Document N28Oq4zVbwe38QpVjD6E6JEdR

[= / Report No. 137 WASTE TREATMENT COSTS by GEORGE E. HADDELAND September 1980 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025 00016369 MCD 0 c For detailed marketing data and information the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicaLs and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod uct, and plant for the United States and Western Europe. o CO CD rH o o o rc r--+ ii O T, C CONTENTS 1 INTRODUCTION......................................................................................................................... 2 SUMMARY................................................................................................................................... Pollution Abatement Legislation ........................................................ ... Pollution Abatement Expenditures............................................................ Capital Costs ............................................................................................................... Operating Costs................................................................................ Waste Treatment Technology......................... Modular Waste Treatment Costs .... ........................................................ Fixed Capital Investment ................................................................................. Operating Costs .......................................................................................................... Examples of Module Cost Estimates ............................................................. 3 POLLUTION ABATEMENT LEGISLATION AND EXPENDITURES.............................. Legislation in the United States....................................................................... Air Pollution............................................................................................................... Water Pollution . ..................................................................................................... Land Pollution (Solids Disposal).................................................................. Selected Reactions to U.S. Antipollution Legislation. ... Information Sources ................................................................................................ Legislation in Japan..................................................................................................... Air Pollution............................................................................................................... Water Pollution.......................................................................................................... Land Pollution. ............................................. Chemical Substances Control Law .................................................................. Expenditures in the United States......................... Capital Expenditures.............................. Operating Costs .......................................................................................................... Expenditures in Japan ................................................................................................ 4A WASTEWATER TREATMENT TECHNOLOGY...................................................................... Pretreatraent......................................................................................................................... Primary Treatment--Chemical................................................................................. Objective......................................................................................................................... Ion Exchange............................. Electrodialysis ..................................................................................................... * Reverse Osmosis .......................................................................................................... Neutralization. . ...................................................................... Oxidation and Reduction...................................................................................... Chemical Addition ..................................................................................................... Hydrolysis....................................................... Primary Treatment--Physical ................................................................................. Sedimentation ............................................................................................................... Hydrocycloning............................................................................................................... 1 3 3 5 5 5 6 8 8 9 9 13 13 13 16 22 24 25 26 28 30 32 32 33 33 38 41 43 45 46 46 54 56 58 58 60 63 65 67 67 67 iii (>00lG3?1 CONTENTS 4A WASTEWATER TREATMENT TECHNOLOGY (continued) Filtration and Centrifuging................................................................................. Flotation.......................................................................................... Solvent Extraction ..................................................................................................... Crystallization..................................................................................................... . . Adsorption on Activated Carbon .............................................. ..... Secondary Treatment.......................................................................................................... Air-Activated Sludge ..... .......................... . ................................... Oxygen-Activated Sludge........................................................................................... Facultative Lagoons..................................................................................................... Trickle Filters .......................................................................................................... Nitrification-Denitrification. .... ................................................... Sand Filters................................................................. Tertiary Treatment .......................................................................................................... Foam Fractionation..................................................................................................... Chlorination.......................................................................................................... ..... . Ozonation.............................................................................................................................. Toxic Liquids Disposal ................................................................................................ 70 72 76 77 77 80 80 82 85 85 87 89 90 90 91 92 95 4B GASEOUS WASTE TREATMENT AND DISPOSAL TECHNOLOGY................................... 97 Pretreatment........................................ 97 Dry Systems........................................................................... 100 Gas-Solid Separation................................................................. 100 Adsorption on Activated Carbon . . ................................................................... 101 Liquid Systems........................................ 105 Water and Solvent Scrubbing....................................................................................... 105 Acid or Ammonia Neutralization ....................................................................... 105 Limestone Desulfurization............................................................................................ 105 Waste Gas Disposal................................................................................................................ 106 Steam Generation and Incineration. ................................................................... 106 Emergency Flaring................................................................................................................ 107 Dispersion by a Stack...................................................................................................... 108 4C SOLID WASTE TREATMENT AND DISPOSAL TECHNOLOGY...............................................Ill Waste Solids Treatment ....................................................................... ..... Ill Dewatering............................................................ Ill Drying ............................................................ 115 Incineration...................................................................................... 116 Combustion...................................................................... 119 WTaste Solids Disposal............................................................ 121 Land Fanning.......................................................................................................................... 121 Stacking.................................................................................................................................... 122 Sanitary Landfill. ..................................................................................................... 122 Hazardous-Waste Landfill ................................................... , ......................... 124 Other Disposal Methods ........................................................................................... 125 iv 6'3'7 2 noOO j- CONTENTS 5 COST CALCULATIONS FOR WASTE TREATMENT MODULES......................................... Capital Cost Methods Used in This Study........................................................ Operating Costs.................................................................................................................... Module Cost Curves .......................................................................................................... 6 WASTE TREATMENT COSTS FOR SELECTED CHEMICAL INDUSTRIES .... Methanol Plant Wastes. ................................................................................................ Treatment Methods.......................................................................................................... Treatment Costs............................................................................................................... Discussion of Costs..................................................................................................... Ethylene Plant Wastes...................................................................... Treatment Methods.......................................................................................................... Treatment Costs............................................................................................................... Discussion or Costs..................................................................................................... Multiplant Wastes............................................................................................................... Treatment Methods.......................................................................................................... Treatment Costs............................................................................................................... Discussion of Costs...................................................................... Phosphoric Acid Plant Wastes ................................................................................. Treatment Methods.......................................................................................................... Treatment Costs............................................................................................................... Discussion of Costs..................................................................................................... Conclusion............................................ APPENDIX A Cost Basis............................................................................................................... APPENDIX B Calculations for the Equalization of a Waste Stream Flow Variable..................................................................................................... APPENDIX C Design Steps for a Completely Mixed Activated Sludge System........................................ APPENDIX D Fixed Bed Active Carbon Adsorber Capacity .............................. CITED REFERENCES 127 130 133 134 189 190 190 190 193 195 195 195 199 200 200 200 204 205 205 207 207 208 211 213 217 223 225 ILLUSTRATIONS 3.1 3.2 3.3 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 Annual Capital Expenditures by the U.S, Chemical Industry for Pollution Abatement. ............................................................................................ 34 Annual Operating Costs of the U.S. Chemical Industry for Pollution Abatement............................................................ 39 Annual Capital Expenditures by the Japanese Chemical Industry for Pollution Abatement as a Percentage of Total New Capital Investment ................................................................................. Wastewater Treatment Alternatives....................................................................... 42 44 Multiple-Chamber Alternate-Membrane Electrodialysis Cell ... Settling Curves at Various Suspended Solids Concentrations . , 57 68 3atch Suspended Solids Flux Curve for Design ........................................ 69 Approximate Solid Size Range for Solid-Liquid Separation Equipment ..................................................................................................... 71 Schematic Diagram of Dissolved-Air Flotation Tank with Recycle......................... Activated Sludge System................................................................................................ 75 81 Waste Gas Treatment Alternatives....................................................................... 98 Compressor Horsepower for Various Air Flow Rates .............................. 99 Pressure Drop for Air Flow Through Active Carbon at 70F and 760 run Hg.............................. 104 Waste Solid Treatment Alternatives .................................................................. 112 Effect of Feed Size on Drying Centrifuge Capacity.....................................113 Effect of Feed Rate and Size on Drying Centrifuge Product Moisture............................................................................................... 114 Stacking Procedure for Waste Gypsum........................................................................ 123 Guthrie Method for Modular Cost Estimates.........................................................129 Module Cost: Tanks.................................... Module Cost: Thickener, Clarifier .................................................................. 136 137 Module Cost: Settling Lagoon ............................................................................. 138 Module Cost: Oil Separators .................................................................................. 139 Module Cost: Filters............................................................................................................ 190 Module Cost: Centrifuges.................................................................................................. 191 Module Cost: Hydraulic Cyclones ........................................................................ 192 vii 000016374 MOD ILLUSTRATIONS 5.9 5.10 5.11 5.12 5.13 5.14 5.15 5.16 5.17 5.18 5.19 5.20 5.21 5.22 5.23 5.24 5.25 5.26 5.27 5.28 5.29 5.30 5.31 5.32 5.33 5.34 5.35 5.36 Module Cose: Distillation System................................................................... Module Cost: Evaporators............................... Module Cost: Stripper, Steam or Flue Gas. ......................................... Module Cost: Lime Neutralizer........................................................ Module Cost: System for Chemical Reaction or Precipitation................................................................................................................. Module Cost: Ion Exchange System. ...... ................................ Module Cost: Electrodialysis and Reverse Osmosis Cells.................................................. Module Cost: Dissolved-Air Flotation Cell .......................................... Module Cost: Crystallization System ......................................................... Module Cost: Active Carbon Adsorber for Liquid Stream . . . Module Cost: Solvent Extraction System.................................................... Module Cost: Biological Oxidation System Including Sludge Separation........................................................................................................... Module Cost: Faculative Lagoon........................................................................ Module Cost: Filters, Dual Media and Sand.......................................... Module Cost: Foam Fractionator................................................... Module Cost: Ozonation System ........................................................................ Module Cost: Denitrification System ............................................... . . Module Cost: Hydrolyzer ............................................................. ..... Module Cost: Chlorinator for Ammonia Removal..................................... Module Cost: Chlorinator for Disinfection and Equipment for Water Quality Control....................................................................... Module Cost: Pumping System and Deep-Welling System .... Module Cost: Liquid Incinerator ................................................................... Module Cost: Steam and Cooling Water Utilities................................ Module Cost: Gas Combustor for Steam Generation ........................... Module Cost: Gas Incinerator........................................................................ Module Cost Flue Gas Desulfurization System. ....... Module Cost: Hydrocarbon Gas Flare.............................................................. Module Cost: Gas Dispersion Stack ..... ............................... . 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 viii mcd 0000 -10.375 ILLUSTRATIONS 5.37 5.38 5.39 5.40 5.41 5.42 5.43 5.44 5.45 5.46 5.47 5.48 5.49 5.50 5.51 5.52 5.53 6.1 6.2 6.3 6.4 B. l C. l C.2 C. 3 D. l D.2 Module Cost: Ammonia Neutralizer.................................................................. Module Cost: Acid Gas Neutralizer............................................................. Module Cost: Scrubbers, Hydrocarbonor Water....................................... Module Cost: Active Carbon Adsorberfor Gaseous Stream. . . Module Cost: Gas Compressor........................................ Module Cost: Dust Separator ............................................................................ Module Cost: Gas Coolers................................................................................. Module Cost: Gas Refrigeration System ................................................... Module Cost: Rotary Direct Dryer.................................................................. Module Cost: Dewatering Centrifuge............................................................. Module Cost: Solids Incinerator .................................................................. Module Cost: Solids Combustor ............................................. ..... Disposal Cost: Land Farming .................................... ........ Disposal Cost: Gypsum Stacking....................................................................... Disposal Cost: Sanitary Landfill.................................................................. Disposal Cost: Hazardous-Waste Landfill ...................... ..... Transportation Cost............................................................................................... Treatment of Methanol Plant Wastes ............................................................ Treatment of Ethylene Plant Wastes (Ethane/Propane Pyrolysis) .................... ...................................................... Treatment of Multiplant Wastes ...................................................................... Treatment of Process Phosphoric Acid Plant Wastes (Dihydrate Wet Process).......................................................................................... Probability Plot of BOD Value. ....................................................................... Determination of BOD Removal Rate Coefficient..................................... Determination of Oxygen Utilization Coefficient. ...... Determination of Sludge Production Coefficient ................................ Breakthrough Curves for Three Columns in Series................................. Service Time as a Function of Bed Depth..................................................... 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 191 196 201 206 214 218 220 221 224 224 ix TABLES 2.1 A Comparison of Modular Waste Treatment Estimates With Independently Estimated Values..................................................................11 3.1 U.S. National Ambient Air Quality Standards............................................. 15 3.2 Typical Effluent Limitations Promulgated by U.S. EPA According to the Federal Water Pollution Control Act ^ Amendments of 1972 ............................................... 17 3.3 U.S. EPA List of Priority Toxic Pollutants as of December 1978......................................................................................................................... 19 3.4 U.S. EPA-Proposed Water (Micrograms/Liter) Quality Criteria for Selected Toxic Pollutants ........................................................ 21 3.5 Major Pollution Control Legislation by the U.S.Congress ... 27 3.6 U.S. Pollution Abatement Expenditures for Air, Water, and Solids, by Chemical Industry Segment .................................................. 36 3.7 U.S. Pollution Abatement Operating Costs for Air, Water, and Solids, by Chemical Industry Segment .................................................. 40 3.8 Japanese Pollution Abatement Expenditures.........................................................41 4.1 Typical Thickener and Clarifier Design Criteria..........................................46 4.2 Water Pollutant Treatment Methods ... .................................................. 47 4.3 Toxic Inorganic and Organic Pollutants and Methods for Their Control. ................................................................................................................ 48 4.4 Materials Rejected by Reverse Osmosis................................................................... 59 4.5 Commercial Oxidizing and Reducing Agents and Their Possible Applications to Waste Treatment ................................................... 62 4.6 Typical Flocculants and Coagulants and Their Applications. . . 64 4.7 Some Typical Filter Applications ............................................................................. 73 l 4.8 Typical Centrifuge Performance Characteristics ................................... 74 4.9 Activated Sludge Process Characteristics .................................................. 83 4.10 Typical Compounds Susceptible to Ozonation .... ......................... 93 4.11 Applications of Gas-Solid Separation Equipment ................................... 101 4.12 Vapors Adsorbed by Activated Carbon..................................................................... 103 4.13 U.S. EPA-Sponsored Waste Incineration Demonstration Plants............................................................................................................................................ 117 MCI) oooo i ft 77 xi TABLES 5.1 5.2 5.3 6.1 6.2 6.3 6.4 B.l SRI Module Investment Estimation Factors.............................................. Comparison of Chemical Equipment Module Costs Estimated by Different Methods....................................................................... SRI Module Maintenance Cost Estimation Factors. ...... Treatment Costs for Methanol Plant Wastes ............................... . . Treatment Costs for Ethylene Plant Wastes ......................................... Treatment Costs for Combined Multiplant Wastes............................... Treatment Costs for Phosphoric Acid Plant Wastes (Dihydrate Wet Process) ...................................................................................... Cumulative Normal Probability Distribution.......................................... 131 132 134 192 197 202 09 2 ..5 ,Vifcr<n (-]00o j637q xii 1 INTRODUCTION For Process Economics Program reports, in the past, we have usully added a standard fixed percentage to the capital investment for control of water, air, and land pollution. In this study we have developed a convenient method to approximate the capital and operating costs for pollution control in specific chemical plants or complexes. We believe that this method will improve the accuracy of pollution control estimates in future PEP reports and at the same time provide a better understanding of the nature of these costs and how they might be minimized. Sufficient information is provided to enable PEP users to independently estimate or compare the pollution control costs of other plants or processes. Sections 4A., 4B, and 4C briefly describe operations with present or potential application to the abatement of water, air, and land (solids) pollution. Their areas of utility are indicated and informa tion is provided to enable one to roughly relate equipment size to pollutant stream flow rate. Previously published capital costs for these operations, where available, are also reported. Section 5 details the procedures used in this study to derive module capital costs and operating requirements for the above pollution abatement operations. Module capital cost curves and tables of opera ting requirements, so obtained, are included. These cost data apply to a PEP Cost Index of 290 and a time base of January 1, 1979. Section 6 illustrates the use of the above module cost curves and operation data to estimate the capital investment and operating costs of pollution control for a methanol plant, an ethylene plant, a wet process phosphoric acid plant, and a multiplant complex for making acrylonitrile, ethylene, propylene, hexamethylenediamine, and methanol. These estimates are compared with similar estimates derived independently elsewhere. \ <fottf9 nOO 1 Section 3 first outlines the major pollution abatement legislation enacted in the United States and Japan over the past decade. It then summarizes the overall financial impact of the legislation on chemical and allied industries. With many pollution abatement deadlines now set for the mid-1980s, little or no near-term easing of this burden appears likely for the chemical industry in the United States. Only fragmentary information on European pollution control legisla tion and on the costs of implementation was found in recently published literature. Thus, no European information is included 'in this report. OQi 70J6380 2 2 SITtMARY Pollution Abatement Legislation Much of the motivation for pollution abatement in the United States stems from legislation enacted by Congress over 'the past decade. The Clean Air Act Amendments of 1970 and 1977 define three area classifications: Class I - Virtually no increase in air pollution is allowed (national parks and wilderness areas) Class II - Limited increases in air pollution are allowed (city, urban, and rural areas) Class III - Higher air pollution in Class II areas is allowed on special request by the governor of the state. The materials controlled are SO2, NO2, CO, ozone, hydrocarbons, lead, and particulates. A criticism of the Clean Air Act is that it allows pollution to increase in populated areas, where the most people are exposed to possible long-term effects. The Occupational Safety and Health Act of 1970 regulates the con centration of hazardous vapors and gases in working environments. The Federal Water Pollution Control Act Amendments of 1972 and the Clean Water Act of 1977 empower the Environmental Protection Agency (EPA)--which has the responsibility for administering most of the pollution control legislation--to establish purity standards for wastewater discharges from publicly owned treatment works (POTW) and industrial plants. These standards, to be established by mid-1980 and implemented by 1985, should prevent adverse effects on humans, fish, or wildlife. oooo16381 3 EPA is developing a program requiring industrial plants to pretreat their wastes before discharging them to a POTW. Technical and financial assistance is available through EPA for implementation of the above legislation. The volume of solid industrial waste generated in the United States is estimated at 336 million metric tons/yr, with about 9" of this being potentially hazardous waste. The Resource Conservation and Recovery Act of 1976 recognizes that, in the past, waste disposal precautions have been inadequate and provides for the identification and monitoring of hazardous wastes through generation, transportation, storage, and final disposal. A companion piece of legislation, the Toxic Substances Control Act of the 1976, requires extensive testing and record keeping before a new chemical material can be produced commercially. The Marine Protection, Research, and Sanctuaries Act of 1972 has largely eliminated the ocean dumping of industrial wastes from the United States. Ocean dumping of sewage sludge (still several million tons annually) is to be eliminated by the end of 1981. Incinerator ships--currently in use in Europe--are being considered for the burning of U.S. industrial wastes at sea. Legislation in Japan to control air and water pollution is similar to that in the United States but generally more restrictive. The Basic Law for Environmental Pollution Control was enacted in 1967 and was aug mented by the Air Pollution Control Law in June, 1968 and the Water and Marine Pollution Control Law of 1970. These laws set national stand ards for air and water pollutant concentrations, and the Environmental Agency has responsibility for their implementation. However, local governments have the authority to set and enforce standards * ' 'ch are 2 more severe than the national ones. G Pollution Abatement Expenditures Capital Costs The capital investment in facilities for pollution abatement by the U`.S. chemical and allied products industries has risen steeply from less than $150 million in 1972 to almost one billion in 1977. Most of this cost pertains to water (60%) and air (35%). By 1985, capital expenditures for pollution control are expected to reach $1.3 billion/yr, with most of this increase going for water pollution aba t enent. Capital expenditures for pollution abatement since 1973 have been in the range of 10 to 13.5% of total new capital spending by the U.S. chemical industry. This is projected to continue until 1985. These are average figures and they differ appreciably for different segments of the chemical industry. For example, pollution abatement expendi tures in 1976, as a percentage of new capital investments, was 22% for inorganic chemicals, 15% for organic chemicals, and 4% for drugs and pharmaceuticals. Moreover, expenditures within these segments vary widely. Annual expenditures by the Japanese chemical industry reached a peak of 17% of new capital investment in 1975. They have since declined to about 4%. Water pollution represents about 50% of the 4.5 x 10^ yen pollution abatement expenditure in 1979. Air pollution accounts for 30%, with solid waste disposal and noise pollution taking the balance. Incineration is the principal means for disposal of solid and hazardous wastes in Japan. Operating Costs Operating costs for air, water, and land pollution abatement have also been rising steadily in the United States since 1973, at an average annual rate of 24%. They currently amount to $1.7 billion/yr, or about 2.2% of the value added by the chemical and allied industries. By 1985, annual operating costs may reach $1.7 billion, or 2.7% of the value added. \Qn0 cA6,36* ^\CVD 5 The operating coses vary appreciably among industry segments. In 1976, pollution abatement operating costs as a percentage of the value added averaged 3.5% for industrial organic chemicals, 2.7% for inorganic chemicals, and 0.4% for drugs and pharmaceuticals. Within a given segment, however, the costs may vary widely. A sulfate process titanium dioxide pigment plant, for example, may have a pollution abatement cost equal to 10% of value added. Waste Treatment Technology The technology for pollution abatement consists mainly of the same physical and chemical separations and reaction technologies used in chemical manufacture. For wastewater, pretreataent by screening, settling, or steam stripping, may be used to remove suspended solids or immiscible liq uids. This can be followed by a primary treatment consisting of physical operations such as centrifuging, flotation, reverse osmosis, and evaporation, or chemical reactions such as neutralization, precipi tation, and ion exchange to separate dissolved or finely suspended impurities. Secondary treatment consists of biological oxidation (this is the only technology pertaining primarily to wastewater treatment). The oxidation can be performed in tanks, deep shafts, lagoons, or trickle filters, with air or oxygen being used to convert nontoxic organic impurities to an insoluble sludge. This sludge can then be separated by thickening, filtration, or centrifuging and sent to solids disposal. When the wastewater is to be recycled or used by animals or humans, tertiary treatment r.av be necessary. This consists of ozona tion, distillation, or absorption by activated carbon to remove traces of organic colors, tastes, and odors, or of ion exchange, electrodialy sis, and precipitation to eliminate residual dissolved solids. Finally, the water is chlorinated or ozonated to destroy bacteria and other microorganisms. ^ aao,o 6 <51 The choice of operations for treating a given aqueous waste is determined by: Quantity and composition of waste stream Existing or impending pollution abatement laws and regulations ( Nature of surrounding facilities and environment. In some cases, it may be more economic to eliminate a waste stream by modifying the process or raw materials from which it is generated. Gaseous wastes may need to be precooled or compressed to facili'v- tate subsequent treatment. Suspended solids are separated by cyclone, bag filter, or electrostatic precipitator. Harmful gaseous impurities are removed by adsorption on active charcoal or by scrubbing with water, solvent, or aqueous acid or alkaline solution. Combustible impurities in the waste gases can be burned or flared. Residual inert, or largely inert, gases are released to the atmosphere. The treatments and disposal alternatives available for solid wastes are few. Moisture or adsorbed liquids can be separated in a dewatering centrifuge or a drier. Incineration can be used to convert toxic wastes to gaseous and solid wastes more easily disposed of. A combustible solid waste can be used as a fuel in the plant. The disposal of waste solids, as previously indicated, is coming under increasing regulations and record keeping. Ocean dumping is no longer permitted from the United States. Deep-welling of slurried solids is feasible only for some areas and with extensive precautions, monitoring, and record keeping. The same is true for hazardous-waste landfill. Nonhazardous waste solids can be stored in sanitary land fills, stacked or, in the case of biologically decomposable solids, destroyed by land farming. These methods can require sizable land areas. 00 7 Modular Waste Treatment Costs Fixed Capital Investment The several methods normally used for estimating the capital cost of waste treatment facilities are cumbersome, expensive, and/or requiring of detail more akin, to a final engineering design than to a preliminary cost estimate. In this study, we developed a quick and simple procedure to estimate both capital investments and operating costs. Typical installed costs for chemical equipment ranges from about 1.8 to 5.0 times the equipment f.o.b. price, depending on the extent of foundations, supports, field labor, piping, insulation, electrical wiring, instrumentation, and building enclosure that is required. Thus, by placing each of these installation requirements at "little," "some," or ''extensive," as shown below, we obtain installation factors varying between 1.8 and 5.0: Little Some Extensive Base factor 1.0 1.0 1.0 (A) Foundations, steel supports, field labor (B) Connecting piping (C) Insulation, electrical connections, ins trumentation CD) Building or enclosure Totals (module factor * f\j) 0.2 0.6 0.2 0.6 0.2 0.6 0.2 0.6 1.8 3.4 1.0 1.0 1.0 1.0 5.0 A centrifuge with "sone" foundations and supports; "some" connect ing piping; "little" electrical, insulation, or instrumentation; and complete enclosure in a building would have a module factor (fvj) * 1.0 + 0.6 + 0.6 + 0.2 + 1.0 * 3.4. The module cost is then the equip ment price of $25,000 x 3.4, or $85,000. A comparison of equipment nodule costs so obtained with those by Icarus Corporation and Guthrie showed individual variations of +30% but, when nine modules were totalled, the differences were less than 5%. a mod 0016386 The total fixed capital investment is the sum of the modular costs plus 30% to allow for indirect costs--construction, overhead, engineer ing, freight, equipment rental, etc.