000 0.041 0.067 0.084 0.069 0.047 0.000 N20/C02 (BCRI) 0.041 0.030 0.041 0.041 0.051 0.009 0.000 0.033 0.040 0.048 0.014 0.000 0.013 0.035 0.044 0.036 0.023 0.000 3 2 f£ 3 era B. to a vi 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.000 000 0 0.000 0.000 0.001 0.000 N03 and N02  liquid [mol/min]* 0.079 0.080 0.074 0.076 0.068 0.108 0.109 0.081 0.080 0.075 0.123 0.110 0.091 0.081 0.077 0.087 0.096 0.123 Njgas [mol/min] 0.269 -0.139 -0.038 0.017 0.292 0.303 0.317 -0.065 0.042 0.275 0.299 0.296 -0.195 -0.050 0.052 0.281 0.279 0.304 g . g 0.269 0.000 0.000 0.017 0.292 0.303 0.317 0.000 0.042 0.275 0.299 0.296 0.000 0.000 0.052 0.281 0.279 0.304 Ip K " 0.912 0.617 0.631 0.658 0.937 0.852 0.770 0.632 0.687 0.930 0.915 0.736 0.446 0.635 0.697 0.935 0.888 0.858 Total gas flow rate [mol/min] 0.942 0.638 0.652 0.680 0.968 0.880 0.795 0.653 0.709 0.961 0.945 0.761 0.461 0.656 0.721 0.966 0.917 0.886 Total gas flow rate (with wate vapour) [mol/min] 23.182 15.693 16.040 16.742 23.830 21.657 19.575 16.061 17.461 23.651 23.258 18.720 11.354 16.146 17.738 23.776 22.571 21.812 Total gas flow [L/min] (with water vapour) P a; X 4^ N i o a. o 5-3 CD 3 cr o Table H.5 2,4 DNP and ammonia experiments. Predicted gas percentages from molar flows (not considering air contamination) Run Location C02[%] CO [%] N2[%] N 2 0 [%] o2[%] H 2 0 vapour [%] 1 PHI 47.25 1.35 13.88 0.00 34.31 3.32 PH2 52.00 1.44 10.42 2.47 30.46 3.32 Effluent 54.91 0.00 8.99 3.76 29.12 3.32 2 Effluent 72.81 0.00 10.63 6.13 7.21 3.32 2b Effluent 79.09 0.00 12.39 5.30 0.00 3.32 2c Effluent 70.55 3.58 19.73 2.93 0.00 3.32 3 PHI 40.65 2.69 14.51 0.00 38.94 3.32 PH2 48.87 1.82 12.99 1.48 31.62 3.32 Effluent 55.34 0.00 7.83 5.00 28.63 3.32 4 Effluent 73.97 0.00 11.28 5.63 5.91 3.32 4b Effluent 79.21 0.00 12.49 5.09 0.00 3.32 5 PHI 39.94 3.25 13.73 0.00 39.87 3.32 PH2 41.93 7.12 12.26 0.98 34.49 3.32 Effluent 54.30 0.00 6.98 5.31 30.19 3.32 6 Effluent 77.07 0.00 11.16 6.07 2.50 3.32 6b Effluent 79.10 0.00 11.37 6.31 0.00 3.32 6c Effluent 78.20 1.29 12.53 4.77 0.00 3.32 7 Effluent 55.58 0.00 8.35 4.33 28.53 3.32 Table H.6 2,4 DNP and ammonia experiments. Air contamination Run Location x 0 2 ) BCRI x N 2 , BCRI x C 0 2 l BCRI x0 2 , vent x N 2 ) vent x C0 2 , vent Best fit xa Deviation from x 0 2 , BCRI [%] Deviation from x N 2 , BCRI [%] Deviation from x C0 2 , BCRI [%] Average deviation of the errors [%] 1 PHI 0.526 0.302 0.143 0.343 0.139 0.472 0.280 24.1 -1.0 -22.6 15.90 PH2 0.386 0.112 0.436 0.305 0.104 0.520 0.100 9.1 -6.0 -3.2 6.10 Effluent 0.292 0.333 0.321 0.291 0.090 0.549 0.360 3.0 -0.9 -3.0 2.30 2 Effluent 0.235 0.299 0.401 0.072 0.106 0.728 0.420 10.5 -9.5 -2.1 7.37 2b Effluent 0.163 0.471 0.313 0.000 0.124 0.791 0.540 5.0 -1.3 -5.1 3.80 2c Effluent 0.140 0.581 0.227 0.000 0.197 0.706 0.660 0.1 -0.8 -1.3 0.73 3 PHI 0.571 0.186 0.200 0.389 0.145 0.407 0.120 20.3 -3.7 -15.8 13.27 PH2 0.365 0.174 O.402 0.316 0.130 0.489 0.100 5.9 -2.1 -3.8 3.93 Effluent 0.293 0.389 0.264 0.286 0.078 0.553 0.440 4.1 -0.3 -4.6 3.00 4 Effluent 0.213 0.507 0.231 0.059 0.113 0.740 0.600 6.4 -1.2 -6.4 4.67 4b Effluent 0.181 0.623 0.154 0.000 0.125 0.792 0.760 2.1 -0.7 -3.6 2.13 5 PHI 0.555 0.194 0.204 0.399 0.137 0.399 0.100 17.5 -0.9 -15.6 11.33 PH2 0.555 0.195 0.184 0.345 0.123 0.419 0.120 22.6 -0.7 -18.5 13.93 Effluent 0.393 0.226 0.322 0.302 0.070 0.543 0.240 11.3 -1.7 -9.1 7.37 6 Effluent 0.236 0.284 0.416 0.025 0.112 0.771 0.440 13.0 -12.6 -1.6 9.07 6b Effluent 0.179 0.310 0.444 0.000 0.114 0.791 0.300 11.6 -0.6 -11.0 7.73 6c Effluent 0.065 0.295 0.564 0.000 0.125 0.782 0.260 1.0 -0.3 -1.4 0.90 7 Effluent 0.434 0.174 0.335 0.285 0.083 0.556 0.160 16.1 -2.3 -13.1 10.50 144 2.4 DNP and ammonia Run 1 Date of test: Data file Feed Feed concentration Feed total ammonia Feed TOC Feed Flow rate 02 flow rate Stoichiometric 02 flow rate Vent Gas Flow rate July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as 2,4 Dinitrophenol 0.243 wt% as NH3 0.886 wt% as TOC 0.780 litres/min 1.450 kg/h 24.166667 g/min 0.83 kg/h 0.9660 gmol/min See Note 7470 % Excess Aqueous Stream Analysis Sample Location Feed Effluent PH1 in PH2ln Ph2out RL2 in RL6 in (GLS) Total Ammonia (pgN/g) 2000 868 723 1130 1000 1020 1010 Ratio NH3/TOC (mole/mole) 0.19367496 0.49954751 0.6444757 1.6649408 291.5562 433.0467 Total Orqanic Carbon (pgC/g) 8855.23043 1490 962 582 - 3 2 PH 9.2 8.22 8.08 8.14 8.44 8.37 7.95 Picric Acid (pg/g) < 1 < 1 <1 <1 < 1 < 1 <1 2,4-Dinitrophenol (ug/g) 22630 877.7 489.1 153.8 < 1 < 1 <1 2,6-Dinitrophenol (ug/g) 111.8 < 1 <1 <1 < 1 < 1 <1 2-Nitrophenol (pg/q) < 1 358.6 < 1 < 1 < 1 < 1 < 1 4-Nitrophenol (pq/q) < 1 115.3 < 1 < 1 < 1 < 1 <1 Phenol (uq/q) < 1 < 1 <1 < 1 < 1 < 1 <1 Nitratefas N) (pq/q) <0.1 1 1.2 7.3 0.2 0.8 0.6 Nitrite (as N) (pg/g) <0.1 7.3 1.6 12 <0.1 0.2 <0.1 carbonate (pq/q) 3953.33 40 0 40 520 360 60 bicarbonate (pg/g) 1893.33 2100 2160 3380 3300 3380 3480 Metals Calcium (pq/q) N. M 0.2 Chromium (pg/g) N. M 0.32 Copper (pq/q) N. M <0.1 Iron (pg/q) N. M <0.2 Potassium (pq/q) N. M 1.64 Molybdenum (pg/q) N. M 0.16 Sodium (pq/q) N. M 0.82 Nickel (pg/g) N. M 0.34 Gaseous Stream Analysisi(not considering air contaninatlon) Sample Location PH1 PH2 Effluent Oxygen (%) 34.31 30.46 29.12 Nitroqen (%) 13.88 10.42 8.99 Nitrous Oxide (%) 0.00 2.47 3.76 Carbon Monoxide (%) 1.35 1.44 <0.1 Carbon Dioxide (%) 47.25 52.00 54.91 Nitrous Dioxide (%) <0.1 <0.1 <0.1 Methane (%) n.d n.d n.d Ethane (%) n.d n.d n.d water vapor [%] 3.32 3.32 3.32 total 100.11 100.11 100.10 Abbreviation Feed Effluent • PH2_in PH2_out Rl_2_in RL6_in Gaseous stream Gaseous stream Gaseous stream effluent Sample Location Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet PH1 Vent gas (GLS) PH1 in PH2 Vent gas (GLS) PH2 Vent gas (GLS) effluent 145 2.4 DNP and ammonia Run 1 Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36.6% Total Ca rbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2 .686 6.909 7.670 63 .0% 88 .0% 21.6% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 .1% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.000 0.000 0 .0% 0.0% Nitrate (N03) 61.99 0.00078 0.00267 0 .0% 0.0% Nitrite (N02 ) 45.99 0.00078 0.00240 0 .0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 Oxygen (02) 32.00 24.167 6 8 . 