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K ADDITIONAL DATA AND MATERIAL BALANCES FOR WET AIR OXIDATION, SUPERCRITICAL WATER 281 OXIDATION, AND THE SYNTHETICA DETOXIFIER Both conditions will lead to a shutdown. In the first case, the unreacted material is recycled to a feed tank. SUPERCRITICAL WATER OXIDATION Supercritical water oxidation has been applied experimentally a number of materials. (See Table K-1) Process Material Balance Estimated feed and product analyses and flow rates are shown below for destruction of 1,000 kg of GB. The case assumes a first-stage hydrolysis with NaOH followed by supercritical water oxidation of the hydrolysis product. Excess sodium hydroxide would be used in the hydrolysis reactor; this excess is then consumed in the oxidation reactor. The NaOH is limited, however, so that CO2 remains in the gas phase. (This is in contrast to the wet air oxidation case shown previously, where a large excess of NaOH was used for pH control and most of the CO2 ended up in solution as sodium carbonate.) Oxygen-enriched air (O2/N2 = 1:1) is assumed with 25 percent excess O2. The GB is 15 percent by weight of the feed solution. The over-all reaction assumed is Feed: GB: 1,000 kg NaOH: 286 kg H2O: 5.526 kg 6,812 kg
K ADDITIONAL DATA AND MATERIAL BALANCES FOR WET AIR OXIDATION, SUPERCRITICAL WATER 282 OXIDATION, AND THE SYNTHETICA DETOXIFIER TABLE K-1 Chemicals Successfully Treated by Supercritical Water Oxidation and Typical Destruction Efficienciesa Organic Compound Bench Scale Pilot Scale Destruction Efficiencyb, % Acetic acid x Acetylsalicylic acid (aspirin) x Ammonia x >99.71 Aroclors (PCBs) x x >99.995c Benzene x Biphenyl x 99.97 Butanol x Carbon tetrachloride x >96.53c Carboxylic acids x Carboxymethyl cellulose x Cellulose x Chlorinated dibenzo-p-dioxins x >99.9999 Chlorobenzene x Chloroform x > 98.83 c 2-Chlorophenol x > 99.997 c o-Chlorotoluene x x >99.998c Cyanide x Cyclohexane x 99.97 DDT x 99.997 Decachlorobiphenyl x Dextrose x 99.6 Dibenzofurans x 3, 5-Dibromo-N-cyclohexyl-N-methyltoluene-α, 2- x diamine Dibutyl phosphate x Dichloroacetic acid x Dichloroanisole x Dichlorobenzene x 4, 4'-Dichlorobiphenyl x 99.993 1, 2-Dichloroethylene x 99.99 Dichlorophenol x Dimethyl sulfoxide x Dimethylformamide x 4, 6-Dinitro-o-cresol x 2, 4-Dinitrotoluene x 99.9998
K ADDITIONAL DATA AND MATERIAL BALANCES FOR WET AIR OXIDATION, SUPERCRITICAL WATER 283 OXIDATION, AND THE SYNTHETICA DETOXIFIER Organic Compound Bench Scale Pilot Scale Destruction Efficiencyb, % Dipyridamole x Ethanol x Ethyl acetate x Ethylene chlorohydrin x Ethylene glycol x >99.9998c Ethylenediamine tetraacetic acid x Fluorescein x x >99.9992c Hexachlorobenzene x Hexachlorocyclohexane x x >99.9993c Hexachlorocyclopentadiene x 99.99 Isooctane x Isopropanol x x Mercaptans x Methanol x x Methyl cellosolve x Methylene chloride x x Methyl ethyl ketone x 99.993 Nitrobenzene x >99.998c 2-Nitrophenol x 4-Nitrophenol x Nitrotoluene x Octachlorostyrene x Octadecanoic add magnesium salt x Pentachlorobenzene x Pentachlorobenzonitrile x Pentachloropyridine x Phenol x Sodium hexanoate x Sodium propionate x Sucrose x Tetrachlorobenzene x
K ADDITIONAL DATA AND MATERIAL BALANCES FOR WET AIR OXIDATION, SUPERCRITICAL WATER 284 OXIDATION, AND THE SYNTHETICA DETOXIFIER Organic Compound Bench Scale Pilot Scale Destruction Efficiencyb, % Tetrachloroethylene x x 99.99 Tetrapropylene H x Toluene x Tributyl phosphate x Trichlorobenzenes x 99.99 1, 1, 1-Trichloroethane x x >99.99997c 1, 1, 2-Trichloroethane x >99.981c Trichloroethylene x Trichlorophenol x Trifluoroacetic acid x 1, 3, 7-Trimethylxanthine x Urea x o-Xylene x 99.93 Complex Mixed Wastes/Products (Bench-Scale Tests) Adumbran Human waste Bacillus stearothermophilus (heat-resistant spores) Ion exchange resins (styrene-divinyl benzene) Bran cereal Malaria antigen Carbohydrates Olive oil Casein Paper Cellulosics Protein Coal Sewage sludge Coal waste Soybean plants Corn starch Sulfolobus acidocaldarius Diesel fuel Surfactants E. Coli Transformer oild Endotoxin (pyrogen) Yeast
K ADDITIONAL DATA AND MATERIAL BALANCES FOR WET AIR OXIDATION, SUPERCRITICAL WATER 285 OXIDATION, AND THE SYNTHETICA DETOXIFIER Inorganic Compounds (Bench-Scale Tests)e Alumina Magnesium phosphate Ammonium chlorided Magnesium dulfate Ammonium sulfate Mercuric chloride Boric acid Potassium bicarbonated Bromides Potassium carbonated Calcium carbonated Potassium chlorided Calcium chlorided Potassium sulfated Calcium oxided Silica Calcium phosphated Sodium carbonated Calcium sulfated Sodium chlorided Fluorides Sodium hydroxided Heavy metal oxides Sodium nitrate Hydrochloric acidd Sodium nitrite Iron Sodium sulfated Iron oxided Sod Lithium sulfate Sulfur, elemental Magnesium oxide Titanium dioxide a Sources: Thomason et al. (1990), Thomason and Modell (1984), Modell (1985, 1989), and unpublished data from MODAR, Inc. b No entry for destruction efficiency indicates that a quantitative determination was not reported. c Compound undetectable in effluent; quoted efficiency is based on analytical detection limit. d Pilot-scale tests were also performed successfully. e Inorganic compounds were not destroyed but the process was operated successfully with those compounds present.
OXIDATION, AND THE SYNTHETICA DETOXIFIER FIGURE K-1 Apparent first-order Arrhenius plot for oxidation of model compounds in supercritical water at 24.6 MPa. K ADDITIONAL DATA AND MATERIAL BALANCES FOR WET AIR OXIDATION, SUPERCRITICAL WATER Source: Tester et al. (1991), Tester (1992). 286