--and general facilities such as stores, maintenance shops, change rooms, roads, and fencing. Operating Costs The operating costs for each equipment module are functions of capital cost, feed rate, and process complexity. Capital-related costs--i.e., taxes, and insurance, depreciation, return'on investment, and maintenance--are,, with the exception of maintenance, defined in PEP estimates as given percentages of the capital investment. Factors influencing maintenance costs are: Corrosivity and special construction materials Operating temperatures above ambient Power usage and numerous moving parts Connecting equipment Abrasive solids handling. If each of these five factors is given a value of zero, one, or two--depending on whether it has no influence, some influence, or appreciable influence--the annual maintenance cost can readily be estimated as a percentage of the process module cost. Process materials and utilities usages are normally specific to a particular waste treatment operation and feed flow rate, and labor is related to the type of processing, with only minor sensitivity to feed rata. Thase relationships are given in tables on the graphs of module costs. Thus, using the table and the graph, one can derive the approximate capital and operating costs for each equipment module. Examples of Module Cost Estimates Modular capital and operating cost curves and data were employed to estimate waste treatment costs for the following chemical plants or complexes: ooooi6387 tfCti 9  A 660 million lb/yr methanol plant A 1.0 billion lb/yr ethylene plant A multiplant complex of adiponitrile, ethylene/propylene, hexamethylenediamine, and methanol with capacities of 210, 900, 200, and 750 million lb/yr respectively. A 50 million Lb P205/yr wet process phosphoric acid plant. These costs, together with comparative figures obtained from independ ent sources, are shown in Table 2.1. Modularly estimated fixed capital investments for each of the three single-process plants and for the multiplane complex are well within ^20% of the comparison estimates. Similarly, annual operating costs--except those for the methanol plant--are generally within the same range. In all cases, the invest ment in waste treatment is less than 5. of the plant investment, and operating costs represent 0.4c/lb or less of the product value. Minimizing the waste treatment cost of any new chemical plant necessitates judicious selection of process, location, and raw materials. 338e mod oooc 10 Tibi# 2.1 A COMPARISON OF MODULAR WASTE TREATMENT ESTIMATES WITH INt>EFEN!m.r ESTIMATED VALUES* Pep Cost Index: 290 Chemical plants (capacity, l.COO t/yr) Waite Treatment fixed Capital I of Plant 51.000 Investment Module estimates voerstm* Cose s 1 ,:ccfvr :/lb of Product Mechanoir (130) Ethylene* (fT01 asa 1,370 Multi plant complex adiponitrili (105) Ethylene/propylene (ISO) rlexasetnylenedlamlnc ( 1Q0> Hsthanoi (37 5 ) )1 / ) 12,400 Wet proceaa phoaphotlc ecld i:;:)n 430 1.7 0. 7 3.2 4. 3 162 735 3,210 19* 0.16 3.07 ) 0.1S } ) 0.40 Independent Waste Treatment Estimates rlxed Capital '.derating Cost I Ztviaeian uviit_an SI .000 frota Hodule Sl.OOO/vr roa kc :o 1 712 1.400 -17.0 -2.2 :J4 520 -2= - ;.6 9,100 or 14,100 368 -6,S** -14.4 } / 1.630 ' 1 3,100 ) <0C -26.8 -26.8** *1.5 "independent value* nave been adJutcM where necessary to a PIP Coat Index of 290, corresponding co a tine basis of January, 1979. These figures include only one biological air oxidation of metnacoi aqueous wastes, natural gas raw material Is assumed to oe delivered with a low sulfur contsnt. Ccner wastes are negligible or are returned to supplier far recovery of aetais. ^Waste treatment costs nave been djusted to a small plant capacity for the Independent estimates to correspond to waste stream quantities used for the module estimates. '*--e Independent waste treatment estimate Includes two systems--one according to the best available demonstrated technology (3ADT) and also according to tne best available technology ilAtl. The average of these is useo :.r comparison. Capital and operating cost co pump slurry wastes to the disposal area are not Included In eicher sec of figures. 0Q 11 3 POLLUTION ABATEMENT LEGISLATION AND EXPENDITURES Legislation in the United States Air Pollution The first legislation in the United States directed to the control of air pollution was the Air Quality Act of 1963. This act provided for research, technical assistance, matching grants to state and local agencies, and enforcement authority for the abatement of air pollution (B-13932). This was followed by the Air Quality Act of 1967, which initiated a two year study of air pollution, the issuance of air quality criteria, and the development of methods for their control. Primary enforcement was placed at the state level with federal fallback, authority when needed. The Clean Air Act Amendments of 1970 was next, with the following provisions: Inclusion of all areas of the United States in air quality control regions. Promulgation of performance standards for new sources. Development of national standards for deleterious pollutants. Monitoring and record keeping of emission sources. Imposition of fines and criminal penalties for violation of air quality standards. Administrative responsibility for overseeing the implementation of these provisions was given to the Environmental Protection Agency. The most recent and comprehensive legislation is the Clean Air Act Amendments of 1977 (447094). This legislation set up three area clas sifications: Class I, which permits virtually no pollution increase; Class II, which allows for a moderate increase; and Class III, which provides for a more extensive increase. Class I includes national 391 ooocn6 v\Ct> 13 parks and wilderness preserves. All other areas are Class II, except where a Class III designation has been requested by the state governor. The act also sets national air quality standards (see Table 3.1), with a January 1979 deadline for meeting these standards--now extended to December 1982 (B-13938). The major sources of pollution (each capable of emitting more than 100 tons of pollutant per year) have been identified in the United States (B-13938). Out of approximately 23,000 major sources, 87% were in compliance as of October 1977. However, prior'enforcement actions initiated by EPA and the states exceeded 16,000. Pollution increments--intended for the prevention of significant deterioration (PSD)--have been established for new sources, and a complicated pro cedure is required to obtain a permit for a new source. The time interval for completion of this procedure ranges from 18 to 43 months (447002). Local concentrations of toxic gases resulting from various manu facturing and chemical processing operations are covered by the Occupational Safety and Health Act of 1970 (OSHA) (447095). This act, administered by the U.S. Dept, of Labor, provides for a network of inspectors to investigate working areas. OSHA can issue citations when the concentration of a hazardous material--such as vinyl chloride vapor--is above a specified safe concentration. Fines and/or imprison ment can be imposed for noncompliance with OSHA safety standards. Some of the problems arising from OSHA inspections of a working environment have been discussed by Horan (447096)* The above acc also sets up a National Institute for Occupational Safety and Health (NIOSH), which operates within the Dept, of Health, and Human Services to measure and report the safe exposure limits for hazardous materials. Over 16,000 toxic substances have been identified and threshold concentrations for their toxicity to marine and animal life have been established (B--13937). Safe concentration limits for over 300 gases have also been published (447006). v) 14 -(a J. Table 3.1 U.S, NATIONAL AMBIENT AIR QUALITY STANDARDS Pollutant Tine Period Units Primary* Standa rd Secondary 1 Standard Sulfur dioxide 3 hr5 ug/m3 __ 1,300 24 hr lig/m3 365 -- Annual ug/m3 80 -- Nitrogen dioxide Annual U g/n3 100 100 Total suspended particulates 24 hrs Ug/m3 260 150 Annual Ug/m3 75 60 Carbon monoxide V 1 hr^ 8 hr mg/m3 rag/m3 40 10 40 10 Lead 3 month avg. tig/m3 1.5 1.5 Hydrocarbons (other chan methane 3 hr5 Ug/m3 160 160 Ozone 1 hr^ ppm 0. 12 0. 12 Pollutant Particulate natter Annual mean 24 hr maximum Sulfur dioxide Annual mean 24 hr maximum 3 hr maximum Prevention of Significant Deterioration, Maximum Allowable increment (ug/m3) Class I Class II' Class III 5 19 10 37 2 20 5 91 25 512 37 75 40 182 700 *Threshold level for effects on human health . ^Threshold level for environmental effects , foliage, visibility, etc. ^Levels not Co be exceeded more than once per year. '^Suggested maximum if ozone limits are to be realized. Source: 447094 oO'o **- 15 Water Pollution The Federal Water Pollution Control Act Amendments of 1972, which replaced all previous federal water laws, was the most comprehensive water control legislation to come cut of the Congress of the United States. It empowered EPA to set stanaarcs for wastewater discharges from existing industries to be achieved by July 1, 1977, by the "best practicable control technology currently available" (5PCTCA or B?7). New plants were required to file for a National Pollution Discharge Elimination System (NPQES) permit 21 months before beginning the discharge and to meet an effluent concentration according to the "best available demonstrated control technology" (3ADCT or BADT). Industry was directed to attain, by July 1, 1983, aqueous pollutant discharge levels consistent with the "best available control technology economi cally achievable" (BATEA or BAT) and 1985 was set as the year for achieving zero pollutant discharge. Monitoring and reporting could be required and fines up to S25,000 and/or 1 year imprisonment could be imposed for the first conviction of false reporting, negligence, carelessness, or willful violation. Discharges to publicly owned treatment works did not require a permit provided they did not contain pollutants which interfere with normal operation and provided the discharger bore a proportionate share of the POTW capital and operating costs. EPA implementation of this law separated the chemical and related industries into subcategories ranging from through Cj_]_. Each cate gory was allowed a maximum one day and a maximum 30 day discharge of chemical oxygen demand (COD), biological oxygen demand measured over 5 days at a constant temperature (BOD5), total suspended solids (TSS), and pH, as shown in Table 3.2, for the three control levels 3PT, SDT, and BADT. The above law was not sufficiently specific--small quantities of chlorinated organics or heavy metal salts, which can be very damaging to the environment, were not covered by effluent specifications. 16 39 A ;\00lS Table 0. TYPICAL EFFLUENT LIMITATIONS PROMULGATED BY U.S. E?A ACCCRDINC TO THE FEDERAL WATER POLLUTION CONTROL ACT AMENDMENTS OF L9 72 Subcatg tor/ Prague t and Processes Effluent Characce ris t its Lb/l.OOO lb of :?7 Average of )0 Maxlaua Consecutive for l Devs Shall Dav Not Exceed Prsduct Maxlaua for l -4Y or ke-1.000 ks of Prsduet 3 ADT ! AT Average Average of 30 of 30 Consecuclve HaxL&UB Consecutive Dayi Shall Not Exceed for l Devs Shall Not Exceed A 3TX aroeatics bv hydration of COD pyrol-ns gason.'.e; iTX arooac- ldS by solvent excradtion of 3OD5 reformate; cyclohexane by hydro genation of benzene; and vinyl TSS chloride by KCL addition to acetylene. pH --- 0.045 O.O: 0.06? 0-03 6.0 to 9.0 2.037 0.017 0.034 0.01 5 6. 0 to 9.0 D.C62 2.015 0.015 0.022 0.CC85 `.013 0 C to 9 .C St Acetone by dehvdrogenation of V Isapropanol; butadiene By-product of ethylene; crvlbenzene by alkylation of Benzene: ethylene and sropylene by hydrodarbon COD 0.80 0.53 pyrolysis; ethylene dlchiorlde by chlorination of ethylene; BOD5 0.13 0.58 3. 1 l 0.048 0.3:5 ethylene oxide :y catalytic 0x1datioo of ethvlene; foraaldehyde TSS o.:o 0.083 0.10 0.044 J.Cbe C, C by oxidation of acthanol; aectianol by stcaa reioreing of pH 6.0 to 9.0 6. 0 to 9.0 *0 co 9. ? natural gas: aetnyl aalnei by addition of anoonia to aetnane; vinyl acetate free ethylene and acetic acid; vmvl chloride by cracking of ethylene dlchiorlde. 5 Adlpomtrile bv chlorination of bentadleoa; oenzeic acid by catalytic oxidation of toluene: and sethyl chloride by KQ reaction with oachanol. COO BOD5 TSS pH -- 0.94 1.11 C. 4 2 0.49 Between 6 and 9 ---- C.78 0.35 0.56 0.25 Between 6 and 8 Sourca: Federal Register, \'ol. 39, Ho. 81. pp. 14676-14685, April 25, 1976. (Also 1395*.) 16.6 11.9 :.:s 2.14 0.37 :.:i Between 6 and 3 MCD 000016395 17 Moreover, some of the deadlines for compliance were impractical and the BAT, BADT, and BPT classifications of pollution control technology were confusing The Clean Water Act of 1977 was designed primarily to overcome the deficiencies of the 1972 law. It includes the following provisions (3-13938): EPA was permitted to issue individual extensions up to April 1979 to the 1977 deadline, if there was a genuine commitment to compliance. A list of toxic pollutants which must be controlled by July 1, 1984 and to which EPA could add or subtract was issued. (This list as of December 1978, is shown in Table 3.3.) EPA was directed to publish a list of conventional pollutants -- BOD, suspended solids, fecal coliform, and pH--which industry must control by July 1, 1984, using best available current pollution control technology (BACT or BCT). This new standard of control was to be specified by EPA through effluent limitation guidelines. Discharger of nonconventional pollutants--neither toxic nor con ventional--must install best available control technology by July 1, 1984 or, within 3 years after EPA issues effluent limi tation guidelines, whichever is later, but not later than July 1, 1987. Variances from this requirement are possible if it can be shown that this variance will not adversely effect water supplies, shellfish, fish, wildlife, or recreational use of the water. Provisions in the 1972 law which allowed EPA to grant economic variances from toxic pollution standards were eliminated. A partial listing of water quality criteria proposed by EPA, is shown in Table 3.4. Additional criteria and revised effluent standards for the organic and inorganic chemical industries, as well as for petroleum refining, were scheduled for publication before mid-1980. To achieve the goals of the Clean Water Act, EPA is developing a national program to pretreat nondomestic wastes before their discharge to municipal plants (Federal Register, 27736, June 26, 1978). Each publicly owned treatment works (POTW) with a design flow above 5 mil lion gallons per day is required to develop and enforce pretreatment C L 3 O 18 -u CC' 05 Table 3.3 lr.5. EPA LIST OF PRIORITY TOXIC POLLUTANTS AS OF DECEMBER 1978* Yolat ile Kalogenated Or2ani.cs ('*110) 6. 7. 8. 10. 11. 12. 13. 1-. 15. 16. 23. 25. 2 6. 27# 29. 30. 32. 33. ^H a -5. 46. 47, 43. 49. 50. 51. 52. 53. 35. 87. 88. Carbon tetrachloride Chlorobenzene 1 , 2,4-Trichloroben2ene 1,2-Dichloroethane l, L, 1-Trichi0roethane Hexachloroethane 1,1-Dichloroethane 1, 1,2-TrichLo roethane 1,1,2,2-Tetrachloroethane Chlo roethane Chlorororu 1,2-0ichlo robenzene 1,3--Dichlorobenzene 1,4-Qichlo robenzene 1,1-Dichloroethylene 1,2-t-Dichloroethvlene 1,2-Dichloropropane 1,2-Dicnloroprooyiene Methylene chloride Mechvl chloride Methyl brooide Srccotora Di chlo rob rcrtotr.e thane Trichlorofluoromethane Dichiorodifluoromethane Chlorodibronomethane Hexachlorobutadiene 'Hexachlorocyc lo pent ad iene Tetrachloroethylene Trichloroethylene Vinvl chloride 00 r- Aromatic Hvdrocarbona 1. Acenaphthene 4 Benzene Ethylbenzene 39. Fluo ranthene 55. Naphthalene 72. 1,2-Benzanthacene 73. Benzo[a]pyrene 74. 3,4-Benzofluoranthene 75. 11,12-Benzofluoranthene 76. Chrysene 7 7. Acenapnthylene 78. Anthracene 79. l,12-Benzoperylene 80. Fluorene 81. Phenanthrene 32. 1,2:5,6-Dibenzanthracene 83. Indeno[1,2,3-C,Dipy rene 84. Pyrene 86. Toluene Phthalate Esters 66. Bis(2-echylhexyl)phthalai 67. Butyl benzyl phthalate 68. Di-n-butyl phthalate 69. Di-n-octyl phthalate 70. Diethyl phthalate 71. Dimethyl phthalate Amines 5. Benzidine 28. 3,3'-Dichlorobenzidine 37. 1,2-Diphenylhydrazine A r\V<b~' sO sjS> 19 'able 3.3 (Concluded) U.S. E.PA LIST OF PRIORITY TOXIC POLLUTANTS AS OF DECEMBER 1978* Chlorinated Esters 1?. 3is(chloromechvl)ether id. Bis( 2-chlorcetr.v 1 )ether 19. 2-CUloroetnvi vir.vl ether (mixed) -0. 4-Chloropnenyl phenyl ether 41. 4-Braroophenyl phenyl ether 42. 3is(2-chloroisopropyl)ether 43. Bis(2-chloraethoxy)methane Other Aromatic Conoounds 9. 2C. 35. 36. 56. 106. 107. 108. 1C9. 1 10. 111. 112. 129. Hexachlo robenzene 2-Chioror.aohthalene 2,4-Dinitrotoluene 2,6-Dinicrctoluene Nitrobenzene PC3-1242 (Aroclcr3 1242) FC8-1254 (Aroclor- 1254) PCB-1221 (Aroclor-' 1221) PC3-1232 (Aroclor5 1232) PC3-1248 (Aroclor'' 1 248) PC3-126C (Aroclor5 1260) PC3-1016 (Aroclor~ 1016) 2,3,7,8-Tecracnlorodibenzo-p--cioxin Pesticides and Metabolites 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101 102. 103. 104. 105. 113. A1 d r i n Dieldrin Chlordane (technical mixture & metabolites) 4,4'-DDT 4,4'-DDE (p.p'-DDX) 4,4'-DDD (p,p'-IDE) Alpha-Endosulfan Se ta--End os uif an Endosulfan sulfate Er.d rin Endrin aldehyde Keptachlor Heotachlor epoxide Alpha-BHC 3eta-BHC Camma-SHC (lindane) Delta-BHC Toxaphene Nitrosamines 61. N-Ni t rosocinethvlanir.e 62. N-Nit rosodiphenylamine 63. N-Nitrosodi-n-propylami Phenols 21. 2,4,6-Trichlorophenol 22. p-Chloro-n-c resol 24. 2-Chlorophenol 31. 2,4-Dichlo ropheno1 34. 2,4-Dimetnyl phenol 57. 2-Nitrophenol 58. 4-Nitrophenol 59. 2,4-Dinitrophenol 60. 4,6-Dinit ro-o-cresol 64. Pentachlorophenol 65, Pheno L Misce ilaneous Compounds "1 3. 54. 116. 121. Acrolein Acrylonitrile Isophorone Asbestos (fibrous) Cyanide (total) Elements (total) 114. 115. 117. 118. 119. 120. 122. 123. 124. 125. 126. 127. 128. Antinony Arsenic Beryllium Cadmium Chromium Cop per Lead Nickel Me rcury Selenium Silver Thallium Zi nc *The categorization of impurities has been done by SRI. Source: B -- 13938 c 'v c c 20 MCD 000016398 V /&9S Table 3.4 u.