1 % Wate r (H20 ) 18.00 0.000 0.0% Total Influent 4.261 7.853 35.509 Liquid Effluent Total A m m o n i a (as N) 17.031 0.788 18 .5% T O C 12.011 0.002 0 .0% 0.0% Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.001 0.000 0 .0% 0.0% 0.0% Nitrate (N03 ) 61.99 0.00569 0.00160 0 . 1 % 0.0% 0.0% Nitrite (N02 ) 45.99 0.00936 0.00018 0 .2% 0.0% Carbonate ( C 0 3 ) 60.00 0.00937 0.02811 0 . 1 % 0 . 1 % Bicarbonate ( H C 0 3 ) 61.00 0.53447 1.60341 6.8% 4 . 5 % Water (H20 ) (see note) 18.00 4.3955925 Vent Gas Oxygen (02) 32.00 9.0012 2 5 . 3 % Nitrogen (N2) 28.01 2 .4328 5 7 . 1 % Nitrous O x i d e (N20) 44.01 1.0174 0.5811 2 3 . 9 % Carbon Monox ide (CO) 28.01 0.0001 0.0002 0 .0% 0.0% Carbon Diox ide ( C 0 2 ) 44.01 6.3710 16.9731 8 1 . 1 % 47 .8% Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.5131 0 .0% Total Effluents 4.253 6.919 32.586 Recove ry (effluent/influent)x100 % 99.82 88.11 91.77 Destruction Efficiencies Effluent C o m m e n t s 99 .996% N o n e detected in effluent Total A m m o n i a 4 9 . 5 0 % T O C 9 9 . 9 8 % N o n e detected in effluent C O yield 0.002 C 0 2 yield 0.92 N 2 0 0.16 N2 yield 0.390 Notes: Vent gas f low ca lcu la ted from molar ba lance, Tab le H.4 Water molar f lows calcu lated according to Equat ion [31] 146 2.4 DNP and ammonia Run 2 Date of test: Data file Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 flow rate Stoichiometric 0 2 flow rate Vent Gas Flow rate July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 1.016 kg/h 16.93817 g/min 0.83 kg/h 0.7210 gmol/min See Note 22.44 % Excess Aqueous Stream Ana lys is Sample Location Feed Effluent PH1 In P H 2 i n Ph2 out RL2 in RL6 in (GLS) Total Ammonia (pgN/g) 2000 1090 Ratio NH3/TOC (mole/mole) 0.19367496 467.3474 Total Organic Carbon (pgC/g) 8855.23043 2 pH 9.2 Picric Acid (pq/g) < 1 <1 2,4-Dinitrophenol (pq/q) 22630 < 1 2,6-Dinitrophenol (pq/q) 111.8 <1 2-Nitrophenol (pq/q) <1 < 1 4-Nitrophenol (pq/q) <1 < 1 Phenol (pq/q) < 1 < 1 Nitrate (pg/g) <0.1 0.4 Nitrite (pq/q) <0.1 0.2 carbonate (pq/q) 3953.33 40 bicarbonate (pq/q) 1893.33 3920 Metals Calcium (pq/q) 0.21 Chromium (pg/g) 0.17 Copper (pq/q) 0.42 Iron (pg/q) <0.2 Potassium (pq/q) 1.31 Molybdenum (pq/q) <0.1 Sodium (pq/q) 0.69 Nickel (pg/g) 0.17 G a s e o u s Stream Ana lys is Sample Location effluent Oxygen (%) 7.21 Nitrogen (%) 10.63 Nitrous Oxide (%) 6.13 Carbon Monoxide (%) <0.1 Carbon Dioxide (%) 72.81 Hydrogen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.10 Abbreviat ion Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream Sample Locat ion Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 147 Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36.6% Total Carbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88.0% 2 7 . 1 % 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 . 1 % 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Pheno l ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0.0% Nitrate (N03) 61.99 0.00078 0.00267 0.0% 0.0% Nitrite (N02) 45.99 0.00078 0.00178 0.0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 O x y g e n (02) 32.00 16.938 5 9 . 9 % Wa te r (H20) 18.00 0.000 0 .0% Total Influent 4.261 7.853 28.280 Liquid Effluent Total A m m o n i a (as NH3) 17.031 0.850 20 .0% T O C 12.011 0.002 0 .0% 0.0% Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2-Nitroph'enol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.001 0.000 0.0% 0.0% 0.0% Nitrate (N03 ) 61.99 0.00031 0.00000 0.0% 0.0% 0 .0% Nitrite (N02) 45.99 0.00016 0.00018 0 .0% 0 .0% Carbonate ( C 0 3 ) 60.00 0.00625 0.01874 0 . 1 % 0 . 1 % Bicarbonate ( H C 0 3 ) 61.00 0.60205 1.80614 7 .7% 6.4% Water (H20) (see note) 18.00 4.2885581 Vent Gas O x y g e n (02) 32.00 1.6634 5 .9% Nitrogen (N2) 28.01 2.1470 50 .4% Nitrous Ox ide (N20) 44.01 1.2380 0.7072 2 9 . 1 % Carbon Monox ide (CO) 28.01 0.0001 0.0001 0 .0% 0.0% Carbon Dioxide ( C 0 2 ) 44.01 6.3053 16.7981 80 .3% 59 .4% Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.3830 0 .0% Total Effluents 4.236 6.917 25.284 Recovery (effluent/influent)x100 % 99.42 88.09 89.41 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 9 9 . 9 9 6 % None detected in effluent Total A m m o n i a 4 5 . 5 0 % T O C 9 9 . 9 8 % None detected in effluent C O yie ld 0.001 C 0 2 yield 0.91 N 2 0 0.20 N2 y ie ld 0.34 Notes: Vent gas f low calculated from molar ba lance, T a b l e H.4 Wate r molar f lows calculated according to Equat ion [31] 148 2.4 DNP and ammonia Run 2b Date of test: Data file Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 tlowrate Stoichiometric 0 2 flow rate Vent Gas Flow rate Aqueous Stream Ana lys is July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.78O litres/min 0.833 kg/h 13.883333 g/min 0.83 kg/h 0.656O gmol/min See Note 0.36 % Excess Sample Location Feed Effluent PH1 In PH2 In Ph2 out R L 2 In RL6 In (GLS) Total Ammonia (pgN/q) 2000 1260 Ratio NH3/TOC (mole/mole) 0.19367496 540.2365 Total Organic Carbon (pgC/g) 8855.23043 2 pH 9.2 Picric Acid (pq/q) <1 < 1 2,4-Dinitrophenol (pq/q) 22630 < 1 2,6-Dinitrophenol (pg/g) 111.8 < 1 2-Nitrophenol (pq/g) < 1 < 1 4-Nitrophenol (pq/q) < 1 < 1 Phenol (pq/q) <1 < 1 Nitrate (pq/q) <0.1 0.2 Nitrite (pg/q) <0.1 0.1 carbonate (pq/q) 3953.33 500 bicarbonate (pq/q) 1893.33 3940 Metals Calcium (pq/q) Chromium (pq/q) Copper (pg/g) Iron (pg/g) Potassium (pg/q) Molybdenum (pg/q) Sodium (pq/q) Nickel (pg/g) G a s e o u s Stream Analys is Sample Location effluent Oxygen (%) 0.00 Nitrogen (%) 12.39 Nitrous Oxide (%) 5.30 Carbon Monoxide (%) <0.1 Carbon Dioxide (%) 79.09 Hydroqen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.1O Abbreviat ion Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream Sample Locat ion Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 149 2.4 DNP and ammonia Run 2b Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M.W. g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total Carbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88 .0% 30 .4% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 .2% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0.0% Nitrate (N03) 61.99 0.00078 0.00267 0 .0% 0.0% Nitrite (N02) 45.99 0.00078 0.00178 0 .0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 Oxygen (02) 32.00 13.883 55 .0% Wate r (H20) 18.00 0.000 0.0% Total Influent 4.261 7.853 25.225 Liquid Effluent Total A m m o n i a (as NH3) 17.031 0.983 2 3 . 1 % T O C 12.011 0.002 0.0% 0.0% Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.001 0.000 0 .0% 0.0% 0.0% Nitrate (N03) 61.99 0.00016 0.00000 0 .0% 0.0% 0.0% Nitrite (N02) 45.99 0.00008 0.00018 0 .0% 0.0% Carbonate ( C 0 3 ) 60.00 0.07807 0.23421 1.0% 0.9% Bicarbonate ( H C 0 3 ) 61.00 0.60512 1.81535 7.7% 7.2% Water (H20) (see note) 18.00 4.0611101 Vent Gas Oxygen (02) 32.00 0.0000 0 .0% Nitrogen (N2) 28.01 2.2769 53 .4% Nitrous O x i d e (N20) 44.01 0.9739 0.5563 22 .9% Carbon Monox ide (CO) 28.01 0.0001 0.0001 0 .0% 0.0% Carbon Dioxide ( C 0 2 ) 44.01 6.2317 16.6020 79 .4% 65 .8% Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.3485 0 .0% Total Effluents 4.234 6.918 23.271 Recovery (effluent/influent)x100 % 99.37 88.10 92.25 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 99 .996% None detected in effluent Total A m m o n i a 37 .00% T O C 99 .98% None detected in effluent C O yield 0.001 C 0 2 yield 0.90 N 2 0 0.16 N2 yield 0.36 Notes: Vent gas f low calculated from molar ba lance, Tab le H.4 Water molar f lows calculated according to Equat ion [31] 150 2.4 DNP and ammonia Run 2c Date of test: Data file Feed Feed concentration Feed total ammonia Feed TOC Feed Flow rate 0 2 flow rate Stoichiometric 0 2 flow rate Vent Gas Flow rate Aqueous Stream Ana lys is July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 0.590 kg/h 9.8310757 g/min 0.83 kg/h 0.4610 gmol/min See Note -28.93 % Excess Sample Location Feed Effluent PH1 In P H 2 i n Ph2 out RL2 In RL6 In (GLS) Total Ammonia (uqN/q) 2000 1690 Ratio NH3/TOC (mole/mole) 0.19367496 16.10229 Total Organic Carbon (jjgC/g) 8855.23043 90 PH 9.2 Picric Acid (ug/q) <1 < 1 2,4-Dinitrophenol (uq/q) 22630 < 1 2,6-Dinitrophenol (uq/q) 111.8 < 1 2-Nitrophenol (uq/q) < 1 < 1 4-Nitrophenol (uq/q) < 1 < 1 Phenol (pg/g) < 1 10.3 Nitrate (uq/g) <0.1 <0.1 Nitrite (uq/q) <0.1 <0.1 carbonate (uq/q) 3953.33 0 bicarbonate (uq/q) 1893.33 5940 Metals Calcium (uq/q) Chromium (uq/q) Copper (uq/q) Iron (ug/g) Potassium (ug/q) Molybdenum (uq/q) Sodium (uq/q) Nickel (ug/g) G a s e o u s Stream Ana lys is Sample Location effluent Oxygen (%) 0.00 Nitrogen (%) 19.73 Nitrous Oxide (%) 2.93 Carbon Monoxide (%) 3.58 Carbon Dioxide (%) 70.55 Hydrogen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 100.11 Abbreviat ion Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Locat ion Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet • Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 151 2.4 DNP and ammonia Run 2c Mass Balance Nitrogen C a r b o n O x y g e n Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M.W. g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 3 6 . 6 % Total Ca rbon less T O C n/a in 2 .4dnp T O C n/a in 2 .4dnp Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2,4-Dini trophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 ' '6.909 7.670 63 .0% 8 8 . 0 % 3 6 2 % 2,6-Dini trophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0 .4% 0 .2% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0 .0% Nitrate (N03) 61.99 0.00078 0.00267 0 .0% 0 .0% Nitrite (N02 ) 45.99 0.00078 0.00178 0 .0% 0 .0% Carbona te 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 O x y g e n (02) 32.00 9.831 4 6 . 4 % Wate r (H20 ) 18.00 0.000 0 .0% Total Influent 4.261 7.853 21.173 Liquid Effluent Total A m m o n i a (as NH3) 17.031 1.318 3 0 . 9 % T O C 12.011 0.070 0 .0% 0 .9% Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2,4-Dini trophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2,6-Dini t rophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% Pheno l ( C 6 H 6 0 ) 94.11 0.006 0.001 0 .0% 0 . 1 % 0 .0% Nitrate (N03 ) 61.99 0.00008 0.00000 0 .0% 0 .0% 0 .0% Nitrite (N02) 45.99 0.00008 0.00018 0 .0% 0 .0% Carbona te ( C 0 3 ) 60.00 0.00000 0.00000 0 .0% 0 .0% Bicarbonate ( H C 0 3 ) 61.00 0.91228 2.73685 11 .6% 12 .9% Water (H20 ) (see note) 18.00 3.4858005 Vent Gas O x y g e n (02) 32.00 0.0000 0 .0% Nitrogen (N2) 28.01 2 .5480 5 9 . 8 % Nitrous O x i d e (N20 ) 44.01 0.3783 0.2161 8 .9% Carbon Monox ide (CO) 28.01 0.1982 0.2641 ' 2 . 5 % 1.2% Carbon D iox ide ( C 0 2 ) 44.01 3.9064 10.4071 4 9 . 7 % 4 9 . 2 % Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.2449 0 .0% Total Effluents 4.245 5.095 17.113 Recove ry (eff luent/influent)x100 % 99.63 64.88 80.82 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 9 9 . 9 9 6 % None detected in effluent Total A m m o n i a 15 .50% T O C 9 8 . 9 8 % C O yie ld 0.03 C 0 2 y ie ld 0.57 N 2 0 0.06 N2 y ie ld 0.41 Wofes; Vent gas f low ca lcu la ted from molar ba lance , Tab le H.4 Wate r molar f lows ca lcu la ted accord ing to Equat ion [31] 152 2.4 DNP and ammonia Run 3 Date ot test: Data tile Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 flow rate Stoichiometric 0 2 flow rate Vent Gas Flow rate Aqueous Stream Ana lys is July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as 2,4 Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 1.438 kg/h 23.968452 g/min 0.83 kg/h 0.9610 gmol/min See/Vote 73.27 % Excess Sample Location Feed Effluent PH1 In PH2in PH2out R L 2 In RL6 In Total Ammonia (as N) (ugN/q) 2000.00 1230.00 1280.00 479.00 380.00 989.00 1010.00 ratio NH3/TOC (mole/mole) 0.23 Total Organic Carbon (ugC/g) 8858.04 2560.00 1110.00 752.00 45.00 5.00 2.0 pH 9.22 8.02 7.97 7.99 9.24 8.24 7.9 Picric acid (ug/g) <1 14.8 25.8 0 0 <0.1 <0.1 2,4-Dinitrophenol (ug/g) 22630 1581.5 421.4 91.5 0.3 <0.1 <0.1 2,6-Dinitrophenol (ug/g) 111.8 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 2-Nitrophenol (ug/g) <1 231.1 < 1 < 1 1.9 < 1 < 1 4-Nitrophenol (ug/g) < 1 166.1 < 1 < 1 0 < 1 < 1 Phenol (ug/g) <1 0 < 1 < 1 0 < 1 < 1 Nitrate (N03) (as N) (uq/q) <0.1 1.4 0.7 3 0.5 <0.1 <0.1 Nitrite (N02) (as N)(uq/q) <0.1 0.6 5.7 8.8 <0.1 <0.1 <0.1 Carbonate(C03) 3953.33 0 0 0 520 320 0 Bicarbonate(HC03) 1893.33 3080 1220 3560 760 3220 3470 Metals Calcium (ug/g) 0.27 Cobalt <0.05 Chromium (ug/g) 0.24 Copper (ug/g) 0.13 Iron (ug/g) <0.2 Potassium (ug/g) 0.69 Molybdenum (uq/q) 0.11 Sodium (uq/q) 1.03 Nickel (ug/g) . 0.13 G a s e o u s Stream Ana lys is Sample Location. . PH1 PH2 Effluent Oxygen (%) 38.94 31.62 28.63 Nitrogen (%), 14.51 12.99 7.83 Nitrous Oxide (%) . 