$. EFA-FROROSED L'aTTR (TdCROCRAHS/LITER) QUALITY CRITERIA FOR SELECTED TOXIC POLLUTANTS Freshwater Aouartr ! Ife - Kr iveriae letilne Acenephthene Acrolein Ar.clnony Chlorinacea phenols *-Ohloropnno l 1,4 , o-Trtcnlo ropnenoi 3-Chle ropnenoi 2,5-Dlchlorophenol 2.6-Dleftlorophenol 2,4, 5-Trlchlarapnenal 2, 3,4,9-Tetrachloropnenol Copper Cyanide 3,3'-Dlchlorobenzldlne Dlchloropropanesl enes) ;,l-Diehlaropropane 1, 2-Dlchlaropropene l, 3*Dicftloropropene 1, 3-Dichlofopropane Dlnitrotpiuene 2,3-Dinttratoluene 2,4-Dlnlcrotoluene Diphenyinydrastne Endosulfan Endrin Ethvlbenzeoe Halocthen 4-Brcoophenylpnenyl Haloactnanes llechvl chloride lethyl bronioe 'iethyierte chloride Srcootora Brceoehlaroatnane Sic hi o rod If 1 joroaecnane Trlchiorocluronethane Isopnorone S* phchaicne Nickel Nitrobeniene Nltrophenols 2-Nttropnenol --SI trophenoi 2,4-Olnicropnanol 2,4-Olnitrocresol 2.4.6-Trlm trophenoi Phenol no i-: 120 240 2.7 1,000 45 `2 -- -- -- -- -- .(C.65 lo(hardness)-I.03) -- 180 150 -- -- -- -- -- .(0.88 In (hardness 1-1.03) 38 -- 410 920 4,aco 18 12 620 0.042 T.C020 -- 930 :co 11,000 250 27 l,00 38 0.49 0.10 -- 9.2 14 7,000 140 4.000 840 -- -- -- 2,100 -- lh( hard ness)-).02) 430 16,000 320 9.000 1.900 -- -- -- 4,700 -- .(0.47 ln(hardness )^4.19) 1,100 2,700 240 79 57 1,500 600 6,200 550 '.80 130 3.400 3.400 Fhthalace esters Disecnvl pncnalate Cietnvi onchalate Ttbutyl phthalate Ti*2-echvihexvl pnehalate PCS Toluene Toxepnene -inc -- -- -- -- eCC.b7 o.:: 15 2,300 O.C37 iruherc~.esa (*0. b 7 ) -- -- -- -- 6.2 5,200 0.47 .(0.64 in( herd ness ) .*6 ) Saltwater Aouatlc Life hr Average leilir.r Human Health rffeets 7.5 0.33 17 2-0 -- (0.02 o*/l) 6.5 1.-5 -- -- -- -- -- -- -- 0.79 -- -- -- 30 -- -- 50 -- 3.3 -- 3-3 -- 10* -- 263* IS (t ag/11 -- (0.2 a*/11 -- o' -- 400 79 5.5 -- 9 30 180 14 :o3 ; 33 :o3 0.63 4.4 -- -- -- 0.0047 -- 10 -- -- -- 0.031 -- (0. 1 0* 0* 3* ag/1) ( .. 1 ag/1) ---- -- 3.700 1 70 1,900 180 -- -- -- 97 -- -- 53 -- 53 37 -- 150 8.400 380 4,400 420 -- -- -- 220 -- -- 120 -- 120 84 -- 340 -- 2 : 2 2 2 3,000 3.200 460 143 133 30 (3.4 -- -- 68.6 12.8 10 L.0* -- -- -- -- 0.024 100 0.19 " -- -- -- -- .20 230 0.12 -- (160 ag/ U (60 ag/1) (5 ag/1) (10 og/1) (12.4 ag/1) 0* (5 ag/1) Proposed levels not yet eatab!ithed. 'Data are Inautflcient to sec criterion, but FA recoooends aimainng exposure*. *Organoleptic el facet. joucca; Toxic 'laterul >v, '.'eekiy Business letter, July 2J, 1978, Business Publishers Inc., P. 0. Bo* 1067, Sliver Springs :o9nr. MCD 000016399 21 programs in accordance with the standards issued by EPA. By 1983, this could affect as many as 38,000 to 55,000 dischargers in the United States (B-13938). Technical and financial assistance is available through EPA to industries and to POTW's for the implementation of this program CB--13939)- User charges are designed to fairly apportion POTW capital, and operating and maintenance costs between public and private sources (Federal Register, 17690, April 25, 1978). Land Pollution (Solids Disposal) The secure disposal of solid wastes presents an enormous environ mental problem in the United States* EPA estimates the output of solid industrial wastes at 336 million metric tons/yr (wet basis)--enough to fill the New Orleans Superdome, from floor to ceiling, four times every day of the year (B-13938). The proportion of potentially hazardous wastes is believed to be about 29 million metric tons/yr (8.6%) and growing at the annual rate of 3 to 4%, mostly generated by the chemical and refining industries* Some of this has been handled by inadequate disposal practices as evidenced by the problems at Love Canal, near Buffalo, New York, and the "Valley of the Drums," near West Point, Kentucky, from wastes discarded as much as 10 years ago. Companies generating these wastes in the United States do not escape legal responsibility for their safe disposal by turning them over to an independently operated for-fee disposal facility. The Solid Waste Disposal Act of 1965 was the first federal legisla tion addressing the solid waste problem. It provided mainly for research and development for waste treatment and resource recovery. The first comprehensive legislation concerning solid waste was the Resource Conservation and Recovery Act of 1976 (RCRA). This act includes the following provisions (B-13938, 447085): 22 MOD 000016400  Federal financial and technical assistance for the development of waste management programs. Identification and regulation of hazardous wastes from point of generation through disposal. Research, demonstration, studies, and information activities relating to solid waste problems. Standards of performance for those who transport, store, treat, or dispose of such wastes, including up to $5 million in liability insurance. Regulatory control of hazardous wastes by EPA, where state or local programs do not meet federal standards. Civil and criminal penalties (up to $25,000 fine and 1 year in jail for the first conviction) for false statements or noncompliance with enforcement orders. An augmenting piece of legislation is the Toxic Substances Control Act of 1976 (TSCA) (B--13938). This regulates the manufacture and use of toxic substances. It provides for a review of materials which may be hazardous to health or environment before they may be manufactured for commercial purposes* This law alone requires a monumental amount of testing and record keeping, since there are over 70,000 chemicals in commerce and over 1,000 new ones are introduced each year. In three years, the budget for EPA implementation of TSCA has grown to $58 million. Violators of this act can be subjected to civil and criminal penalties similar to those of RCRA. A third act of Congress with profound effects on the costs of solid (and liquid) wastes disposal is the Marine Protection, Research, and Sanctuaries Act of 1972, which proposes to phase out all dump ing of sewage sludge and industrial vistes by December 31. 1981 (B-13938). During 1977, ocean dumping of industrial wastes from the United States dropped from 2.7 to 1.8 million tons/yr and sewage sludge dumping declined 122 to 7.4 million tons/yr. The dumping of industrial wastes has now been largely eliminated but sewage sludge still amounts to about 4 to 5 million tons annually. The new restriction on ocean dumping has generated interest in sludge evaporation to yield animal feed, fuel, and fertilizer (447082), and in incineration aboard ocean vessels (447083). EPA has also 23 MOD 000016401 investigated the economics of land-based waste management facilities for hazardous waste disposal (447077) and has published a list of such facilities operating as of January 1977 (447092). Selected Reactions to U.S. Antipollution Legislation The enactment of comprehensive legislation requiring vast expendi tures for reduction of air, water, and land pollution has understand ably given rise to protest from those concerned with meeting and financing compliance standards. Hooker Chemicals for example, esti mates a 10 to 12% loss of existing vinyl chloride plant capacity in meeting EPA standards of 10 ppm for vinyl chloride concentration in air (447097). For vinyl chloride dispersion resins, the limitation of 400 ppm vinyl chloride weighted average on the resins, could reduce plant capacities by as much as 20%. The difficulties in measuring EPA toxic compound concentrations (e.g., those for arsenic) as low as 0.0002 raicrogram per liter (0.2 ppb), let alone controlling them, is dismaying to some segments of the chemical industry (447080). In many cases, it may be less expensive to meet effluent standards by process modifications rather than by end-orpipe treatments. A study of the economic impact of the Federal Water Pollution Control Act of 1972, prepared by 10 major chemical companies (447100), indicated that 80 to 90% of the BAT water pollution levels could be realized with 40 to 50% of the total capital expenditure for water cleanup, and that achieving the last 10 to 20% of the required improve ments (zero pollutant discharge) would take the other 50 to 60% capital investment. Thus, a major portion of the cost is required to meet the last increment of improvement. In this respect, Reference 447099 cites a General Accounting Office opinion that zero pollutant discharge is unnecessary because there is an inherent degree of self-cleansing capability in the nation's waterways. 24 MOD 00001640 The Manufacturing Chemists Association in the United States claims that the economic burden placed on the chemical industry by the Toxic Substances Control Act, for extensive testing and reporting of new products will impact on innovation. MCA has suggested an alternative simplified report form and a three-year status report (447081). MCA also proposes that less hazardous materials, e.g., ignitable wastes, should be given a different classification and standards than severely toxic materials (447084). The hazardous classification is said by others to be too.narrow because it does not include known carcinogens, teratogens, and neurotoxins. The Clean Air Act Amendments of 1970, which established uniform air quality standards across the United States, was controversial because it permitted deterioration of air quality in pristine areas to the same level as that in industrial regions (447098). As a conse quence, the Clean Air Act Amendments of 1977 were passed for the prevention of significant deterioration (PSD) of air quality. The pure air of park lands and wilderness reserves would be maintained while pol lution in urban areas would be allowed to increase to levels believed acceptable. This legislation is also controversial, because it permits increased air pollution in areas where the most people are exposed. Moreover, currently acceptable pollution levels may prove unacceptable for continuous long term exposure. A second point of contention con cerns the accuracy of atmospheric dispersion models (447098). Air quality standards are generally applied at ground level, whereas the concentration issuing from an elevated stack is generally much higher. Under some circumstances--atmospheric or topographical--this dispersion model may be inaccurate. Information Sources The complex and growing array of environmental regulations not including state and local actions, which now pours out of Washington in the form of legislation, implementing standards and requirements, con sent decrees, and informational literature is staggering. There are. MOD 000016403 25 however, a number of publications which are helpful in keeping abreast of this paper torrent. Table 3.5 lists the major legislation dealing with air, water, and solids pollution passed by the U.S. Congress in the past two decades. Actions taken by EPA to implement and enforce this legislation are pub lished daily in the Federal Register. However, since the Federal Register also includes the administrative actions of most other govern ment agencies, it is a very voluminous publication. Fortunately, two weekly reports--one on air/water pollution and one on c'oxic materials -- review current Washington developments in these areas. Both are published by Business Publishers Inc., P.0. Box 1067, Silver Springs, Maryland, 2C910- "Environmental Quality" is an annual publication of the Govt. Printing Office which reviews the developments in pollution abatement. In addition, Pollution Engineering Journal (1301 S. Grove Ave., Barrington, Illinois, 60010), in years past, has published a December status report of EPA actions and regulations. Some recent journal articles dealing with pollution control rules and regulations are listed as References 44.7002, 447085, 447094, 447102, and 447103. Several of the books dealing with pollution con trol legislation are listed as References B-13941, B-13942, and B-13943. Legislation in Japan Pollution abatement legislation in Japan is somewhat similar to that in the United States but with generally stricter limits on the allowable concentrations and quantities of pollutants. Basic pollution laws are enacted by the Diet, with implementation and enforcement being nandled by the Environmental Agency (B-13940). Local governments-- industrial districts and cities--have the authority to require more stringent pollutant limitations and controls than those adopted nationally. Thus, as in the United States, the acceptable levels of pollutants can vary appreciably in different parts of the country. 26 MCD 000016404 Table 3.5 i. MAJOR POLLUTION CONTROL LEGISLATION BY THE U.S. CONGRESS Congressional Act Public Law Numbe r Air Pollution Air Quality Act of 1963 Air Quality Act of 196/ Occupational Safety and Health Act of 1970 Clean Air Act Amendments of 1970 Clean Air Act Anenacents of 1977 88-206 90-U8 91-596 91-604 95-95 Water Pollution Federal Water Pollution Control Act Amendments of 1972 Marine Protection, Research, and Sanctuaries Act of 1972 Clean Water Act of 1977 92-500 92-532 95-217 Solids Pollution Solid Waste Disposal Act of 1965 Toxic Substances Control Act of 1976 Resource Conservation and Recovery Act of 1976 89-272 94-469 94-580 Congress 77th 8 1st 84th S4ch 91st S6ch 86th 91sc 79th 90th 90th Statute 392 485 596 1676 685 816 1052 1566 997 2003 2795 Date Dec. 17, 1963 Nov. 21, 1967 Dec. 31, 1970 Dec. 31, 1970 Aug. 7, 1977 Occ. 18, 1972 Oct. 23, 1972 Dec. 20, 1977 Oct. 20, 1965 Oct. 11, 1976 Oct. 21, 1976 Source: Reports of the L'.S. Congress House of Representatives and Senate, Issued by Superintendent of Documents, Government Printing Office, Washington, D.C., 20402. 000016405 MCD 27 The Basic Law for Environmental Pollution Control, enacted in August 1967, in Japan, set the stage for regulation and abatement of air, water, and noise pollution and, indirectly, of land pollution by solids (B-13940). Air Pollution The subsequent and comprehensive Air Pollution Control Law of June 1968, established national ambient air quality standards in Japan as follows: Sulfur dioxide Carbon monoxide Suspended particulate matter Nitrogen dioxide Photochemical oxidants Daily Average Hourly Value, Max. <0.04 ppm < 10 ppm <0.10 mg/m3 < 0.04-0.06 ppm <0.06 ppm Hourly Value, .lax. <0.1 ppm < 20 ppm for 8 consec. hours < 0.20 mg/m3 A 1978 amendment to the sulfur dioxide emission standards made the following revisions: The hourly volume of S0X (Nm3/hr) from a stack should not exceed: K x 10-3 x He2 where K a constant He effective stack height, meters The total emissions of SO^ (Nm3/hr) from a plant should not exceed: a x Fb where a and b * constants F * fuel oil usage, kl/hr. Small plants, using less than 1 kl/hr, are exempt from the above two rules but they are required to burn fuel oil with less than a designated sulfur content. 28 wcr> 164 os The values of the constants (K, a, and b) and of the sulfur content of fuel oil are set by local governments. In Kawasaki, which has the most restrictive limits of any area in Japan, the values for K, a, and b are 1.17, 1.5, and 0.865 respectively. The maximum allowable sulfur ^ content in fuel oil burned by small industries is 0.30 wt% A June 22, 1971 amendment to the Basic Pollution Law in Japan sets standards for soot and dust particulate emissions depending on the type and size of an industrial operation. For example, a small boiler burning liquid or gas' has a limit of 0.30 g/Nm^, whereas, for a large scale V boiler, this limit is 0.10 g/Nm^ and, for a boiler operating on lower grade coal, it is 0.80 g/Nm^ (B-13940). Continuous incinerators have ordinary solid emission standards of 0.20 and 0.70 g/Nm^ for large and small scales. The most recent amendment for control of NC^ pollutants in air sets upper emission limits for various facilities in Japan: Facility Effluent Flow Rate (10^ Nra^/hr) Upper Limit for NO* Cone, (ppm) Boilers Gas burning Coal burning Oil burning Petroleum fired heaters Cement kilns Nitric acid plants >500 40 to 500 10 to 40 < 10 -- >500 10 to 500 >40 10 to 40 5 to 10 <5 >100 <100 -- 60 100 130 150 400 130 150 100 130 150 180 250 350 200 MCP 000016407 29 These Units apply to new operations installed later than June 1977. Somewhat higher limits are permitted in older facilities. The air pollution amendment of June 1971, also specified emission limits for five types of toxic substances: Substance Cadmium and its compounds Chlorine Hydrogen cloride Fluorine, hydrogen fluoride, and silicon fluoride Lead and its compounds Upper Limit (mg/Me3 ) 1.0 30 80 1 to 20 1 to 20 Hydrogen chloride emission rates as high as 700 mg/Nn^ are possible for incinerators of waste chlorides. The fluorine and lead range between 1 and 20 ng/Nn^, depending on the nature of the manufacturing operation. Water Pollution The Law for the Preservation of Water Quality in Public Water Bodies was enacted in December 1958 in Japan. This was augmented in December i970, by the Water and Marine Pollution Control Law and by the Revised Sewage System Law. National limits have been set for the following conventional water characteristics or impurities: 30 ooooia Allowable Quantity pH. - effluent discharged to public waters - effluent discharged to coastal waters BOD, COD - maximum - daily average Suspended solids - maximum - daily average n-Hexane extract-mineral oil -animal and vegetable fat Colifom groups/cc - daily average 5.8 to 8.6 5.0 to 9.0 160 mg/liter 120 mg/liter 200 mg/liter 150 ng/liter 5 mg/liter 30 mg/liter 3,000 v Limits have also been established in Japan for a number of metals and toxic materials: Phenols Coppe r Zinc Dissolved iron Dissolved manganese Chrome Fluorine Cadmium and its compounds Cyanide compounds Organic phosphorus compounds Lead and its compounds Sexivalent chrome compounds Arsenic and its compounds Total mercury Alkyl mercury compounds PCB Allowable Quantity (mg/liter) 5 3 5 10 10 2 15 0. 1 1.0 1.0 1.0 0.5 0.5 0.005 Not detectable 0.003 0o 31 As in the case of air pollution, local governments have the authority to set and enforce lower limits for these and other pollutants in water effluents. Such areas include the Seto Inland Sea, Tokyo Bay, and Ise 3ay (B-13940). In Japan, it is customary for chemical producers to conclude a pollution prevention agreement with the local authorities or public waste treatment facility. Over 1,250 such agreements had been signed by October 1978. Prospective new chemical producers must have the approval of both 'the Environmental Agency and the local government before plant construction can be started. Land Pollution The high value and limited availability of land in Japan effec tively limits the use of land for solid waste disposal. The incinera tion of solid and liquid wastes is common in Japan, with any ashes going to landfill. In these instances, regulations relating to air pollution and to ground water contamination will apply. A small number of solid waste disposal sites are closely regulated by national and regional government. In some areas of Japan appreciable areas of agriculture land have been contaminated by cadmium, copper, or arsenic resulting from air and water pollution. The total land area affected is about 3,850 ha (9,500 acres). Remedial measures include replacement of top soil, and diversion of water sources. Chemical Substances Control Law The Chemical Substances Control Law, enacted in 1973 in Japan, is designed to cover those areas of chemical production and use not previ ously subject to pollution controls. It requires a thorough screening and testing of any new chemical before a permit for its importation or manufacture is issued. 