0.00 1.48 5.00 Carbon Monoxide (%) 2.69 1.82 <0.1 Carbon Dioxide (%) 40.65 48.87 55.34 Nitrous Dioxide (%) <0.1 <0.1 <0.1 Methane (%) n.d n.d n.d Ethane (%) n.d n.d n.d water vapor [%]' 3.32 3.32 3.32 total . . . 100.11 100.10 100.12 Abbreviat ion Feed Effluent PH2_in PH2_out RL2_in . RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Locat ion Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 153 2.4 DNP and ammonia Run 3 Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total Carbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0 .0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88 .0% 2 1 . 7 % 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 . 1 % 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0.0% Nitrate (N03) 61.99 0.00078 0.00267 0 .0% 0.0% Nitrite (N02) 45.99 0.00078 0.00178 0 .0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 Oxygen (02) 32.00 23.968 67 .9% Wate r (H20) 18.00 0.000 0 .0% Total Influent 4.261 7.853 35.310 Liquid Effluent Total A m m o n i a (as NH3) 17.031 0.788 18 .5% T O C 12.011 0.002 0 .0% 0.0% Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0 .0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.001 0.000 0 .0% 0.0% 0.0% Nitrate (N03) 61.99 0.00008 0.00027 0 .0% 0.0% 0.0% Nitrite (N02) 45.99 0.00008 0.00018 0 .0% 0.0% Carbonate ( C 0 3 ) 60.00 0.00000 0.00000 0 .0% 0.0% Bicarbonate ( H C 0 3 ) 61.00 0.53293 1.59880 6 .8% 4 . 5 % Water (H20) (see note) 18.00 4.3955925 Vent Gas Oxygen (02) 32.00 8.8040 2 4 . 9 % Nitrogen (N2) 28.01 2.1079 4 9 . 5 % Nitrous Ox ide (N20) 44.01 1.3459 0.7688 31 .6% Carbon Monox ide (CO) 28.01 0.0001 0.0002 0.0% 0 .0% Carbon Dioxide ( C 0 2 ) 44.01 6.3877 17.0175 8 1 . 3 % 4 8 . 2 % Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.5105 0 .0% Total Effluents 4.242 6.925 32.587 Recovery (effluent/influent)x100 % 99.56 88.18 92.29 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 99 .996% None detected in effluent Total A m m o n i a 49 .50% T O C 9 9 . 9 8 % None detected in effluent C O yield 0.002 C 0 2 yield 0.92 N 2 0 0.22 N2 yield 0.34 Notes: Vent gas f low calculated from molar ba lance , Tab le H.4 Wate r molar f lows calculated according to Equat ion [31] 154 2.4 DNP and ammonia Run 4 Date of test: Data file Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 flow rate Stoichiometric 0 2 flow rate Vent Gas Flow rate A q u e o u s Stream Ana lys i s July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 1.00 kg/h 16.745879 g/min 0.83 kg/h 0.7090 gmol/min See Note 21.05 % Excess Sample Location Feed Effluent PH1 in PH2 In Ph2 out R L 2 in RL6 in (GLS) Total Ammonia (pqN/q) 2000 1130 Ratio NH3/TOC (mole/mole) 0.19367496 484.4978 Total Organic Carbon (pgC/g) 8855.23043 2 pH 9.2 Picric Acid (pg/g) < 1 < 1 2,4-Dinitrophenol (pq/q) 22630 < 1 2,6-Dinitrophenol (pq/g) 111.8 < 1 2-Nitrophenol (pq/q) < 1 < 1 4-Nitrophenol (pq/q) <-1 < 1 Phenol (pq/q) <1 < 1 Nitrate (pq/q) <0.1 0.3 Nitrite (pq/q) <0.1 <0.1 carbonate (pq/q) 3953.33 60 bicarbonate (pq/q) 1893.33 3940 Metals Calcium (pg/g) 0.670853 Chromium (pg/g) 0.14165 Copper (pq/q) 0.223907 Iron (pq/q) <0.2 Potassium (pq/q) 1.212058 Molybdenum (pq/q) <0.1 Sodium (pq/q) 1722236 Nickel (pg/g) 0.126336 G a s e o u s Stream Ana lys i s Sample Location effluent Abbreviat ion Sample Locat ion Oxyqen (%) 5.91 Feed Feed prior to test Nitrogen (%) 11.28 Effluent Final effluent Nitrous Oxide (%) 5.63 PH2 in Preheater 2 Inlet Carbon Monoxide (%) <0.1 PH2 out Preheater 2 Outlet Carbon Dioxide (%) 73.97 RL2 in Reactor Section 2 Inlet Hydroqen (%) <0.1 RL6 in Reactor Section 6 Inlet Methane (%) n.d Gaseous stream PH1 Vent gas (GLS) PH1 in Ethane (%) n.d Gaseous stream PH2 Vent gas (GLS) PH2 water vapor [%] 3.32 Gaseous stream Vent gas (GLS) effluent total 100.11 155 2.4 DNP and ammonia Run 4 Mass Balance Nitrogen Carbon O x y g e n Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Tota l A m m o n i a (as NH3) 17.031 1.560 3 6 . 6 % Tota l Ca rbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp P ic r i c A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2 ,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2 .686 6.909 7.670 63 .0% 8 8 . 0 % 2 7 . 3 % 2 ,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0 .4% 0.1 % 2-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% P h e n o l (C6H6O) 94.11 0.000 0.000 0 .0% 0 .0% Nitrate (N03) 61.99 0.00078 0.00267 0 .0% 0 .0% Nitrite (N02) 45.99 0.00078 0.00178 0 .0% 0 .0% C a r b o n a t e 60.00 0.61728 2.46679 B ica rbona te 61.00 0.29078 1.16203 O x y g e n (02) 32.00 16.746 59 .6% W a t e r (H20) 18.00 0.000 0 .0% Total Influent 4.261 7.853 28.088 Liquid Effluent Tota l A m m o n i a (as NH3) 17.031 0.881 2 0 . 7 % T O C 12.011 0.002 0 .0% 0 .0% P i c r i c A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2 ,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2 ,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% P h e n o l (C6H6O) 94.11 0.001 0.000 0 .0% 0 .0% 0 .0% Nitrate (N03) 61.99 0.00008 0.00000 0 .0% 0 .0% 0 .0% Nitr i te (N02) 45.99 0.00008 0.00018 0 .0% 0 .0% C a r b o n a t e ( C 0 3 ) 60 .00 0.00937 0.02811 0 . 1 % 0 . 1 % B icarbona te ( H C 0 3 ) 61.00 0.60512 1.81535 7 .7% 6 .5% W a t e r (H20 ) (see note) 18.00 4.235041 Vent Gas O x y g e n (02) 32.00 1.3408 4 . 8 % Ni t rogen (N2) 28.01 2.2404 5 2 . 6 % Ni t rous O x i d e (N20 ) 44.01 1.1181 0.6387 2 6 . 2 % C a r b o n Monox ide (CO) 28.01 0.0001 0.0001 0 .0% 0 .0% C a r b o n Diox ide ( C 0 2 ) 44.01 6.2991 16.7817 8 0 . 2 % 5 9 . 7 % Hydrogen (H2) 2 .016 M e t h a n e (CH4) 16.04 0.0000 0 .0% E thane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.3766 0 .0% Total Effluents 4.240 6.917 24.841 R e c o v e r y (effluentVinfluent)xlOO % 99.52 88.09 88.44 Destruction Efficiencies Effluent C o m m e n t s Dini t rophenol 9 9 . 9 9 6 % None detected in effluent To ta l A m m o n i a 4 3 . 5 0 % T O C 9 9 . 9 8 % C O yie ld 0.001 C 0 2 yield 0.91 N 2 0 0.18 N2 y ie ld 0.36 Notes: Ven t gas f low ca lcu la ted from molar ba lance , T a b l e H.4 W a t e r molar f lows ca lcu la ted accord ing to Equat ion [31] 156 2.4 DNP and ammonia Run 4b Date of test: Data file Feed Feed concentration Feed total ammonia Feed TOC Feed Flow rate 02 flow rate Stoichiometric 02 flow rate Vent Gas Flow rate Aqueous Stream Analysis July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as TOC 0.780 litres/min 0.81 kg/h 13.5705 g/min 0.83 kg/h 0.6530 gmol/min See Note -1.90 % Excess Sample Location Feed Effluent PH1 in PH2in Ph2 out RL2 in RL6 in (GLS) Total Ammonia (uqN/g) 2000 1320 Ratio NH3/TOC (mole/mole) 0.19367496 226.3848 Total Organic Carbon (ugC/g) 8855.23043 5 PH 9.2 Picric Acid (ug/g) < 1 < 1 2,4-Dinitrophenol (ug/g) 22630 < 1 2,6-Dinitrophenol (ug/g) 111.8 <1 2-Nitrophenol (uq/g) <1 < 1 4-Nitrophenol (uq/g) < 1 < 1 Phenol (uq/g) <1 < 1 Nitrate (uq/q) <0.1 0.1 Nitrite (uq/g) <0.1 <0.1 carbonate (uq/q) 3953.33 0 bicarbonate (uq/g) 1893.33 4580 Metals Calcium (ug/g) 0.23 Chromium (uq/g) 0.09 Copper (ug/g) 0.46 Iron (ug/g) <0.2 Potassium (uq/g) 0.75 Molybdenum (uq/q) <0.1 Sodium (uq/g) 0.82 Nickel (ug/g) 0.20 Gaseous Stream Analysis Sample Location effluent Oxygen (%) 0.00 Nitrogen (%) 12.49 Nitrous Oxide (%) 5.09 Carbon Monoxide (%) <0.1 Carbon Dioxide (%) 79.21 Hvdroqen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.11 Abbreviation Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Location Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 157 2.4 DNP and ammonia Run 4b Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total C a r b o n less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0.0% 0 .0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88 .0% 30 .8% 2,6-Dinrtrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 .2% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0.0% Nitrate ( N 0 3 ) 61.99 0.00078 0.00267 0 .0% 0.0% Nitrite ( N 0 2 ) 45.99 0.00078 0.00178 0 .0% 0.0% Carbona te 60.00 0.61728 2.46679 B icarbonate 61.00 0.29078 1.16203 O x y g e n (02) 32.00 13.571 5 4 . 5 % Water ( H 2 0 ) 18.00 0.000 0 .0% Total Influent 4.261 7.853 24.912 Liquid Effluent Total A m m o n i a (as NH3) 17.031 1.030 2 4 . 2 % T O C 12.011 0.004 0 .0% 0.0% Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0 .0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.001 0.000 0 .0% 0.0% 0.0% Nitrate ( N 0 3 ) 61.99 0.00008 0.00000 0 .0% 0 .0% 0.0% Nitrite ( N 0 2 ) 45.99 0.00008 0.00018 0 .0% 0.0% Carbona te (C03) 60.00 0.00000 0.00000 0 .0% 0.0% Bicarbonate ( H C 0 3 ) 61.00 0.70341 2.11023 9 .0% 8 .5% Water ( H 2 0 ) (see note) 18.00 3.9808344 Vent Gas O x y g e n (02) 32.00 0.0000 0 .0% Nitrogen (N2) 28.01 2.2848 53 .6% Nitrous O x i d e (N20 ) 44.01 0.9310 0.5318 21 .8% Carbon M o n o x i d e (CO) 28.01 0.0001 0.0001 0 .0% 0.0% Carbon D iox ide ( C 0 2 ) 44.01 6.2126 16.5511 7 9 . 1 % 66 .4% Hydrogen (H2) 2.016 Me thane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water v a p o r 18.00 0.3469 0 .0% Total Effluents 4.246 6.922 23.176 Recove ry (effluent/influent)x100 % 99.65 88.15 93.03 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 9 9 . 9 9 6 % None detected in effluent Total A m m o n i a 3 4 . 0 0 % T O C 9 9 . 9 4 % C O y ie ld 0.001 C 0 2 y ie ld 0.90 N 2 0 0.15 N2 yield 0.37 Notes: Vent g a s flow ca lcu la ted from molar ba lance, Tab le H.4 Water molar f lows calculated according to Equat ion [31] 158 2.4 DNP and ammonia Run 5 Date of test: Data file Feed Feed concentration Feed total ammonia Feed TOC Feed Flow rate 02 flow rate Stoichiometric 02 flow rate Vent Gas Flow rate A q u e o u s Stream Ana lys is July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as 2,4 Dinitrophenol 0.243 wr% as NH3 0.886 wt% as TOC 0.780 litres/min 1.483 kg/h 24.709772 g/min 0.83 kg/h 0.9680 gmol/min See Note 78.62 % Excess Sample Location Feed Effluent PH1 in PH2in PH2out RL2 In RL6 In Total Ammonia (as N) (ugN/q) 2000.00 1280.00 1140.00 1160.00 812.00 1040.00 1160.00 ratio NH3/TOC (mole/mole) 0.23 Total Organic Carbon (ugC/g) 8858.04 2290.00 1870.00 1300.00 130.00 21.00 3.0 PH 9.22 7.97 7.97 8.07 8.88 8.38 7.9 Picric acid (uq/q) < 1 14.6 48.2 <1 0.6 <1 <1 2,4-Dinitrophenol (uq/q) 22630 1556.9 1083.1 587.7 2.5 <1 <1 2,6-Dinitrophenol (uq/q) 111.8 <1 <1 <1 <1 <1 <1 2-Nitrophenol (uq/q) < 1 534.5 <1 <1 4.6 1.1 <1 4-Nitrophenol (uq/g) < 1 234.2 <1 <1 0.5 <1 <1 Phenol (uq/q) < 1 < 1 <1 <1 <1 <1 <1 Nitrate (N03) (as N) (uq/q) <0.1 <0.1 1.5 1.1 0.4 0.2 0.1 Nitrite (N02) (as N)(uq/q) <0.1 <0.1 2.1 0.4 <0.1 <0.1 <0.1 Carbonate(C03) 3953.33 0 0 120 0 360 200 -Bicarbonate(HC03) 1893.33 3420 4860 3380 2720 3760 3740 Metals Calcium (uq/q) 0.36 Cobalt <0.05 Chromium (uq/q) 0.24 Copper (uq/q) 0.49 Iron (uq/q) <0.2 Potassium (uq/q) 1.35 Molybdenum (uq/g) 0.12 Sodium (ug/q) 1.44 Nickel (ug/g) 0.14 G a s e o u s Stream Ana lys i s Sample Location PH1 PH2 Effluent Oxyqen (%) 39.87 34.49 30.19 Nitroqen (%) 13.73 12.26 6.98 Nitrous Oxide (%) 0.00 0.98 5.31 Carbon Monoxide (%) 3.25 7.12 <0.1 Carbon Dioxide (%) 39.94 41.93 54.30 Nitrous Dioxide (%) <0.1 <0.1 <0.1 Methane (%) n.d n.d n.d Ethane (%) n.d n.d n.d water vapor [%1 3.32 3.32 3.32 total 100.11 100.10 100.10 Abbreviation Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Location Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 159 2.4 DNP and ammonia Run 5 Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M.W. g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36.6% Total Ca rbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88 .0% 2 1 . 3 % 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 . 0.034 0.038 0 .3% 0.4% 0 . 1 % 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.000 0.000 0 .0% 0.0% Nitrate (N03 ) 61.99 0.00078 0.00267 0.0% 0.0% Nitrite (N02) 45.99 0.00078 0.00178 0.0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61 .00 0.29078 1.16203 Oxygen (02) 32 .00 24.710 6 8 . 5 % Wate r (H20) 18.00 0.000 0 .0% Total Influent 4.261 7.853 36.051 Liquid Effluent Total A m m o n i a (as NH3) 17.031 0.905 2 1 . 2 % T O C 12.011 0.002 0.0% 0.0% Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0.0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.001 0.000 0 .0% 0.0% 0 .0% Nitrate (N03) 61.99 0.00008 0.00027 0 .0% 0.0% 0 .0% Nitrite (N02) 45 .99 0.00008 0.00018 0 .0% 0.0% Carbonate ( C 0 3 ) 60.00 0.03123 0.09369 0.4% 0 .3% Bicarbonate ( H C 0 3 ) 61.00 0.57440 1.72320 7 .3% 4 .8% Water (H20) (see note) 18.00 4.1949031 Vent Gas Oxygen (02) 32.00 9.3513 25 .9% Nitrogen (N2) 28.01 1.8928 44 .4% Nitrous O x i d e (N20) 44.01 1.4397 0.0000 33 .8% Carbon Monox ide (CO) 28.01 0.0001 0.0002 0 .0% 0.0% Carbon Diox ide (C02 ) 44.01 6.3133 16.8193 80 .4% 46 .7% Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.5142 0 .0% Total Effluents 4.238 6.924 32.185 Recovery (effluent/influent)x100 % 99.46 88.17 89.27 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 9 9 . 