32 O0OOV641C MOD Existing chemicals are being catalogued and checked for biodegrad ability and for hazards to humans or to the environment by the Ministries of International Trade and Industry and of Health and Welfare. If a substance is found to be environmentally harmful , such f as in the case of a polychlorinated biphenyl (PCB), the government can ^ halt its importation or manufacture. The checking and control of potentially hazardous materials in working environments is covered by the July 1977, revision of the Labor Safety and Sanitation Law, with implementation by the Ministry of \ Labor. Expenditures in the United States Expenditures for pollution abatement in the United States have been recorded since 1973 by the Bureau of the Census and the Bureau of Economics Analysis--both divisions within the U.S. Dept, of Commerce. These are the sources for most of the U.S. information on pollution expenditures and performance. The census figures, which cover manufac- /' turing industries, are believed to give the more detailed classification by industry type, nature of pollutant, and state and urban locations. BEA figures include manufacturing pollution sources as well as nonmanufacturing pollution sources such as utilities and transportation. Capital Expenditures Capital spending in the United States, since 1973, for the allevia tion of air, water, and land pollution is shown graphically in Figure 3.1. Also shown are the projected estimates for 1982 and 1985, together with the pollution abatement capital expenditure (PACE) as a percentage of total new capital spending by the chemical industry. Capital investment for pollution abatement in 1977 was almost $1,000 million, or about 13.5% of total new capital spending. Water treatment accounted for 60% of this cost, air cleaning for 35%, and solids MOD 000016411 33 Figure 3.1 ANNUAL CAPITAL EXPENDITURES BY THE U.S. CHEMICAL INOUSTRY FOR POLLUTION ABATEMENT I'ERCEN f OF T O T A L NEW C A P IT A L E X P LN U I l NHL S $ in.lim n. POl LU IIO N ABATEMENT EXPENDI Source: Pollution Abatement Costs and Expenditures Current Industrial Reports. MA-200. 1973 thru 1977, Bureau ol Census. U S. Dept. o Commerce, Washington, D.C and Reference 447003. 3-J MCI) 000016412 disposal for Che remaining 5%. Most of the air and water expenditure (88%) was for end-of-line treatment, and only 12% was for in-process changes Between 1979 and 1985, PACE is expected to rise from $830 million/yr to about $1,300 million/yr, with practically all of this increase going for water treatment facilities. This represents an average increase of about 8%/yr in current dollars or 16% per year, if 8.0% inflation is assumed. As a percent of total new capital expendi tures, PACE is expected to remain in the range of 10 to- 12%. Presuma bly, if the goals of the 1977 Clean Water Act are met by 1985, this percentage will then drop to some lower figure corresponding only to new plant pollution control requirements. The distribution of pollution abatement expenditures among air, water, and land for the eight sections of the chemical industry as reported by the U.S. Census Bureau is shown in Table 3.6. The major abatement expenditures, in column one of this table, are made by inorganic chemicals (16% of total expenditures), plastic materials (15%), industrial organic chemicals (45%), and agricultural chemicals (15%). Drugs, soaps, paints, and miscellaneous chemical products make up the remaining 9%. While PACE for the overall industry is 13.2%, for the organic and inorganic segments, the expenditures are 15.4 and 21.8% respectively. The distribution of capital expenditures in 1977 for the composite chemical industry is 35, 60, and 5% respectively between air, water, and land pollutants. For air purification, particulate removal represents the major portion (43%) of its capital investment; N0X is next at 32%; heavy metals, radioactive materials, toxics, and others represent 19%; and sulfur oxides are last at 6Z. In 1977, the esti mated amounts of pollutants removed from air by the U.S. chemical industry were as follows: 000016413 35 T*bl 3-6 U.S. POLLLTIOS AMiriSVT EXFSVDI7T;*S FOR AIR, WATER, AND SOLIDS. BY CHEMICAL INDUSTRY SEGMENT (Millions ot Current Dollars) *.ojstrv s*_*~enc Pollull on Abatement Capital Expenditure ?ALt ) pace as i ot Total S'e Capital Ixsencvt - :* * Distribution of Air Pollution Abaeeoenc expenditure End or Partlc- Octal I Line Process uiaces SO' :<%. Oerter lnor;jn*c ^.eiua.s, a.-alics, - -,; r; " e , g&aes, pigments, CISC Plastic materials resins . rvbber , cellulose ar.a organic libers Drugs and pharaaceuc ica Is Soaps, oeterger.ts, ;c.ishes , :ci let r repa rat: ons , etc* Paines and allied p r ocuc t s Industrial a rear, ic meaicals, inter mediates. -ood chemicals, guns and cyclic organics Agricultural chemicals and fertilizers miscellaneous chemi cal products, adhe sives, explosives, carbon Place, etc* Industry tscaL 15 0,0 151.4 ::.i 5.- 137.0 1-9.3 -4.7 982.4 11.3: 9.6 -0 -. 5 56.0 35.9 51.5 -. 5 3C.2 3.4 5.9 !0.5 88.6 57.4 77.9 10.7 3. 3 22.9 3.1 0. 2 -8. 7 0. 3 27.6 12.0 1.8 0. ) 0.5 0. 7 3.9 i0.2 1.1 32-4 8. 5 1.0 3.4 0. 1 5 L. 5 1.0 3.9 0.8 -- 0. 2 3.1 15.4 10. S 13.22 1 11.2 25.4 93.6 17.6 22.3 11.0 59.4 18.4 52,3 34.9 -5. 3 7.0 25. 7 2. 4 9.- 14. 1 18.6 340 41.6 34.6 10.0 296.9 2.6 43.1 12.0 145 1.2 2C. 1 5.1 1 29.1 0.2 o5.a r"'' MCD 000016414 36 c 0 I Tabic 3.6 (Concluded) L'.S. ?0U.!TT10N ABATEMENT ES7ESTIITV7ES FOR AIR. WATER, AST) SOLIDS. Bf CHEMICAL IKDCSTRT SEGKEVT (Millions of Current Dollars) Industry Seepent Distribution of Pol luc lor. Abatement ExDer.dl ture Total end of Line Process Total " Inorganic cr.eaicais , dLiulies , :r.iv r;fit, gases, pigacnts, 3L5C e 86.; 55.1 91-2 5.2 13.6 8.6 Plastic materials reaina , russer, cellulose end organic fibers 62.9 40.7 55.2 7.7 2.9 1.9 V Drugs and pharmaceuticals 3.9 61.8 8.7 0.2 2.2 15.3 Saaos, detergencs, tolishes, toilet prepe rat ions , etc i:.i 56. 1 12.3 2.1 0.8 3.7 Paints and silled P roauc c s 1.7 50.0 1.5 0.2 0.7 17.6 Industrial organic cheoicals, ictersedlates, wood chesleals , guns, and cyclic organics 302.3 69. 1 276.0 26, 3 24. 2 5. 5 Agricultural tneaicais and fertilizers 93.1 62.1 77.6 '.5.5 4.4 3.0 I'.lacel laneoua cheaical products, adbeslvss, explosives. Industry total 25.3 593 56.6 60.1 17.5 530 7.8 63.0 0.8 49.1 1.8 5.0 *All figures arc for eric calendar year 197?, except the pollution ebsteaent apenditure* (PACE) as a Z of eoeal new capital expenditures, rfilch are for 1976. Source: Current Industrial Reports. "Pollution Abatenenc Costs and Expenditures", 1976 and 1977, ?*A-200( 76)-2 and KA-200(77)-2, U.S. Dept, of Conaeree, Bureau of the Census, U.S. Cove. Printing Office, Washington, D.C. V 000016415 MOD 37 Particulates Nitrogen oxides, hydrocarbons, and CO Heavy metals, radioactive materials, toxics, others Sulfur oxides Total Thousands of Short Tons 3,447 1,815 700 1,033 7,024 Operating Costs The growth of operating costs for pollution abatement by the U.S. chemical industry between 1973 and 1978 was approximately 3-fold as shown in Figure 3.2. This corresponds to average annual growth rates -- in current dollars--of 1S%, 26%, and 29% for air, water, and land. (Constant dollar percentages are 6, 14, and 17%). The combined annual operating costs for pollution abatement were equal to 2.0% of the value added by the chemical industry in 1977. By 1985, this percentage could reach 2.7 to 3.0% of value added. Pollution abatement operating costs by chemical industry segment are reported in Table 3.7. Also shown is the distribution among air, water, and land, and the nature of the costs. Pollution abatement operating costs for drugs, soaps, and paints are 0.6% or less of their value added. However, for inorganic chemicals, they are 2.7%, and for industrial organic chemicals and agricultural chemicals, they are 3.5 and 3.7% Sizable variations in operating costs also occur within the chemical industry sections. Within the industrial inorganic chemical section, for example, which includes pigments and industrial gases, pollution abatement costs for a sulfate process titanium dioxide pigment plant can equal 10% of value added, whereas those for an air separation plant are less than 0.20%. Reported research and development expenditures by the U.S. chemical industry for pollution control has grown from $55 million in 1973 to $84 million in 1977. However, this latter figure is exceeded MCI) 000016416 38 Figure 3.2 ANNUAL OPERATING COSTS OF THE U.S. CHEMICAL INDUSTRY FOR POLLUTION ABATEMENT AN N U AL OPERATING COST FOR PO LLUTIO N ABATEM ENT. $ millions A N N U A L O PERATING COSTS AS A % OF V A LU E ADDED Sources: See Figure 3.1. YEAR 39 MCD 000016417 Table 3.7 C.S. POLLlTtCN A8A7EIEN7 OPERATING COSTS FOR AIR. -ATER. A.STI SOLIDS 'Million* of Current Collars) CHE11CAL ISD-STRT SECIIST jf T c e r a t: i Total Operating Cost industry 1 e t ce n c i iue \aced Inorganic cr.eaic a 1 s , a 1 la i 1 e s , chlorine. gases, pigments, disc. Plastic saranals. resins, rucoer cellulose ana organic fibers Drugs and pharmaceuticals soaps , ie ce rgenc s , polishes, toilet prepara t ions , etc. Paints and allied products Industrial rrgsnic chemical 5, ;:.ter* mediates , ood chemicals, gums ana cvclic organics Agricultural chemicals and fe rt ll lie rs Ml seel laneout chosical pro ducts , adhesives, explosives. carbon black, etc. Industry local 1,138.3 Bv -sro or .Abatement De rec rat ion labor .8.5 38.3 =8.7 13.1 3.7 38.6 -c.9 87.1 2-.3 335. 5 585.3 217.5 238.9 . la c e r i a i Supc. les. Serv ices . Ipp.er 13.0 .- 5 M.5 -CSCS c:verec 1.8 2C6.6 All figures are roc the calendar var 1977, except the total ooeraclng costs as a percent of value added, which Is let 1375. Value added lnc.jdes all cianutacturlng costs ocher than raw materials. Recovered coses are the value of salable wastes such aa scrap and fertilizer or of recyclable material. Sources: Current Industrial Reports. "Pollution Abatement Costs and Expenditures", 19 7 7. MA-ZOOl743-2., also Annual Survev of Manufactures, General Statistics :cr Industry Groups-1375 and 1976. Roth .'.i. Dept, ox Coemerce, 3uceau or the Census, L'.S. Govt. Printing Office, Washington, D.C. c / t MOD 000016418 c 40 by the petroleum refining industry, with $88 million, and vastly so by motor vehicles and equipment, with $485 million. Expenditures in Japan Expenditures by the Japanese chemical industry for pollution abate ment have grown from 7.5% of new capital investment in 1971 to 17.7 % in 1975, as shown in Figure 3.3. However, since 1975, this percentage has declined steadily to 3.7% in 1979. The yearly expenditure for pollution abatement in 1979, was 4,5 x 10^ yen ( = $18 million). V The distribution of pollution abatement expenditures in Japan, by type of pollutant, for the years 1977 through 79 are given in Table 3.8. Table 3.8 JAPANESE POLLUTION ABATEMENT EXPENDITURES Pollution abatement expenditure (10^ yen) Distribution of expenditure (%) Air pollution abatement Water pollution abatement Noise reduction Waste disposal (mainly incineration) Other related activities Total % 1977 14.2 1978 6.2 1979 4.5 36.6 33.8 4.9 9.9 14.8 100.0 33.9 33.9 1.6 22.5 8.1 100.0 29.3 47.3 0.9 13.5 9.0 100.0 Source: Ministry of International Trade and Industry. MOD 000016419 41 Figure 3.3 ANNUAL CAPITAL EXPENDITURES BY THE JAPANESE CHEMICAL INDUSTRY FOR POLLUTION ABATEMENT AS A PERCENTAGE OF TOTAL NEW CAPITAL INVESTMENT PERCENT Oni " J^2o 42 4A wastewater treatment technology The various levels of wastewater treatment may be defined as follows (447041): (1) Pretreatraent: To equalize flows and separate immiscible oils or quick settling solids. (2) Primary Treatment: To eliminate dissolved or finely sus pended solids and liquids by chemical or physical means. (3) Secondary Treatment: To make a biomass sludge from organic materials by biological oxidation. (4) Tertiary Treatment: To remove residual impurities or make the water sufficiently pure for human use. Each of these stages may consist of one or several operations, depending on the impurities in Che wastewater and on the degree of purification desired. Figure 4.1 illustrates most of the operations which are currently available commercially for the treatment of aqueous wastes (B-1393, B-1394). Wastewater streams such as process water, boiler blow-down, and runoff water may be treated separately or col lectively through the appropriate operations in one or more of the treatment stages shown. Streams requiring different methods are kept separate and then combined at that point where subsequent treatment beccr.es similar. For example, runoff waters might be settled in a thickener; process water might be neutralized and filtered; and the sanitary sewer flow might be treated by secondary activated sludge and vacuum filtration. All three streams might then be combined for a water quality check, flow equalization, and discharge to a municipal sewer or an adjacent water body. Where an additional liquid waste stream is generated, such as by thickening or ion exchange, a treatment flow path is developed for it in the same manner as for the original waste stream. ,, aO' 43 WASTEWATER TREATMENT ALTERNATIVES rtCD 00001^2- Pretreatment The equalization of flow to a waste treatment plant serves several purposes: Easier control of subsequent operations and a more uniform conposition. Saving in capital investment since the plant can be designed for smaller flows. Surge capacity (in the equalization reservoir) for short downstream stoppages or for an orderly shutdown of industrial waste flows. Appendix B gives an example of a typical equalization calculation to minimize the BOD variation in a waste treatment plant. BOD values range from 200 to 1,100 ng/liter over a 12 hour cycle in a waste flow of 1 ngd (million gallons per day). To control the BOD in the feed at 630 mg/liter (-H3 cg/liter) would require an equalization reservoir of 1.3 million gallons. The flow equalization function can be combined with that of a thickener so that settleable solids are simultaneously removed. Table 4.1 gives typical settling areas for a variety of solids in aqueous suspension. These vary from 0.4 sq ft/ton solids/day for -325 mesh iron ore to 600 sq ft/con solids/day for a manganese sulfide precipi tate. Thickener design requires laboratory data on the settling rate of the suspended solids at various concentrations, and on the thickness of clear water, feed, settling and solids contact zones. From this, the thickener area, depth and underflow solids concentration are calculated (B-l, B-1395). Floating solids or oils can be removed by a skimmer on top of the thickener (447043). Emulsified volatile liquids can be separated after equalization by stripping with steam or flue gas. MCD 0000VS4-3 45 Table 4.1 TYPICAL THICKENER AND CLARIFIER DESIGN CRITERIA Suspended Solids Perce nt Solids reed Underflow Settling Area* (sq ft/ton solids/dav) Equivalent Solids Flux (lb/sq ft/dav) Asbes tos Cement kiln dust 9-12 9-10 Cyanide slimes 16-33 Iron ore, -325 mesh 20-35 Line slurry (acetylene) 12-15 Manganese sulfide precipitate 0. 5 Power plant flue dust 1-5 20-27 45-55 40-55 60-70 30-40 5-8 50-60 7-15 3-18 5-13 0.4-0.8 15-33 400-600 2-10 133-285 111-666 154-400 2,500-5,000 60-133 3.3-5 200-1,000 *Depths noraally range from 8 to 15 feet for diameters from 10 to 150 feet. Source: B-l, page 19-55. Primary Treatment--Chemical Objective The purpose of primary treatment is to prepare the waste stream for biological oxidation by removing those materials which are not amenable to, or which interfere with, bacterial oxidation. It also removes those suspended liquids or solids v;hich are not removed in the pretreatraent reaction by simple sedimentation or skimming methods. The chemical and physical methods employed here are well established indus trial practices. This report will deal with these technologies only as they relate to waste treatment. Pre- or primary treatment is generally necessary when the pollutant levels in Table 4.2 are exceeded. MOD 000016424 46 Table 4.2 WATER POLLUTANT TREATMENT 1ETHODS Pollutant Suspended solids Oil or grease Heavy metals Alkalinity Acidity Toxic organics Sulfides Phenols Ammonia Dissolved salts Limiting Concentration 125 mg/liter 50 mg/liter See Table 4.3 0* 5 mg as CaC03 per mg BOD Free mineral acid See Table 4.3 100 mg/liter 70-160 mg/liter 1,600 mg/liter 16,000 mg/liter Treatment Lagooning, sedimentation, filtration, centrifuging, flotation. Skimming, centrifuging, separation. Precipitation, ion exchange, active carbon adsorption, reverse osmosis. Neutralization. Neutralization. Active carbon adsorption, ion exchange, evaporation. Precipitation, stripping. Active carbon adsorption, solvent extraction. Dilution, neutralization, stripping Dilution, ion exchange. Sources: B-1394 and 5-13913. Table 4.3 Uses certain Inorganic and organic chemical pollutants which are toxic to humans and animals and which, at sufficient concen trations, inhibit biological oxidation systems. It includes 129 elements and compounds'--a large portion of which consists of halogenated organics--selected by the U.S. Environmental Protection Agency (EPA) as priority pollutants (i.e., those waste materials in need of immediate attention). Suggested maximum concentrations in aquatic freshwater for many of the insecticides and herbicides included above are in the range of 0.001 to 0.1 mg/liter Cl to 100 ppb). Control -'X) O0001642& 47 (Text continues on page 54) Tibi* 4.1 TOXIC INORCANIC and ORGANIC FCLLLTANTS AND METHODS FOR THEIR CONTROL Pollutant Ir.orianii Aaaon l m Ant laony' An enic 7 *.sbescos (f ibrous} Soron (bailees) Beryl 11 ua7 C^daluD 1 Calelun O.rsoiuD-rtexavalent Trivalenc1 Copper1 Cyanide7 I roo Lead7 ^ognje Magnee lua M* rcury* Nickel7 Selenlus' Silver7 Sodluo Suliare Sulfide Thai llua7 ZittC7 Ionic State 'cxlc ltv or Hatard (Huna ns > TLV* >jiuCion iai tS ACLivateo Sludge Anaerooic Digest ion Mtrlilc VH,,*! Sb*> A**3 -- ao^'J 8*2 Cd*2 Ca*2 Or*3 Cu** CT"` Fe*3 Pb*2 Mn*3 Mg*1 Kg*3 si+z. SI*** Se04*3 A*` Sa*l SO (.