9 9 6 % None detected in effluent Total A m m o n i a 4 2 . 0 0 % T O C 9 9 . 9 7 % C O yield 0.002 C 0 2 yield 0.91 N 2 0 0.23 N2 yield 0.30 Atofes: Vent gas f low calcu lated from molar ba lance, Tab le H.4 Wate r molar f lows calculated according to Equat ion [31] 160 2.4 DNP and ammonia Run 6 Date of test: Data file Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 flow rate Stoichiometric 0 2 flow rate Vent G a s Flow rate A q u e o u s Stream Ana lys is July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 0.96 kg/h 16.058348 g/min 0.83 kg/h 0.6800 gmol/min See Note 16.08 % Excess Sample Location Feed Effluent PH1 in P H 2 l n Ph2 out RL2 In RL6 in (GLS) Total Ammonia (ugN/g) 2000 1230 Ratio NH3/TOC (mole/mole) 0.19367496 105.4747 Total Organic Carbon (ugC/g) 8855.23043 10 PH 9.2 Picric Acid (ug/q) <1 <1 2,4-Dinitrophenol (ug/g) 22630 < 1 2,6-Dinitrophenol (uq/q) 111.8 <1 2-Nitrophenol (uq/q) <1 < 1 4-Nitrophenol (uq/q) <1 < 1 Phenol (uq/g) < 1 < 1 Nitrate (ug/g) <0.1 0.1 Nitrite (uq/q) <0.1 <0.1 carbonate (uq/g) 3953.33 40 bicarbonate (uq/q) 1893.33 3980 Metals Calcium (uq/q) 0.77 Chromium (uq/q) 0.13 Copper (uq/q) 0.37 Iron (uq/q) <0.2 Potassium (ug/g) 1.64 Molybdenum (ug/g) <0.1 Sodium (uq/q) 1.93 Nickel (ug/g) 0.13 G a s e o u s Stream Ana lys is Sample Location effluent Oxygen (%) 2.50 Nitrogen (%) 11.16 Nitrous Oxide (%) 6.07 Carbon Monoxide (%) <0.1 Carbon Dioxide (%) 77.07 Hydroqen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.12 Abbreviat ion Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Locat ion Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 161 2.4 DNP and ammonia Run 6 Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M.W. g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total Carbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88 .0% 2 8 . 0 % 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 . 1 % 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0.0% 0.0% Nitrate (N03) 61.99 0.00078 0.00267 0 .0% 0.0% Nitrite (N02) 45.99 0.00078 0.00178 0 .0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 Oxygen (02) 32.00 16.058 58 .6% Water (H20) 18.00 0.000 0 .0% Total Influent 4.261 7.853 27.400 Liquid Effluent Total A m m o n i a (as NH3) 17.031 0.959 2 2 . 5 % T O C 12.011 0.008 0 .0% 0 . 1 % Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol (C6H6O) 94.11 0.001 0.000 0 .0% 0.0% 0.0% Nitrate (N03) 61.99 0.00008 0.00000 0 .0% 0.0% 0 .0% Nitrite (N02) 45.99 0.00008 0.00018 0 .0% 0 .0% Carbonate (C03 ) 60.00 0.00625 0.01874 0 . 1 % 0 . 1 % Bicarbonate ( H C 0 3 ) 61.00 0.61126 1.83378 7.8% 6 .7% Water (H20) (see note) 18.00 4.101248 Vent Gas Oxygen (02) 32.00 0.5440 2 . 0 % Nitrogen (N2) 28.01 2 .1259 49 .9% Nitrous O x i d e (N20) 44.01 1.1561 0.6604 2 7 . 1 % Carbon Monox ide (CO) 28.01 0.0001 0.0001 0 .0% 0.0% Carbon Dioxide ( C 0 2 ) 44.01 6.2947 16.7698 8 0 . 2 % 61 .2% Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0.0% Ethane (C2H6) 30.07 0.0000 0.0% water vapor 18.00 0.3612 0 .0% Total Effluents 4.242 6.922 23.930 Recovery (effluent/influent)x100 % 99.56 88.15 87.33 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 99 .996% None detected in effluent Total A m m o n i a 3 8 . 5 0 % T O C 9 9 . 8 9 % C O yield 0.001 C 0 2 yield 0.911 N 2 0 0.185 N2 yield 0.341 Atofes: Vent gas f low calcu lated from molar ba lance, Tab le H.4 Water molar f lows ca lcu la ted according to Equat ion [31] 162 2.4 DNP and ammonia Run 6b Date of test: Data file Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 flow rate Stoichiometric 0 2 flow rate Vent Gas Flow rate Aqueous Stream Ana lys is July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 0.86 kg/h 14.307429 g/min 0.83 kg/h 0.6520 gmol/min S e e Wore 3.43 % Excess Sample Location Feed Effluent PH1 in P H 2 i n P h 2 out RL2 In RL6 in (GLS) Total Ammonia (pqN/g) 2000 1300 Ratio NH3/TOC (mole/mole) 0.19367496 222.9547 Total Organic Carbon (pgC/g) 8855.23043 5 PH 9.2 Picric Acid (pq/q) <1 < 1 2,4-Dinitrophenol (pg/g) 22630 < 1 2,6-Dinitrophenol (pg/g) 111.8 < 1 2-Nitrophenol (pg/g) < 1 < 1 4-Nitrophenol (pg/g) < 1 < 1 Phenol (pg/g) < 1 < 1 Nitrate (pq/q) <0.1 <0.1 Nitrite (pq/q) <0.1 <0.1 carbonate (pq/q) 3953.33 0 bicarbonate (pq/q) 1893.33 4660 Metals Calcium (pq/q) 0.31 Chromium (pq/q) 0.11 Copper (pq/g) 0.44 Iron (pg/g) <0.2 Potassium (pq/q) 0.63 Molybdenum (pq/q) <0.1 Sodium (pg/q) 1.00 Nickel (pg/g) 0.15 G a s e o u s Stream Ana lys is Sample Location effluent Oxygen (%) 0.00 Nitrogen (%) 11.37 Nitrous Oxide (%) 6.31 Carbon Monoxide (%) <0.1 Carbon Dioxide (%) 79.10 Hydroqen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.10 Abbreviat ion Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Locat ion Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 163 2.4 DNP and ammonia Run 6b Mass Balance Nitrogen C a r b o n Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total Carbon less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2.686 6.909 7.670 63 .0% 88 .0% 2 9 . 9 % 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 . 1 % 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0.0% 0.0% Nitrate (N03) 61.99 0.00078 0.00267 0.0% 0.0% Nitrite (N02) 45.99 0.00078 0.00178 0 .0% 0.0% Carbonate 60.00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 Oxygen (02) 32.00 14.307 55 .8% Wate r (H20) 18.00 0.000 0 .0% Total Influent 4.261 7.853 25.649 Liquid Effluent Total A m m o n i a (as NH3) 17.031 1.014 2 3 . 8 % T O C 12.011 0.004 0 .0% 0.0% Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0.0% 0.0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.001 0.000 0 .0% 0.0% 0.0% Nitrate (N03) 61.99 O.00008 0.00000 0 .0% 0.0% 0.0% Nitrite (N02) 45.99 0.00008 0.00018 0 .0% 0.0% Carbonate (C03 ) 60.00 0.00000 0.00000 0 .0% 0.0% Bicarbonate ( H C 0 3 ) 61.00 0.71570 2.14709 9 . 