*2 S-2 Tl*3 2n*3 :i ppo Skin burns 3oo explosive 0.5 og/a3 Skin irritation Poisonous (sol. salts) 0.5 sg/a3 Skin Irritation Poisonous 1 fibers/c-3 (carcinogenic) -- -- (1 ?pa) Skin burni (hftildca > Very toxic 0.002 eg/a3 - Poisonous 0-05 ag/a3 -- Toxic (sage explosive) -- Skin irritant -- (alkali ag/n3 <CrO-)l -- Skin irritant -- Toxic (cn rosaces) -- Toxic (dust) 10 ppa (HCS) Toxic Poisonous Toxic Poisonous ~ Deconp to HC1 Toxic, sue burns (FeClj) 15 ag/a3 Toxic Poisonous - 0.01 ag/a3 (aetal) (HnP^ very reactive ) -- Toxic Toxic 0.1 ag/a3 Irritating Toxic 0.2 ag/a3 Toxic 3.01 ag/a3 Toxic 2 og/m3 (NaOH > Skin burns (HaOK) t ag/B-3 (H;S04) Sums (H2S04) 15 ag/a3 ( rl; S > 0.1 Bg/B3 Poisonous -- Poisonous Toxic -- Toxic (H2S) Poisonous -- .SO 0. 1 r.one -- 1C-10C :.5co .-10 5C o. ;-5.a I, coo a. i 10 0.1-5 1.0-2.5 5 a. 500 - 0.3 1. 500 1.6 none -- a.a: -- 5-50 50-500 :.a 5 l.CCO 1,365 2.0 -- 50 _ -- none -- - - -- 0.25 -- a.aos-o. 0.34 -- 0.5 50 -- 0.53 -- 500 - 0.08-0.5 MCD OOOO x $426 48 ( S' C e Table *.3 (Continued) TOXIC INORGANIC AND ORGANIC POLLUTANTS AND METHODS FOR THEIR CONTROL Pollutant Carbon Miorpuon Control Methods Preeipicacion with________ CaCOH) a SaS Ion Exchange Reverse Parents* nor game I/ V, Aanoaia Anc iscny" X Arsenic' Asbescos (fibrous)' Boroo (halides) X XX 3eryiliuor Cadmus' XX X XX Calciuo Chraoiua-Nexavalenc ' T rlvaient' Copper' Cyanide1 Iron Lead r Ilanganese Magneslua Mercury' Nickel1 Selenlus' Stiver' Sediua X X XXX X X XX XX XX X X x X XX x X X x X X X X Sulfate Sulfide T-.alUuaZinc' X XX X Threshold Halt values for repeated 8 hour day exposures without adverse effect. ^Reverse oteosis gives a 94 to 99t rajectlon of rest Decal Iona froa feed solutions of up to 12 wtZ concentration. Slectredlalyits concentrates sost aqueous inorganic salts froe 1,000 to 5.000 ppa to about 10.000 pf* but with 100 to 300 ppa left in the purified streaa. Sources: 8-1394, 8-1397, 8-1398, 447028. MCD 000016427 49 Table *.J (Continued) TOXIC INORCAH 1C AND ORGANIC POLLUTANTS AND METHODS FOR THEIR CONTROL ?* 1 Vacant 'raamc icenapntr.ene Acrolein 1 Acrylonitrile1 Allyl alconol Allyl chloride Benzene1 Noraal State Liauid . Soild. CdS Soiling Point '> SODt _S '7? - s:.5 J.O L 7.- 0. 7 2 5- 96. 9 C 2 L -5.3 0.23' L 30.1 2.13 ienzldfi n* Carbon tecrAchXoxlie Chloroiora Iresol Orotonyl alcohol Chrvse n 1.--Diae t r.v Ipner.ol .S -c: -- '6. 7 7.0 L 62 ;.c 2 L 191 l b 121 - S --8 - S Tl 1-5 - 1,--Diniirnttluere' Dl-(2-e thy 1 hexyl Ipnthil ateT Ol-n-hutvi pnchalace" Ethylbenzene r.-Heptyl alcohol n-Hexyl alcohol s L L L L L 300 335 3*0 136.2 176 153 0.*3 322 of ThOD 282 of ThOD Theoretical Oxygen 2emeno, ThOO Toxlcitv to Ooldfljh, Concentration and 7loe for 502 Fatality _ cccd) 3. 17 2.2 :. 64 2. 10 _ 008 ag/ l, 2 :.r 11.8 ag/1, 96 hr (Bluegill 1.0 og/ 1, 2* hr 20.9 sg/1, 96 hr *6 *g/ 1, 2* hr C.21 1.2*6 2.52 - *9 ogii, 96 hour 13 ag;1, 96 hour - 10 og/1 -- - 96.4, 96 hr ----- Isophotone lie thy lene crtia ride hapht haiene Nitrobenzene o-Nitrophenol^ p-Hitropneool* nKletanol ?henolr L 215 - -- L *2 -- S 213 0 L 211 0 S 214-217 - s 279 - -- 2.99 1.95 - -- L 195 382 ThOD. 2.95 - L 132 1.4 2.4 57 ng/1, 96 hr MCI) 000016428 50 r V r c c ( c s' Table 4.3 (Continued) TOXIC INOftCANtC AND ORCANIC POLLUTANTS AND METHODS FOR THEIR CONTROL Pol lucent_______________ Threshold Cone. Inhibitory to Slaiozical ?rcdess tog;liter; Act lVi tea Ar.aerooic Sludge Digeacian M: rlf tear tan Control Methods ';<mc Aceaapntheoe Ac ro.*in' Acrylonitrile' Allyl alcohol Ailyl chloride Beotene7 -- 53 92 Senzidene' Catoon tetrachloride7 Chlorof ora -rtgol Crotjnyl alcor.ol Chrysene I. l-OloetKviphenol7 2,-blnlirocomene7 3l-(2-e thylhexyDphthalace" Ol-S-butyl phthalace7 E t hvlbenaene' n-depcyl alcohol n-Hexyl alcohol :c 115 33 5C0 (E. Coll) 57 12 67 -100 -- .0-10 10-16 500 -- 500 1.000 19.5 180 -- *- i6 -- - Tsophorone Met hv lene chloride Naphthalene Ml trobeaaeoe' o-Sicropneooi p-Nltrophenol7 n^Dc tanol Phenol7 -- 1 7 0.9 * 50 200 -- 100-500 -- 200 -- -- 4-10 15 vt! retention on active carton, water scrubbing, Qir.0* Biodegradation By autanc microorganisms Activated carbon (retention - O.C24 g/g) Evaporation 4 25C (901 of 1 pps after 39 am) Active carbon (0.08 g/g), air stripping, anaerobic lagoon (13 lb/day/1,000 sq ft; 10 ag/l In, 5 ag/1 out/ Evaporation 3 25C (90! of . ppm after 9' min) Evaporation <? 25C (90! of 1 ppa after a) cm) Ion exenange (100! retention on Aaberiite* XaD-2) - ton exchange (100! retention on Aaoerlite9 .5X3-2) Biodegradation in fresnvater hydrosoil Active carbon (85! retention at 100 g/1) Activated sludge (27! oxidation at 500 ppa after 12 hr) Aetlvaced sludge (29! of ThOO efter 24 hr) Active carbon (absorbability - 0.19 g/g); reverse osmosis (47! rejection froa 0.01 71 solution); Ion exenange on berllta XAD-2 (85! retention at 200 ppa). Anaerobic lagoon (48 lb COD/day 3 1-0 mg/1 in and 30 ag/l out) Active carbon (0-193 g/g, 97! retention from l.CCO mg/ 1 Inf low) Evaporation from water at 15C (90! of 1 ppa after 30 aln Ion exchange, 100! absorption on Aoberlire XAG-2 Active carbon <3 .196 g/gC (96! adaorbance 9 1 , 223 ag/1) Biodegradation by soil microflora Ion exchange (100! retention on Aaberlite7 XAD-2 at 0,2 ppa) Reverse osmosis (68! rejection from 0.01 M Sola) (1) Active carbon 0-161g/g C <81! adsorption froa 1,000 og/1) (2) Adsorption on Aaberiits* XAD-7 (86! effee at 0.4 ppa) (3) Solvent extraction with light oil (95!) (4) Trickling filter (100! reaovai at 20 ppa) 0000164^9.9 mod 51 = 3 Llutanc rrj:ar?;-C a.:: -.cl Cc t racn .g;oe t r.-. iene Tr lchlorae t.-.v ler.e 'Inyl chloride' Table <i.3 ; Cent Lnuefi ) TOXIC INORGANIC AND CPCAN' 1C PCLL-TANTS .AND 'ZTHODS FOR 7H IS. CONTROL Noraal State Licuid. Solid. Gas __3oil mg ?o me : 15 Cl.do. ' SCPt P-.OC Toxic icv to Colarish. ConcentratLon ana TIse tor Fatal.c- 53 aii1. 96 nr c. mod 000016430 52 c 0 l Table -,.3 (Concludes) tdt.ic ;norca.nic and organic pcllltasts and iithcos for their control Pol lutant_______________ Propargvl alcohol Tetracnioroetnvlene^ 7 tic n 1 o caetr.v .e ne * Toluene Vinyl chloride1 Threshold Cone. Inhibitory to Slcl.-fid.il Process i-g. l:tri c.vatec i. ud <e * A.',a erotic Digestion vitrification -- SCO -- *=*.! :i SCO -- -- Control Method* Evaporation freo water at 1SC (90X of l ppm after 90 oia) Evaporate iron water at 1SC (9CT of 1 ppm after 0 ain) Acciue carton 0.05g/gC (79* adsorption iron 317 ag/1). Active s.edge algestlon ' -,C mg/l. Evaporation troo water at 1SQC (901 at 1 ppa after 96 min] `Threshold mmbitory concent rat ions here wre deteramed with bacteria "Pseudomonas put Ida" and biological decooposi clan .s possible m sod* cases at higher concentrations. listed as priority pollucants c -c Envi rorcentai Protection Agere-.-- Other prlontv pollutants not listed aBove are as : o 1 lows : Halogen Containing Cosoounds Ihlorooentene, 1,1, -~crichi or oneczene . r exachlcroBen tene , [ . D-d ichiofcechar.e , 1. [, 3 -cricnlore tr.ane , 1, 3 -dichioroe thane , 3, :,1-t nc nl or oe thane . 1,1.1.1-tetracn-- o roe chare, tnloroecnane, bisi cnlorometnv . j etner, bis(chloroethyl) ecner, 1-chioroecnyi r i ?: ne r - . <ec >, I-c.nlcr-'ar.it.na. .te , J.-,c-trichic re prenoi . pa racnio reactac re sol. 1-cniorop nenoi , 3, D-ciomorooenter.e , 3,3-2 nr.icrooentene , i--"-o.c.n.ortpenaene, 3.3-aicniorobena:ccne, [..-cicriaroetr.vlehe, .l-trsns-dlchloroecnvcene, ., I-dicnioropnenoi, 3, 3 --ci;r_ or aeropace , 3,l-aicnioropropyiene, i iuoranenene , --cr.oropnenyi pnenyl ether, --oromoonenvi pnenvi ether, si J i I-cnloroethoxv > tecnane, patr.vi chloride, nethvi bromce, prccoform. o Ichlorobromooet nane , t r ichloror luorooe tnane . Jichiorooif 3 uo rone t.nane . c- _ : roci troccne tr.ane , hex ach Lo ro duC ad i ene , -exacnioroc -c 1 opencaalene . pencacnioropnenoc , 3,'-bento fluoranthene, rluorer.e aldrir., dieldrm. cniordane. IDT, DDE. DDD, heptacnioc, neptacnlor/e?ox lae, a.pna-3HC, beca-aHC, gaaea-flHC, delLa-o-D, Aroc.cr' 1116, .113, [131, !D2. 1116, 115, ana 3160, ana taxapnen* Dthers 1,6-Dlnitrotolu* ne , 3 ,1-d i pr< nvlhvdra ti r.e , 1, i-o ini t ropnenol, a , o-a m 11 roc resoi , N-altrosodloechylamine . S-ni t rpsoaipngny iazine. -- 11 ris cci-t-o ropy laame , butyl bensyl phthalate, dl-a-octal phthalate, diethyl phthalate, aiaechyL pnthalate, .. 1-oentar.tr. rac toe , ). .-bet :op y rent, anthracene, 1,! D-bensoperylene , phenanchr me , dlbenzo (a, h) anthracene, indot l. 1,1-ca) pyrene, p/rer.e, a.pna-etcosuutaa, beta-enaosuifur, ana enoosuitaa sulfate. Sources: 5-1396, B--X 397. mod o01G43i 53 methods include adsorption on resins or active carbon, reverse osmosis, and ozone oxidation. Dissolved metal salts such as copper sulfate and lead chloride can be precipitated with calcium hydroxide or hydrogen sulfide, or adsorbed on ion exchange resins (B--1394)* The above control methods, in most cases, serve to concentrate the pollutants. It is still necessary to dispose of or destroy the concen trated wastes by containment, incineration, or chemical degradation (see Section 4C on solid wastes). Ion Exchange Ion exchange can be used to remove or concentrate the following substances (B-1394): Metallic elements present in solution as either cationic or anionic species. Inorganic anions such as halides, sulfate, nitrate, and cyanide. Organic acids such as carboxylics, sulfonics, and some phenols, at a pH sufficiently alkaline to give the ions. Amines, when the solution acidity is sufficient to form the corresponding acid salts. Anionic and cationic surfactants such as quaternary amines or alkylsulfates. Generally, the upper concentration of exchangeable ions for economic operation is about 2,500 mg/liter (0.05 equivalents/liter expressed as CaCC^). At higher concentrations, the resin inventory and the regener ant consumption are sufficiently large, chat other separation methods, such as solvent extraction or precipitation, are more attractive. Ion exchange resins are divided into three classes (3-1399): (1) Sodium cation--where the sodium ion is exchanged for a calcium or magnesium ion such as in water softening. Sodium chloride is the regenerant. (2) Hydrogen cation--where the hydrogen ion is exchanged for all cations, and regeneration is usually with sulfuric acid. MCD 000016432 54 (3) Anion exchangers--nay use two resin types--highly basic or weakly basic. Both types remove strong acids such as sulfuric, hydrochloric, or nitric but only the highly basic exchange resin will remove weakly ionized acids such as silicic and carbonic. Highly basic exchangers are regenerated with caustic soda, and weakly basic exchangers, with caustic soda, soda ash, or ammonium hydroxide. Capacities for anion exchangers average about 5 nilli--equivalents per gram and 3 m.e./g for cation exchangers (3-13910). Most ion exchange operations are fixed bed, requiring only cylindrical ion exchange beds, tanks for regenerant storage, and pumps. Continuous ion exchangers are much more complex and have limited applications (B-1394). The capital investment to treat 80,000 gal/day of metal finishing wastes (Zn:Cu:CM:Cr: = 15:5:19:22 mg/liter) at pH = 10, estimated by A. D. Little (3-1391) and extrapolated to January 1979 is $430,000. Operating costs, consisting principally of labor (36%) and regenerant (38%), are $73,OCC/year. Modular capital costs for ion exchange systems, estimated by Icarus Corporation (B--13919) and adjusted to a 1979 PEP Cost Index by SRI, are as follows, in thousands of dollars for various resin volumes: Sodium cation Hydrogen cation Anion 40 ft3 40 71 91 100 ft3 64 112 144 400 ft3 154 278 353 The use of a stratified bed of weak- and strong-acid cation exchange resin is said to reduce regenerant costs since the resin is regenerated by a lower acid concentration without sacrificing recovery. A natural zeolite (clinopcilolite) has been employed for the selective separation of ammonium ions from sodium, magnesium, and calcium (B--13911)- The regenerant is recycled so that no liquid wastes are produced; activated alumina is suggested as a selective exchange material for removal of phosphate ions <B--13 911). 000016433 55 Electrodialysis An electrodialysis cell consists of multiple compartments sepa rated by alternate cation- and anion-permeable membranes, as illustrated in Figure 4.2. Cations diffuse toward the cathode end of the ceil until they are contained by an anion-permeable membrane. Similarly, anions diffuse toward the anode and are halted by a cationpermeable membrane. In this manner, water is depleted in ions in some chambers and concentrated in adjacent chambers. The ion-permeable membranes can be made of plastic film with the ion exchange resin imbedded in the film, or the ion exchange group may be part of the chemical structure of the membranes. Liquid flow through the cells is continuous and the ions reacting at the end electrodes are a small fraction of the total ions. Electrodialysis performs most efficiently with salt feed concentra tions in the range of 200 to 5,000 ppm. At higher concentrations, oper ating costs become unattractive, and at lower values, reduced electro lytic conductivity reduces cell efficiency (B-1394). In some instances electrodialysis may be followed by reverse osmosis to obtain low salt concentrations in the treated water. Typical applications of electrodialysis to date include the desali nation of brackish water, the demineralization of water from cheese pro duction, the treatment of metal plating and rinse solutions, and wood pulp wash water (B-13912). Estimated capital investment for an electrodialysis plant to treat 1.0 mgd and reduce the dissolved salts from 2,000-5,000 mg/liter to 500 mg/liter is 1 million and 90c/k gal. At 10 mgd, this figure becomes 58.0 million and 78c/k gal (443053, adjusted to January 1979). Energy requirements are 0.5 and 7 kwh per 1,000 gallons of salt water, with 1.000 ppm removal of dissolved solids. Annual maintenance costs are 4 to 6% of investment. 000o^6 4` 56 Figure 4.2 MULTIPLE-CHAMBER ALTERNATE-MEMBRANE ELECTRODIALYSIS CELL; A, THE ANION-SELECTIVE MEMBRANE; C, THE CATION-SELECTIVE MEMBRANE DEMINERALIZED WATER FEED Source: 6-13910. MCD 000016435 57 Reverse Osmosis Reverse osmosis depends on the ability of some membranes and fibers to allow passage of snail molecules but not large ones. Thus, for a solution of sodium chloride, water molecules can pass through the membrane but the sodium chloride cannot. Unlike electrodialysis, the solvent and not the solute, is the diffusing component and it is inde pendent of ionic charges. Diffusion is facilitated by applying a pres sure drop (usually 400 to 600 psi) across the fiber or supported membrane. The membrane can become blocked by film-forming organics cr by insoluble salts. Cellulose acetate; polysulfones, polyurethane, polyamide, and nylon are suitable membrane or fiber materials. Reverse osmosis equipment developed by Du Pont uses hollow fibers 50 ^o.d. and 25 pi.d. packed in bundles of 4 to 8 foot lengths (Permasepw). Solu tion under pressure is introduced around the outside of the fibers, and purified water is removed from the ends of the fibers cemented into plastic headers. One permeator, 4 inch i.d. by 4 feet long with 1,9CC sq ft of fiber surface can treat 2,000 gpd at a pressure difference of 400 psi. (Chemical Engineer, Feb. 8, 1971 and Nov. 29, 1971). Water recovery averages about 75% for feed solids concentrations of 800 ppm CB--13912). Table 4.4 shows the rejections of dissolved salts and organic solids by a cellulose acetate membrane. Capital and operating costs for a reverse osmosis plant to purify 1.0 mgG of brackish water are estimated at $850,000 and 108c/l,00C gal respectively. At 10 mgd these figures are $5.3 million and 84c/l,000 gal (443053, adjusted to January 1979). Neutralization Bacteria and aquatic life are sensitive to rapid pH variations and to pH levels outside the range of 6.5 to 8.5. Consequently, exces sively acid or basic wastewater must be neutralized before discharge. The neutralization system consists essentially of: MCD 0016438 58 Table 4.4 MATERIALS REJECTED BY REVERSE OSMOSIS Cations Ca2+, Mg2+, Fe2+, Mn2+ Nal+, K1+ Al3+ nh4i+ cu2+, si2+, cd2+ AgI+ Percent Rejection 96-98 94-98 99 88-95 95-99 94-96 Anions Cl*", N031+, Fl", Br1SO32-, S042-j HCO31' P043-j S2032-, Fe(CN)63CNl" 93-96 98-96 95-96 99 90-95 Organics Sucrose, lactose Protein (+10,000 mol wt) Dyes (400 to 900 mol wt) BOD Bacteria and virus (5,000 to 100,000 mol wt) 100 100 100 90-99 100% Max. Feed Concentration (%) * 3-4 5-10 3-4 8-12 3-4 8-12 >8 8-12 4-12 25 10-20 -- -- * Precipitation possible, depending on presence of other ions. Source: B-1394, MCI) 000016437 59 (1) Storage and handling of neutralizing liquid or solid (2) Mixing of waste stream with the neutralizing agent (3) Provision for residence time sufficient to attain the desired uniform pH. Suitable metering and pH controls are usually required and when precip itation occurs--such as alkaline precipitation of heavy metals or sulfuric acid precipitation of calcium salts--subsequent separation of solids by filtration, centrifuging, or other means is required. A typical neutralizer for basic wastes is sulfuric or hydrochloric acid, and that for acid wastes is quicklime or calcium hydrate. The dative costs of acid and base neutralizing agents are as follows: Agent H2SO4 (100%) HC1 (28%) CaO Ca(0H) bine s cone Soda ash NaOH (50%) Price ($/ton f. 0. b. works ) 58.00 (tanks) 45.00 (tanks) 32.00 (bulk) 33.50 (bulk) 32.00 (bulk) 61.00 (bulk) 157.501 (tanks) pH Factor 1.00 0. 14 0. 941 0.710 C.489 0. 507 0.450 $ /10 n Ac i d i t y or Basicity 58.00 322.00 34.00 47. 20 65.20 120.40 350.00 Relati' Cost 1.0 5.6 1.0 1.4 1.9 3.5 10.3 The design of neutralization systems is discussed by Adams (B--1395)* The estimated investment for a lime slurry neutralization of a 1 cgd waste stream (1% H2SO4 by vol) is SI.15 million (B-1394, adjusted to January 1979). Operating costs are $2.72/1,000 gal, with material, operating, and fixed charges accounting for 58%, 20%, and 22% respectively. Oxidation and Reduction Oxidation and reduction reactions are used to convert toxic or difficult-to-treat wastes into materials which are nonobjectionable or which are more easily treated or removed. A disadvantage is the addi tion of other, possibly undesirable, chemicals into the waste stream. MOD 000016438 60 A typical oxidation reaction is the destruction of sodium cyanide by reaction with chlorine and sodium hydroxide (B-1394): 2NaCN + 5C12 + 12NaOH-------- -N2 + 2Na2C03 + IONaCl + 6H20 Oxidation with hydrogen peroxide converts the cyanide to the less toxic cyanate: NaCN + H2O2----------- NaCNO + H20 The reduction of chromic acid (Cr^+) by sulfur dioxide gives chromic (Cr3+) sulfate, which precipitates readily in alkaline solution: 2H?Cr04+ 3S02 + 3H20-------- -Cr2(S04)3 + 5H20 Commercially available oxidizing and reducing agents together with their January 1979 list price and potential applications to waste treatment are shown in Table 4.5. In most cases, the waste component is merely converted to a different form and it still must be removed by precipitation, filtration, adsorption, or biological treatment. Equipment for oxidation and reduction reactions is relatively simple. It consists of an agitated vessel to provide contact of agent and wastes and sufficient residence time for the reaction to occur. Reagent storage and metering is also required along with instrumenta tion to monitor the reaction completion. The estimated investment (adjusted to 1979 dollars) required to treat 1,000 gpd of cyanide plating solution containing 7,000 ppm Cu(CN)2 and 1,000 ppm NaCN is $110,000. Production costs are 25c/gallon, with labor and maintenance accounting for 50% of this; chemicals, 14%; utilities, 1%; and taxes, insurance, and 10%/yr amortization, the remaining 35%. The investment needed to treat 2,000 gpd of chrome plating wastes (e.g., 100,000 ppm Cr03 in 20% H2S04) is estimated at $110,000. The production cost is 24c/gallon of wastes treated (B-1394, adjusted to January 1979). MCI) 0000164,39 61 Table 4.5 COMMERCIAL OXIDIZING AND REDUCING AGENTS AND THEIR POSSIBLE APPLICATIONS TO WASTE TREATMENT List Price* Possible Waste Materials Agent____________________________ ( c/lb) for Treatment Oxidizing Chlorine gas Calcium hypochlorite Chronic acid Hydrogen peroxide Potassium permanganate 7. 