1 % 8 .4% Water (H20) (see note) 18.00 4.007593 Vent Gas Oxygen (02) 32.00 0.0000 0 .0% Nitrogen (N2) 28.01 2.0767 48 .7% Nitrous O x i d e (N20) 44.01 1.1524 0.6583 27 .0% Carbon Monox ide (CO) 28.01 0.0001 0.0001 0.0% 0.0% Carbon Dioxide ( C 0 2 ) 44.01 6.1945 16.5028 78 .9% 64 .3% Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.3463 0 .0% Total Effluents 4.244 6.916 23.317 Recovery (effluent/influent)x100 % 99.59 88.07 90.91 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 99 .996% None detected in effluent Total A m m o n i a 35 .00% T O C 99 .94% C O yield 0.001 C 0 2 yield 0.896 N 2 0 0.185 N2 yield 0.333 Atofes; Vent gas f low calcu lated from molar ba lance, Tab le H.4 Wate r molar f lows calculated according to Equat ion [31] 164 2.4 DNP and ammonia Run 6c Date of test Data file Feed Feed concentration Feed total ammonia Feed T O C Feed Flow rate 0 2 flow rate Stoichiometric 02 flow rate Vent Gas Flow rate July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as Dinitrophenol 0.243 wt% as NH3 0.886 wt% as T O C 0.780 litres/min 0.68 kg/h 0.83 kg/h 0.6380 gmol/min 11.29 g/min 13.83 g/min See Note -18.40 % Excess Aqueous Stream Analysis Sample Location Feed Effluent PH1 in PH2 in Ph2 out RL2 In RL6 In (GLS) Total Ammonia (ugN/g) 2000 1480 Ratio NH3/TOC (mole/mole) 0.19367496 40.93958 Total Orqanic Carbon (pqC/q) 8855.23043 31 pH 9.2 Picric Acid (pg/g) < 1 <1 2,4-Dinitrophenol (gq/q) 22630 <1 2,6-Dinitrophenol (uq/q) 111.8 < 1 2-Nitrophenol (pq/q) <1 < 1 4-Nitrophenol (pq/q) <1 <1 Phenol (pq/q) < 1 < 1 Nitrate (pq/q) <0.1 <0.1 Nitrite (uq/q) <0.1 <0.1 carbonate (pq/q) 3953.33 0 bicarbonate (pq/q) 1893.33 5280 Metals Calcium (pq/q) 0.33 Chromium (pq/q) <0.05 Copper (pq/q) 2.42 Iron (pq/q) <0.2 Potassium (pq/q) <0.5 Molybdenum (pq/q) <0.1 Sodium (uq/q) 0.69 Nickel (pg/g) 0.12 G a s e o u s Stream Analysis Sample Location effluent Oxygen (%) 0.00 Nitroqen (%) 12.53 Nitrous Oxide (%) 4.77 Carbon Monoxide (%) 1.29 Carbon Dioxide (%) 78.20 Hydroqen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.11 Abbreviation Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream Sample Location Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 165 2.4 DNP and ammonia Run 6c Mass Balance Nitrogen Carbon Oxygen Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M.W. g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total C a r b o n less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 • 0.000 0.000 0 .0% 0.0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 2 .686 6.909 7.670 63 .0% 88 .0% 33 .9% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 .2% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0.0% Nitrate ( N 0 3 ) 61.99 0.00078 0.00267 0 .0% 0.0% Nitrite (N02 ) 45.99 0.00078 0.00178 0 .0% 0.0% Carbonate 60 .00 0.61728 2.46679 Bicarbonate 61.00 0.29078 1.16203 Oxygen (02) 32.00 11.289 49 .9% Water (H20 ) 18.00 0.000 0 .0% Total Influent 4.261 7.853 22.630 Liquid Effluent Total A m m o n i a (as NH3) 17.031 1.154 2 7 . 1 % T O C 12.011 0.024 0 .0% 0 .3% Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0.0% 2,4-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0.0% 0.0% 2,6-Dinitrophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0.0% 2-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0.0% 4-Nitrophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% Phenol ( C 6 H 6 0 ) 94.11 0.001 0.000 0 .0% 0 .0% 0.0% Nitrate ( N 0 3 ) 61.99 0.00008 0.00000 0 .0% 0 .0% 0.0% Nitrite (N02) 45.99 0.00008 0.00018 0 .0% 0.0% Carbonate ( C 0 3 ) 60 .00 0.00000 0.00000 0 .0% 0.0% Bicarbonate ( H C 0 3 ) 61 .00 0.81092 2.43276 10 .3% 10.8% Water (H20) (see note) 18.00 3.7667657 Vent Gas Oxygen (02) 32.00 0.0000 0 .0% Nitrogen (N2) 28.01 2.2394 52 .6% Nitrous O x i d e (N20) 44.01 0.8524 0.4869 2 0 . 0 % Carbon Monox ide (CO) 28.01 0.0989 0.1317 1.3% 0.6% Carbon Diox ide (C02 ) 44.01 5.9925 15.9647 7 6 . 3 % 7 0 . 5 % Hydrogen (H2) 2 .016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.3389 0 .0% Total Effluents 4.247 6.928 22.784 Recovery (effluent/influent)x100 % 99.67 88.23 100.68 Destruction Efficiencies Effluent C o m m e n t s Dinitrophenol 9 9 . 9 9 6 % None detected in effluent Total A m m o n i a 2 6 . 0 0 % T O C 9 9 . 6 5 % C O yield 0.014 C 0 2 yield 0.867 N 2 0 0.137 N2 yield 0.359 Notes: Vent gas f low calcu lated from molar ba lance, Tab le H.4 Water molar f lows calcu lated according to Equat ion [31] 166 2.4 DNP and ammonia Run 7 Date of test: Data file Feed Feed concentration Feed total ammonia Feed TOC Feed Flow rate 02 flow rate Stoichiometric 02 flow rate Vent Gas Flow rate Aqueous Stream Analysis July 4th, 2002 jul4.txt Ammonium 2,4 Dinitrophenolate 2.264 wt% as 2,4 Dinitrophenol 0.243 wt% as NH3 0.886 wt% as TOC 0.780 litres/min 1.437 kg/h 23.951905 g/min 0.83 kg/h 0.9420 gmol/min See Note 73.15 % Excess Sample Location Feed Effluent PH1 in PH2 in Ph2 out RL2 In RL6 In (GLS) Total Ammonia (pgN/g) 2000 1150 Ratio NH3/TOC (mole/mole) 0.19367496 65.74306 Total Orqanic Carbon (pqC/q) 8855.23043 15 pH 9.2 Picric Acid (pg/g) < 1 < 1 2,4-Dinitrophenol (pq/q) 22630 < 1 2,6-Dinitrophenol (pq/q) 111.8 < 1 2-Nitrophenol (pq/q) < 1 0.5 4-Nitrophenol (pq/g) < 1 < 1 Phenol (pg/q) < 1 < 1 Nitrate (pq/q) <0.1 0.2 Nitrite (pq/q) <0.1 <0.1 carbonate (pq/q) 3953.33 0 bicarbonate (pq/q) 1893.33 4020 Metals Calcium (pg/g) 0.26 Chromium (pg/g) 0.20 Copper (pq/q) 0.41 Iron (pg/g) <0.2 Potassium (pq/q) 0.65 Molybdenum (pq/q) 0.12 Sodium (pq/q) 3.10 Nickel (pg/g) 0.12 Gaseous Stream Analysis Sample Location effluent Oxyqen (%) 28.53 Nitroqen (%) 8.35 Nitrous Oxide (%) 4.33 Carbon Monoxide (%) <0.1 Carbon Dioxide (%) 55.58 Hydroqen (%) <0.1 Methane (%) n.d Ethane (%) n.d water vapor [%] 3.32 total 100.11 Abbreviation Feed Effluent PH2_in PH2_out RL2_in RL6_in Gaseous stream PH1 Gaseous stream PH2 Gaseous stream effluent Sample Location Feed prior to test Final effluent Preheater 2 Inlet Preheater 2 Outlet Reactor Section 2 Inlet Reactor Section 6 Inlet Vent gas (GLS) PH1 in Vent gas (GLS) PH2 Vent gas (GLS) effluent 167 2.4 DNP and ammonia Run 7 Mass Balance Nitrogen C a r b o n O x y g e n Nitrogen Carbon Oxygen 14.0067 12.011 15.9994 % of infl. % of infl. % of infl. Component M . W . g/min g/min g/min Feed Total A m m o n i a (as NH3) 17.031 1.560 36 .6% Total C a r b o n less T O C n/a in 2.4dnp T O C n/a in 2.4dnp Picr ic Ac id ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2,4-Dini t rophenol ( C 6 H 4 N 2 0 5 ) 184.11 2 .686 6.909 7.670 63 .0% 8 8 . 0 % 2 1 . 7 % 2,6-Dini t rophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.013 0.034 0.038 0 .3% 0.4% 0 . 1 % 2-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% Phenol ( C 6 H 6 0 ) 94.11 0.000 0.000 0 .0% 0 .0% Nitrate ( N 0 3 ) 61.99 0 .00078 0.00267 0 .0% 0 .0% Nitrite ( N 0 2 ) 45.99 0 .00078 0.00178 0 .0% 0 .0% Carbonate 60.00 0.61728 2.46679 B icarbonate 61.00 0.29078 1.16203 O x y g e n (02 ) 32.00 23.952 6 7 . 9 % Wate r ( H 2 0 ) 18.00 0.000 0 .0% Total Influent 4.261 7.853 35.294 Liquid Effluent Total A m m o n i a (as NH3) 17.031 0.897 2 1 . 1 % T O C 12.011 0.012 0 .0% 0 . 1 % Picr ic A c i d ( C 6 H 3 N 3 0 7 ) 229.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2,4-Dini t rophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2,6-Dini t rophenol ( C 6 H 4 N 2 0 5 ) 184.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 2-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% 4-Ni t rophenol ( C 6 H 5 N 0 3 ) 139.11 0.000 0.000 0.000 0 .0% 0 .0% 0 .0% Pheno l (C6H6O) 94.11 0.001 0.000 0 .0% 0 .0% 0 .0% Nitrate ( N 0 3 ) 61.99 0 .00008 0.00000 0 .0% 0 .0% 0 .0% Nitrite ( N 0 2 ) 45.99 0 .00008 0.00018 0 .0% 0 .0% Carbonate ( C 0 3 ) 60 .00 0.00000 0.00000 0 .0% 0 .0% Bicarbonate ( H C 0 3 ) 61 .00 0.61740 1.85221 7 .9% 5 . 2 % Water ( H 2 0 ) (see note) 18.00 4 .2082824 Vent Gas O x y g e n ( 0 2 ) 32 .00 8.5998 2 4 . 4 % Nitrogen (N2) 28.01 2 .2035 5 1 . 7 % Nitrous O x i d e (N20) 44.01 1.1425 0.6526 2 6 . 8 % Carbon M o n o x i d e (CO) 28.01 0.0001 0.0002 0 .0% 0 .0% Carbon D iox ide ( C 0 2 ) 44.01 6.2885 16.7534 8 0 . 1 % 4 7 . 5 % Hydrogen (H2) 2.016 Methane (CH4) 16.04 0.0000 0 .0% Ethane (C2H6) 30.07 0.0000 0 .0% water vapor 18.00 0.5004 0 .0% Total Effluents 4.243 6.920 32.068 Recove ry (eff luent/ inf luent)x100 % 99.59 88.12 90.86 Destruction Efficiencies Effluent C o m m e n t s Dini t rophenol 9 9 . 9 9 6 % None detected in effluent Total A m m o n i a 4 2 . 5 0 % T O C 9 9 . 8 3 % C O yie ld 0.002 C 0 2 yield 0.910 N 2 0 0.183 N2 yield 0.353 Notes: Vent gas f low ca lcu la ted from molar ba lance, Tab le H.4 Wate r molar f lows calcu lated accord ing to Equat ion [31] 168 Deviations in oxygen excesses per runs Note: The deviations corresponding to runs 2, 2b, 4, 4b, 6, 6b, 6c, and 7 are referred to in Appendix A, Table A.4 Table H.7 Uncertainties in oxygen flows. 2,4 DNP and ammonia experiment, runs 1, 3, and 5 Parameter Run 1 3 5 02 flow [V] Average 2.11 2.11 2.12 Max 2.14 2.13 2.16 Min 2.10 2.10 2.11 02 flow [kg/h] Average 1.45 1.44 1.48 Max 1.63 1.55 1.73 Min 1.37 1.37 1.41 02 excess [%] Average 74.73 73.27 78.62 Max 95.92 87.31 108.24 Min 65.24 64.74 69.67 02 excess (deviation from the mean) [%] Max 21.19 14.04 29.62 Min -9.49 -8.53 -8.95 169 Appendix I Corrosion Table 1.1 Metals losses. 2,4 DNP, ammonia and ammonium sulphate experiments INC 625 composition (%wt) Lost mg/L (from analyses) Vol of waste treated [L] total loss in g Mi 62.69 81.1 58.00 4.7038 Cr 21.89 4.71 58.00 0.2732 Mo 9.01 231 58.00 13.3980 total 18.3750 Weight of 1 mA3 of INC 625= density [g/m3] 8.44E+06 For 3/8" tubing without corrosion, the area is [m21 4.09E-05 internal diameter [mm] 6.22E+00 Thicness [mm] 1.65E+00 weight of the 3/8" tube per meter [g/m] 3.45E+02 Assuming uniform losses in a length of [m] 1 meter 0.8 meter 0.5 meter 0.1 meter Weight of tube length without corrosion [g] 3.449E+02 2.760E+02 1.725E+02 3.449E+01 Weight of tube after losing material from corrosion [g] 3.266E+02 2.576E+02 1.541 E+02 1.612E+01 new area after losing the material [mA2] 3.869E-05 3.815E-05 3.652 E-05 1.910E-05 New internal diameter (corrosion in inner part of the tube) [mm] 6.431580167 6.485231216 6.643585282 8.143294235 New thicness [mm] 1.546709917 1.519884392 1.440707359 0.690852883 Thickness loss [mm] 0.106 0.133 0.212 0.962 170 Metallic surface 50pm Figure 1.1 Optical microscope image. Preheater 1, corroded section Figure 1.2 Optical microscope image. Preheater 1, corroded section, pits 171 Appendix J Matlab programs and electronic files Matlab files Table J . l Matlab files File name (.m) Text files (.txt) Experiment Functions tables k, cp, enth, prand, vis - Lookup table for thermodynamic data oxygendata oxygenintrapolation densoxygen, visoxygen Lookup table and interpolation for oxygen densities ratelawsanalysys runl,run2,run3, run4, run5, run6,run7,run8,run9 Phenol Residence time calculations, rate laws analyses, error analyses convphenol convphenol Figure 3.7, Chapter 3 temprofiles2 run2percent Temperature profiles runs 2.7 % wt. temprofiles4 test Temperature profiles runs 4 % wt. dnp waste 1 waste 1 2,4 DNP + ammonia + ammonium sulphate Residence time calculations, concentration and conversion profiles, error analyses pressurewastel pwastel Pressure and oxygen flow fluctuations RHEX -Phenol and 2,4 DNP + ammonia + ammonium sulphate Calculate PHI in (RHX out, (cold side)) dnpwaste2 waste2 2,4 DNP + ammonia Residence time calculations, concentration and conversion profiles, error analyses pressurewaste2 pwaste2runl, pwaste2run2, pwaste2run22, pwaste2run23, pwaste2run3, pwaste2run4, pwaste2run42, pwaste2run5, pwaste2run6, pwaste2run62, pwaste2run63, pwaste2run7 Pressure and oxygen flow fluctuations 172 Excel files Table J.2 Excel files File name (.xls) Experiment Information phenol Phenol Runs raw data, oxygen flows and pressure uncertainties, initial molar concentrations sulphate red water 2,4 DNP + ammonia + ammonium sulphate Run 0 raw data, oxygen flow and pressure uncertainties red water no sulphate 2,4 DNP + ammonia Runs raw data, oxygen flows and pressure uncertainties, nitrogen and carbon balances mass balance all experiments All mass balances, gas flow calculations PT calibration Appendix A, first pressure transducer's calibration secondPT calibration Appendix A, second pressure transducer's calibration gas flowmeter Appendix B, gas flow meter correction table Experiment data files (original files) Table J.3 Experiments data files File name (.txt) Experiment Information ju l l l - la Phenol Run 1 jul l l - lb Run 2 jul11-2b Run 3, Run 4 jull9-la Run 5 jull9-lb Run 6 jul25-2a Run 7 jul25-2b Run 8, Run 9 nov2601,nov26b01 2,4 DNP + ammonia + ammonium sulphate RunO jul4 2,4 DNP + ammonia All runs 173 

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