5 47 71 15.5 (35% sole) 68 Sodium hypochlorite Air 68 -- Sulfides, nercaptans, cyanide Cyanide Organic compounds Phenol, sulfur compounds, lead, cyanide Trace amounts only of phenol, diquat^, paraquat*, organic iulfur compounds, rotenone, formaldehyde, manganese, cyanide Lead , cyanide Sulfites, sulfides, ferrous iron Reducing Ferrous sulfate Sodium bisulfate Suflur dioxide Sodium borohydride Scrap iron 2.6 16 10 15 -- Chromium Chromium6* Chromium Mercury, tetraalkyl lead, silver Ferric iron *January 1979. ^Insecticides. Source: B-1394. MCD 000016440 62 Chemical Addition A variety of chemicals can be used to precipitate dissolved salts. Typical precipitants are ionizable compounds which fora an insoluble product with one ion of the dissolved salt. An example is the addition of sodium sulfide to mercury chloride solution at a pH of 6.5 (447028): + 2C1" + 2Na+ + S=--------- -HgSj + 2Na+ + 2C1" This addition is 'relatively straightforward, requiring only a nixing vessel and means for handling and controlling the reagent addition. The flocculation of the precipitate or other finely suspended solids may, however, require additional reagents and considerably longer residence time. This flocculation can be encouraged by one of two means (B-l3914) : Physical enmeshing of the particles in a gelatinous inorganic precipitate such as alum, lime, or ferric salts in alkaline solution (coagulation). Destabilization of the repulsive charges on particle surfaces by the addition of surfactants or polyelectrolytes, thus allow ing the particles to adhere to each other (flocculation). In some instances, a flocculant may also act as a coagulant but not vice versa (B--13915). A few typical flocculancs and coagulants are listed in Table 4.6. Mixing during flocculation or coagulation should be slow and gentle so as to maintain the agglomerates. Also sufficient residence time is required for the agglomerates to settle. Some suggested loadings for clarifiers up to 125 ft in diameter are as follows: MCD 000016441 Table 4.6 TYPICAL FLOCCULAKTS AND CCACULANTS AND THEIR APPLICATIONS Floccuiar.t 0r Coaeuiar.t Centosition Tvpe Typical Aoplicaticn Effective Ranee Approx. Price* pH Concentration (c/lb) Alum jcn.n0 Coagulant Va ter treatment 5-10 15 ppm 8.0 Ferric sulfare Fe SO4)3.xH ?0 Coagulant ?hos peace llaxiDuo Above 1 ag/1 precipicaticn at 1-6 3.7 Sodiun C1C Sodium carboxy Flocculanc Mineral methylcellulose 6 coagulant separation 3-9 0.03 to 0.05 lb/ton _ 76 Separar.- Acrylamide powder Floccuiar.t Chemical processing 2-10 0.2 to 10 ppm 60 F ib ret loc"' Animal glue Floccuiar.t Vasce 1-9 5 to 30 ppm 55 Trea tcent Silica oi Ac civacea silica sol Sodiuc aiuninate NaAl 0 2 Coagulant Coagulant Caste t reaccent la ter creaccent --6 3-1: 1 to 2C ppa 2 to 10 ppa 10 (as sodium silicate) -7 Guar **- rlocculant 'lineral processing 2-12 0.02 to 0.03 lb/ten 55 `Chemical 1 'arkecmj Reporter , Aprii 16, 1979, Schnell Publishing Co., 100 Church Street, New York., NY 10007. Source: 3-13915, except for the prices. c r ^5442 oGOO 64 C e Settling Application Loading (gph/ft^) Lime coagulation Alum/iron coagulation Flue dust Secondary biodegradable solids MLSS* = 2,000-5,000 ng/liter SVIT = 50-100 SVI 200-300 SV1 = 350-400 50 40 30-50 30-40 20-30 20 *MLS S--nixed liquor suspended solids. v ^SVI--sludge-volume index. For clarifiers larger than 125 ft diameter, the suggested loading rates are 15 to 25% lower and, for ULSS values above 10,000 mg/liter, further reductions are applicable (B-13914). In most wastewater treatment applications, the overflow rate varies within the range of 100 gpd/sq ft to 1,500 gpd/sq ft. Where agglomeration takes place as part of primary treatment, the clarifier may serve the additional functions of a pretreatment clarifier and/or a flow equalizer. The capital cost to precipitate and coagulate 410,000 gal of auto motive plating wastes containing 113 mg/liter of zinc is estimated at $360,000 (B-1394, adjusted to January 1979). Operating costs, including 10 year depreciation, are $1.10/1,000 gal. Lime and a polyelectroiyce coagulant (2 mg/liter) are added to the wastewater stream and a sludge (4% solids by wt) is drawn off the bottom of the clari fier. If the scale of operation is reduced by a factor of 5, the capital investment becomes $106,000 and the operating cost is $2.43/1,000 gal. If the scale is raised fivefold, these figures become $1,000,000 and $0.54/1,000 gal. Hydrolysis Hydrolysis is the reaction of a salt or an ester with water, alkali, or acid to decompose the salt or ester. Typical examples are MCI) OQQox 644c 65 Che hydrolysis of ticanyl sulface co yield cicanyl hydroxide and sulfuric acid: Ti0S04 + 2H2O----------- TiO(OH)2 + 2H2SO4 and che hydrolysis of echyl acecace co echyl alcohol and aceCic acid: CH3COOC2H5 + HoO CH3COOH + C2H5OH If sodium hydroxide is che hydrolyzing agent, sodium acecace replaces acecic acid While hydrolysis is a frequencly used reaccion in commercial chemical produccion (B--13910), ics applicaCion co wasce disposal syscems is scill very liniced. Hydrolysis can, in some inscances, convert a wasce material Co more easily recoverable or usable com ponents. The hydrolysis of wasce cellulose to glucose, which can be fermented to ethanol, has been investigated by Fagan (447035). The cellulose is ground, heated co 400 to 450F in dilute acid solution to yield 30 lb of glucose per 100 lb of cellulose. Fagan predicts an optimum yield of 52% glucose sugar at 445F with 1.0% sulfuric acid catalyst. The hydrolysis of waste polyurethane foam to recover toluene diamines (intermediates in toluene dissocyanate production) has been proposed by tlahoney (449593). The reaction is carried out in water at 400F for 30 to 60 minutes to give 65 to 80% theoretical recovery of 2, 4- and 2,6-toluenediamine. Hydrolysis reactions can be performed batchwise in agitated, jacketed reactors, or continuously in heat columns. However, residence tines and construction materials differ sufficiently so that each design is usually specific to a particular application (B-13916). c V C 66 Primary Treatment--Physical Sedimentation Settleable solids are defined as those larger than 0.45 and which are separable by a 2 hour quiescent settling period (B-13914). The rate of settling is affected by particle size, shape, and specific gravity as well as by the water temperature. The settling velocity for a given solids-liquid slurry can be determined by timing the subsidence of a slurry-liquid interface in a graduated cylinder for various sus pended solids concentrations (Figure 4.3). The initial slope of each curve is the zone settling velocity (ZSV) for that percentage of suspended solids. From this can be calculated the settling velocity (ft/min) and hence the solids flux (lb/sq ft/day) for the various suspended solids concentrations (B--1395). This flux is plotted against suspended solids concentrations, as shown in Figure 4.4. A line is drawn through the desired 2.5% underflow suspended solids concentra tion, tangential to the curve and the intersection of this line with the "y" axis is the required solids flux (16.5 lb/sq ft/day). The thickener area is the solids inflow (lb/day) divided by the flux. If the loading is increased to 26.1 lb/sq ft/day, the effluent suspended solids concentration will drop to 2.0%. Because settling velocity decreases with increased suspended solids loadings, as indicated in Figure 4.3, the effluent solids concentration is also reduced. Some typical settling rates for a number of aqueous slurries are shown in Table 4.1. Purchas (B-1395) describes a method for calcu lating settling velocities on the basis of physical properties of the solid and liquid. The accuracy is said to vary by a factor of 2 to 5 for diameters between 20 and 100 feet. Hydrocycloning Hydrocyclones employ stronger centrifugal forces, rather than gravity, to separate liquids and solids of differing densities and thus are able to achieve higher separation efficiencies and rates with smaller equipment sizes. MCD 000016445 67 Figure 4 3 SETTLING CURVES AT VARIOUS SUSPENDED SOLIDS CONCENTRATIONS* e r r HEIG HT OF IN T E R F A C E , oil Measured m a 1,000 ml graduate. Source. 8-1395. MCD 000016446 68 c c SOLIDS F LU X , lb /iq It/Jdy Figure 4.4 BATCH SUSPENDED SOLIDS FLUX CURVE FOR DESIGN MOD 0000164^7 69 Hydrocyclone efficiency is sometimes expressed as the particle diameter which has a 50% separation. This is related to physical properties of the systems by the following equation (3-13915): d50 56.3 Dc3 T1 Q(es - ei) 0.5 where: *n Q e i and es particle diameter with 50% separation efficiency, ^ hydrocyclone diameter, inches liquid viscosity, centipoises liquid feed rate, U.S. gal/min density of liquid and solid, Ib/rtJ Separation efficiency varies from about 0% at 0.25 d5Q to 100% at 2 d^Q. Cyclone size also affects separations efficiency. A 24 inch cy clone may handle 1,500 gpm but might not separate particles smaller than 50ii. A 10 mm cyclone would separate particles down to 5p. but would handle only 1 gpm. Adequate capacity is obtained for the smaller sizes by connecting numerous cyclones in parallel. Pressure drop through a hydrocyclone is typically 40 to 50 psig. Hydrocyclones occupy much less space than gravity settlers and have a lower capital investment (<50%). Disadvantages are higher abrasion, higher pumping costs, and the inability to separate concentrated slurries. Filtration and Centrifuging The choice of a means to separate solids from liquid is often determined by particle size and concentration, as shown in Figure 4.5. Filters generally are used for solids consisting of particles in the range of 0.001 to 5 mm at concentrations up to 20 wt%. The centrifuge is applicable to sizes from 0.001 to 0.01 mm, at lower concentrations. The factors affecting the selection of particular types of filter or centrifuge are covered in Perry (B-l), Ballew (447036), and Cleasby MCD 000016448 70 ri *3 O o G a Y<*s> % Figure 4.5 APPROXIMATE SOLID SIZE RANGE FOR SOLID LIQUID SEPARATION EQUIPMENT inches mm PRESEPARATION Flow Rate < 200 gpm - <0 8 < rv V fS 11 o CO CD Oar racks *1 _ (N ^ OC O ^ >? DO " 1 1 If 1 1 O C* irTo> O oo to - - o. r> 11 1l 1 TYler mesh CD ID 7 O) IO <7 r. .88 5 <N - 8 o O oo o o fN o o 8 1% O Oo o o ___i i t____i_____ J_________1 t J_____1____ 1 ____ 1__1___1__--1________ 1____ 35-50 gpm/ft^ Drum screens 30-40 gpm/ft^ 6eh screens, hydrosieves J SEDIMENTATION Approximate Settling Rale 50- 0.1 It/hr + 1.0 ft/hr I - 0 05 ft/hr Thickeners, clarifiers Hydraulic classifiers Hydraulic cyclones CENTRIFUGATION Density Dependent "No No Lower Solids Cone. Lt. 16 wt% 0 wt% Yes FILTRATION Solids Concentration, wt% _ 0 wt% Filter Rate, g/m/ft^ Solids Loss in Filtrate 50% solids below 100 p Small above 50 n Negligible Rotary vacuum drum Reciprocating pusher High speed, automatic batch f Solid bowl, scroll discharge 10 to 20 1 to 10 -5 5 to 0 2 0.2 to 0 02 0.2 to 0.01 | Tdting pan, scroll discharge Rotary vacuum disc | Continuous precoat or plate and frame (447035). Typical application and performance characteristics for several types of filters and centrifuges are summarized in Tables 4.7 and 4.8. The capital investment to separate 6 tpd of zinc hydroxide sludge (4 wt%) from 36,000 gpi of metal plating wastewater by vacuum filtra tion on a rotary drum is estimated at $240,000 (B-1394, adjusted to January 1979). Operating costs, principally labor and capital-related charges, including straigh:-line depreciation over 10 years, are $43.00/ton of dry -solids. The corresponding costs for centrifuging are placed at $168,000 and $38.5c'ton* Flotation Flotation technology (which is widely used in the mineral indus try) is used in waste treatment principally to separate solids from biological oxidation. It relies on che tendency of some solids to attach themselves to air bubbles rather than to water molecules. This hydrophobic tendency is enhanced by the addition of chemical agents or collectors, which usually have an anionic or cationic group attached to a hydrophobic hydrocarbon group. The ionic group is attracted to the surface of the solid, whereas the hydrocarbon portion repells water molecules. Thus, the particles are carried to the surface of the flotation vessel by rising air bubbles and are skimmed off. Typical collectors are sodium lauryl sulfate (30%) at 2'c/lb, tertiary-butyl amine at 86%/lb, and 2-mercaptobenzothiazole at 94c/'lb. Other reagents may be used to control pH, to promote frothing, or to suppress the flotation of other types of solids. Air is introduced into the suspension through a sparge tube, diffusion plate, or rotating agitator. Alternatively, air may be dissolved in the suspension under pressure and then the pressure is released to generate air bubbles in situ. Figure 4.6 illustrates a dissolved air flotation system for the concentration of a biological sludge. The advantage of the dissolved MCD 000016450 72 Table 4.7 SOME TYPICAL FILTER APPLICATION'S Tvoical Material Cyanide slice, flotation concentrates Cemenc slurry Pulp ar.d paper Crystals, salt, etc. Pigments Sewage sludge Varnish Mineral oil Material Character Finely ground minerals Finely ground limestone, shale and clay Free filtering fibers Granular, crystalline Smeary, sticky, finely divided Colloidal, slimy Cloudy, viscous liquid filtered hot with filter aid Removal of 1 to 20% bleaching clay from oil Approx. Filter Capacity (lb/sa fr/dav) 400-2,cao 400-200 200-L.2CC ( 1^ to 20 gpn/t^) 3,000-12,000 200-500 25-250 (5 gal/sq fc/hr) (3-30 gal/sq ft/hr) rilter ?VDe Continuous vacuum Continuous vacuum Continuous vacuum Continuous vacuum Plate and frame or pressure tank Continuous vacuum Place and frame Pressure tank. Sources: 3-1, 44/034. MOD 000016451 73 Table 4.8 TYPICAL CENTRIFUGE PERFORMANCE CHARACTERISTICS Cer.trifuee Tvoe Tubular Disc Helical convevor Bowl Dia. (inches) 1-3/4 4-1/8 5 7 13 24 6 18 32 54 Motor Horse power 2 3 1/3 6 7-1/2 5 15 60 150 Throu shout Liquid ( EPn) Solids (tons/hr) 0.05-0. 25 0.1-10 0.2-20 0.1-10 5-50 20-2C0 to 20 to 50 to 250 to 750 0.03-0.25 0.5-1.5 3-10 20-60 Sources: B-l, 447033, 447036* MCD OOOOX6450 74 c .m. V Figure 4.6 SCHEMATIC DIAGRAM OF DISSOLVED-AI R FLOTATION TANK WITH RECYCLE CHEMICALS 4k- CHEMICAL MIX TANK PRESSURE % REDUCING VALVE Source. B-1333. ->000 16453 MCI) 75 air flotation here is that it removes the small, light sludge particles more completely and in a shorter time than would be possible by sedimentation. The typical air-to-solids weight ratio encountered in the chicken ing of wastewater biological sludges varies from 0.005 to 0.060 at pressures of 40 to 65 psig (B-1393). The cost of flotation cells ranges from S35 to S65/cu ft for cell sizes from 400 to 60 cu ft (B--1, adjusted to January 1979). Solvent Extraction Solvent extraction is not competitive with biological oxidation and thus it should be considered only for r.onbiodegradable chemicals (B-1394). If these are dilute, active carbon is probably more eco nomic. If they are concentrated, the choice may be between extraction and steam stripping. Solvent extraction generally refers to the extraction of an organic chemical by an organic solvent. However, if a chelating agent is added to the extracting liquid, inorganic anions and cations can be separated from aqueous solutions. A chelating agent forms an ionic complex with the ions in solution. By changing the pH, the ions are released. Typical chelating agents are sodium tripolyphosphate and ethylenediarainetetraacetic acid contained in a solvent such as kero sene, chlorobenzene, or tridecyl alcohol. Their area of application is similar to that of the ion exchange resins. However, they lend them selves better to continuous flow systems and possibly to somewhat higher ion concentrations than does fixed bed ion exchange* A system to recover zinc, copper, cyanide, and chromium ions by chelate extraction from 80,000 gal/day of dilute metal plating wastes is estimated to require a capital investment of $325,000 (B-1394). Operating costs, principally labor, caustic, and capital charges (including 10%/yr depreciation) total $4.32/1,000 gallons adjusted to January 1979. MCD 000016454 76 ^ Cryscallization Crystallization today has only limited application to the treat ment of industrial wastewater. One example of its current use is the reaction of aqueous sulfuric acid wastes from the caprolactam industry ( with ammonia to form ammonium sulfate, which is recovered by crystal- V lization. As the controls on plant waste discharges become more strict, crystallization may find additional applications. Freeze crystallization has been suggested as a possible method for liquid waste streams containing concentrations of 1 to 10 wt% of hazardous materials (B-1394). The design of crystallization operations and the equipment avail able for same have been covered in detail by Bamforth (B--13917) and Perry (B-l). Adsorption on Activated Carbon Adsorption on activated carbon is a practical, well established s method for eliminating organic impurities in wastewater. It is most applicable to organic solutes with large molecules, low water solubility, low polarity, and a low degree of ionization (e.g., phenol, higher alcohols, and chlorinated hydrocarbons). Organics with low molecular weight (methanol), two or more hydrophylic groups (glycols), or high polarity (sugars) are usually poorly adsorbed. Very large molecules relative to the carbon pores, such as some dyes, may also be poorly adsorbed. A number of inorganic elements and compounds, such as iodine, chlo( rine, sodium cyanide, copper, and ammonia are also adsorbed by active carbon. The degree of adsorption varies from one material to another; it is likely to be highly pH-dependent, and regeneration may require acid or alkali washes. Strong electrolytes--sodium chloride, hydrogen chloride, sulfuric acid--are not adsorbed on active carbon (B-1394). In general, active carbon is most useful for the removal of nonbiodegradable (refractory) organics or the residual organics remaining after biological treatment (B-1395). 77 00001*3455 mCD Active carbon adsorption of impurities in aqueous streams may be carried out by various methods: Down-flow alternating fixed beds Up-flow expanded beds Countercurrent continuous moving beds Continuous circulating suspensions. The first is the most common. When the carbon beds are in a fluidized or circulating slurry, the equilibrium concentration of the adsorbate can be expressed by the r'reundlich isocnem: XM = KCel/n where X = weight of adsorbed impurities, g M = weight of activated carbon, g Ce = equilibrium concentration of impurity in solution, mg/liter K, n * experimentally determined constants. Typical liquid flow rates are about 7 to 10 gpm/sq ft, ana when backwashing is required to disengage solids, a flow rate of 15 to 20 gpm/sq ft is normal for 8 x 30 or 12 x 40 mesh granular carbon (B--13918). Typical contact times are 20 to 60 minutes for COD loadings of 0.2 to 0.5 lb/lb carbon (B-13914). Activated carbon can be removed (or returned) from the column as a slurry. The solids are collected and regenerated by heating to 1500 to 1700F in a multiple hearth furnace. Carbon losses due to attrition and burning are usually from 5 to 10%. If the adsorbate is suffi ciently volatile, the carbon can be regenerated with steam (about 1 lb steam/lb carbon). Inorganics are removed by washing the activiated carbon with a suitable solvent, acid or b&se. MCD 000016456 78 d&b V s / The costs of activated carbon treatment vary widely with the type and concentration of impurity to be removed. The removal of 1,000 ppm of phenol from 100,000 gpd of wastewater is estimated to require a capi tal investment of $1.3 million. The cost of removal to 1 ppm, including 10%/yr, depreciation and carbon makeup at 50c/lb, is $18/1,000 gallons (3-1394, adjusted to January 1979). For tertiary treatment of water in publicly owned sewage treatment plants, the cost can be as low as 12c/l,000 gallons at a 10 million gal/day rate. Recent research as been directed coward the combining of carbon adsorption with biologically activated sludge treatment (447044, 357789). The addition of powdered activated carbon to biologically activated sludge systems has, in addition to lowering capital invest ments, the following advantages: Improved removal of organics Reduced carryover of effluent solids Reduced foaming in the aeration system Improved sludge settling characteristics Reduced shock from toxic impurities. The addition of powdered activated carbon (0.076 to 0.20 lb/1,000 gal) to 600 gpm of a refinery wastewater is reported to reduce solids effluent by 50%, BOD by 75%, and suspended solids carryover by 40% (447044). Du Pont (357789) reported similar benefits for its Powdered Activated Carbon Treatment (PACT) process. Here the carbon is regenerated by burning-off the less dense surface sludge layer on the treatment solids. Capital investment for the combined operation was estimated to be 25% lower than the total for separate operations. Operating costs were 10% less. Gitchel (357785) proposes to regenerate the carbon in an aqueous carbon slurry by direct oxidation of the slurry at temperatures of 212 to 600F (100 to 320C) and pressures up to 3000 psig. MOD 000016457 79 The Rohm and Haas Company (447039) has developed a number of porous polymeric adsorbents with capabilities similar to those of active carbon. These adsorbents are cross-linked structures of polymethacrylate or polystyrene. They are easily regenerated by washing with a solvent such as acetone or methanol. The regenerant and the adsorbate are then recovered by distillation. There is little or no attrition or breakdown of cross-linked polymer in several years of operation. An estimated capital cost to treat 115,000 gpd waste stream containing 1.0% phenol is $1.7 million as of January 1979 (447039). Operating costs are $15.60 per 1,000 gallons treated, without the recovered phenol value, and minus S5.30 if phenol is included at 25c/lb. Secondary Treatment Air-Activated Sludge Certain bacteria or microorganisms, in the presence of oxygen and nutrients, feed upon organic liquids and solids in aqueous suspension or solution (aerobic digestion): N, P organic matter + bacteria + O2 more bacteria + C0n + H2O + energy This is a widely used method for the destruction of organic wastes (3-13913). The conditions necessary for aerobic digestion include: Oxygen availability. pH level near neutral. Availability of nitrogen and phosphorus. Absence of bactericidal materials (e.g., halogenated compounds and heavy metals). Adequate mixing. Figure 4.7 illustrates the basic operation of an activated sludge system. The wastewater influent is mixed with recycle sludge and air. The mixture is then settled to separate sludge solids. A portion of the solids is recycled and the balance is filtered and discarded. A 80 qoOO16458 mcd /f*4* v_ Wastewater I nfluent Figure 4.7 ACTIVATED SLUDGE SYSTEM Air Air Source: B-1394 V. 000016459 MC> 81 number of variations are possible in equipment design and in the method and sequence of aeration and separation steps (B--1393, B-13920). The use of a deep shaft (5 ft dia by 5C0 ft deep) for aeration reduces ground area and capital requirements and is said to increase system efficiency or capacity (B--13921, 147040). The design of activated sludge treatment systems requires data on the BOD reaction rate, the oxygen requirement, and the sludge yield (B-1395). If this information is not available from an existing treat ment plant, it can be determined experimentally in the laboratory (B-13922). The aerator size, air requirement, mixing horsepower, and amount of sludge residue are then calculated (B-1395, 3-13922, 447055). Typical design and operating characteristics for three types of acti vated sludge aeration systems are listed in Table 4.9. The approximate investment, adjusted to January 1979, in conven tional aerobic digestion, sludge thickening, and filtration are $1.8, $4.8, and $7.5 for waste feed rates of 1.0, 5.0, and 10 mgd and a BOD reduction from 500 to 25 ppm (349186). The capital investment to treat 1 mgd of wastewater containing 10,000 ppm COD, and 4,000 ppm BOD was estimated at $2.1 million (1979 dollars) (B-1394). This included prinary clarification, equalization, aeration, and sludge separation. Operating costs, including depreciation (10%) and taxes and insurance were $2.20/1,000 gal. Qxvgen-Activated Sludge The use of oxygen in place of air for activated sludge biological treatment is said to have a number of advantages (357787): Higher BOD removal rates Faster sludge settling rates Reduced total oxygen consumption Lower sludge output Reduced aeration horsepower. 82 tabic 4.9 activated sludge process characteristics Characteristic Flow type Aeratloa Agitation BOD5 removal efficiency (Z) 8OD5 removal (lh/day) per lb microorganisms Volumetric loading (lb BODj/l.CQO ft3) MLSS (mg liter) Aeration voluae/hourly feed rate Application Nutrients (total) N P Air required when 8OD5 removal in lb/day per lb of microorganisms is Greater than 0.3 Less than 0.3 Agitation horsepower Sources: 8-1393, B--l395, 8-13922. Conventional Plug flow Diffused air Mechanical 85-95 0.2-0.4 Process Type Complete Mix Completely mixed Diffused air Mechanical 85-95 0.2-0.6 Seep Ae reel or. Plug flow Diffused air Hone 85-95 0.2-0.4 20-40 1,500-3,000 4-8 Low strength, domestic wastes 50-120 40-60 3,000-6,000 2,000-3,500 3-5 3-5 General application, resistant to shoe it loads General application to many wastes 1 lb per 50 lb BOD5 0.2 lb per 50 lb 8OD5 500-900 ft3 of air per lb 8OD5 removed 1,200-1,800 ft3: of air per lb BOD5 removed l hp for *5 lb BOD5 removal/day or 100 hp/lO^ gal aerator volume V MCD 000016461 83 There are also a number disadvantages (357784): Higher capital costs to enclose treatment tanks to contain oxygen-rich gases. pH lowering due to CO2 buildup in solution may require caustic addition. Added cost of oxygen-rich gases. A performance summary for air and oxygen systems is shown below (357786). Oxygen has the advantages of higher throughput and lower sludge production. MLVSS (mg/liter) Dissolved oxygen (rag/liter) Biomass loading (mg BOD5 per mg MLVSS/day) Clarifier overflow rate (m-Vday-ra^) Sludge production (mg TSS/mg BOD5 removed) Air 3,440 0.5-2.0 0.35 0.5 0.91 Oxygen 4,270 15 0.32 2.0 0.52 Eckenfelder (357784) has compared air and oxygen systems treating 60,000 ib/day of BOD. He reports that the added capital investment in closed oxygenation equipment was more than balanced by the savings in agitation power costs. The dispersion of oxygen in open tanks through rotating nicrodiffusers, studied by FMC Corporation (357788), has the advantage of requiring minimal modification of existing equipment while still realizing higher capacity, reduced sludge production, and lower power consumption of the oxygen system. The capacity of an existing L0 mgd open tank, biological oxidation system was doubled by converting to oxygen diffusion at a capital cost of $400,000, adjusted to January 1979, average BOD removal and oxygen were both in excess of 90%, and power consumption was only 25 bhp/mgd. 0000164612 MCP 84 Facultative Lagoons Bacteria and microorganisms which use dissolved oxygen for the conversion of BOD to insoluble sludge are characterized as aerobic. Anaerobic organisms function without dissolved oxygen. Simple organic wastes, primarily carbohydrates, lipids, proteins, alcohols, and or ganic acids, are converted anaerobically to volatile acids by acid forming bacteria and then to methane and carbon dioxide by methane bacteria (B-13923). Facultative lagoons, which operate without agita tion or air oxygen injection, are anaerobic except for a surface zone a few inches deep, which is aerobic by air diffusion. Facultative lagoons vary in depth from 3 to 20 feet. Periodi cally, it is necessary to remove accumulated sludge from the lagoon bottom or increase the height of the containing walls. Advantages are simplicity, low operating costs, and since a portion of the wastes are converted to methane and C02 reduced sludge volume. Disadvantages are the reduced capacity (20 to 50 lb BODj/acre/ day) and the large land area used. Methane-forming bacteria require a relatively narrow pH range (6.8 to 7.5). Long chain or cyclic hydro carbons are not degradable, and microbial activity is inhibited by oil, fat, or grease. Under cetain conditions algae growth can cause toxicity, odors, and a buildup in BOD5 above that of the influent (B-13923). Design of facultative lagoons has been reviewed by Middlebrooks (B-13923) and Clark (B-1393). Trickle Filters Trickle filters are porous beds of crushed stone or of plastic packing over which the wastewater flows. Sufficient void space allows the passage of air for the growth of aerobic bacteria which biodegrade organic impurities in the water. Beds may be up to 30 feet deep and 200 feet in diameter. Wastewater is distributed over the bed by a spray nozzle or rotating arm. High sidewalls are desirable so that the 85 MCD 000016463 media can be flooded with wastewater occasionally to eliminate stagnant volumes and to control fly larvae. Recirculation of the effluent wastes allows a higher loading (1,000 to 5,000 lb B0D5/acre-ft-day) than a one--pass noncirculating operation (300 to 1,000 lb BODj/acre-ft-day. These are referred to as high and low rate filters. Advantages of the trickle filter biological treatment are (B-13913): Simple construction and operation Low operating costs Resistance to organic or toxic shock. Ability to handle high temperature wastewater. Disadvantages are (3-13914): Reduced BOD capacity per unit volume [5 to 25 lb BQDy'1,000 cu ft (low rate) and 25 to 300 lb BODj/1,000 cu ft (high rate) ]. BOD removal efficiencies usually in the range of 50-85%. Presence of odors and flies. Filters are usually followed by a clarifier, and the recycle stream to a high rate filter can be taken before or after the clarifier (B-1393). Using two filters in series with separate recirculation to each filter improves removal efficiency. Removal efficiency can be estimated from the following empirical equation (B-1393): El 1 1 + 0.0085 yw7W 03 o oN 86 where = Fractional efficiency of BOD removal for process, including recirculation and sedimentation. W BOD loading to filter, lb/day. V = Volume of filter media, acre-ft. F = Recirculation factor * l +R (1 + R/10)2 R - Recirculation ratio, i.e., slurry recirculated slurry drawn off Thus, for 2 mgd of industrial wastewater having a BOD5 of 600 mg/liter, the filter area necessary for 71% removal at a 6 ft depth and a recircu lation ratio * 4 is as follows: Recirculation factor 1 + 4/(1.4)2 2.55 BOD5 loading - 600 X 8.34 X 2 = 10,000 lb BOD/day. Then, from the formula above, 0.71 -________________ * 1 + 0.0085 yi0,000/2.55V Solving for V * 1.75 acre-ft, thus, at a 6 ft depth, the area 0.292 acre. Capital and operating costs to treat 2 mgd of wastewater containing 1,250 ppm BOD5 with 50% removal have been estimated by Oliver (B-13920). The capital cost adjusted to January 1979 is $384,000 and direct operating cost is 6c/l,000 gal. Nitrification-Denitrification Nitrogen is present in sewage in the form of urea, proteinaceous matter, and ammonium or nitrate compounds. The first two are readily decomposed by bacteria to ammonia. This ammonia is converted further to nitrites and nitrates in an aerobic environment (B-1393): MCD 000016465 87 NH^"*" + 3/2 O2 Nitrosomonas ----------------------------- NC>2~ + 2H+ + H2O bacteria Nitrobacter N02" + 1/2 02 ----------------------------NO3" Nitrification, given sufficient residence time, will occur in most aerobic biological treatment processes. While the nitrates are oxygenresistant, they do support algae growth and other plant life with a consequent conversion back to ammonia. Thus, it is desirable to carry the nitrification one step further. Under anaerobic conditions, and with the presence of methanol as a carbon source, nitrates are biologically converted to nitrogen and carbon monoxide: N03- + 1.C8 CH3OH + H+-------------0.065 C5H7O2N + 0.47 N2 + 0.76 C02 + 2.44 H20 The methanol requirement, mg/liter, is equal to: Gjjj - 2.47 N0 + 1.53 Nx + 0.37 D0 whe re Nq, Nj_, and Dq = initial concentrations of nitrate-nitrogen, nitrite-nitrogen, and dissolved oxygen, in mg/liter. Nitrification requires from 10 to 20 days at 20C and, while it can take place in activated sludge systems, the additional time is often provided in a separate system following biological sludge removal to reduce sludge volume in the nitrification reactor. Nitrification has been applied to NH3 concentrations as high as 500 cig/liter with 90% removal in a single stage and 97% in two stages. It is most efficient at temperatures of 28 to 32C and a pH range of 7.8 to 8.3 (B-1395). MCI) 000016466 88 s Denitrification has been applied to nitrate levels as high as 10,000 og/liter at pH of 6.5 to 7.0. Holding times are in the range of l to 5 days at 20C. Design calculations and various possible arrange ments for activated sludge, nitrification, and denitrification opera tions are described by Adams (B-1395). r v Capital cost of a nitrification-denitrification system to treat 2.5 mgd of nylon plant nitrogen wastes was estimated at $4 million (B-13914, adjusted to January 1979). Feed composition and percent removal were as follows: V Feed Composition Total organic carbon (TOC) BOD NO3-N N02"N NH3-N \ I j Organic N ) % Removal 80-90 90-95 60-80 s The system consisted of an anaerobic reactor with 36 hr retention and an oxygen concentration less than 0.2 rag/liter. This was followed by an aerobic basin with a 5 day retention. Sludge was separated by dis solved air flotation and a portion of it was recycled to the anaerobic reactor. Effluent from the flotation was filtered for complete removal of solids. Sand Filters Gravity sand filters are widely used for water purification. They consist basically of a layer of sand through which water is passed. Suspended solids are retained by the sand bed. They are removed by scraping the top surface of the sand bed or by backwashing to expand the bed and wash out the filtered solids. Sand filters have been classified as slow and fast (B-13915). The slow sand filter uses a fine sand (0.35 to 0.50 mm dia) with flow rates of 50 to 100 gpd/sq ft. The buildup of a bacterial layer on top of the 89 MCP 000016467 sand aids in the separation of particles as small as 0.5 it* A disad vantage of the slow filter is that it uses only the top inch or two of the bed; therefore, it has to be cleaned frequently. The fast sand filter (2,000 to 3,000 gpd/ft^) uses a larger sand particle (0.50 to 0.60 mm). The addition of poiyelectrolytes to promote agglomeration enables even larger sand particle sizes and faster filtration rates. The use of several bed materials--sand, anthracite, and garnet--of progessively smaller size and greater density permits fuller use of the bed depth. Thus, when the bed is fluidized by backwashing, the coarse, light particles are reclassified on top of the bed, and the fine, heavy particles on the bottom (B-l, B-1393). A continuous sand filter has been developed in which the flow is from bottom to top and a diaphragm continually moves the bed upward in plug-fashion as fresh sand flows in underneath (B--13911). Sand over flow from the top is washed to remove entrapped solids, then recycled. Thus, the entire filter bed depth is in continuous use. A disadvantage of the sand filter is the fact that the solid- liquid feed is concentrated (by backwashing) rather than separated. some instances, using air together with the backwash to expand the In filter bed, reduces the volume of the collected slurry (B-13914). Typically backwash volumes are 5 to 10% of the feed volume, and solids separation efficiency is 65 to 95% of the feed solids. The capital cost, for a 7.5 mgd sand filtration system--including automatic controls, auxiliary equipment, and building--is $1.56 million (B--13911, adjusted to January 1979). Tertiary Treatment Foam Fractionation Foam fractionation is the concentration of dissolved nonvolatile surface active agents (i.e., molecules with both hydrophobic and hydrophilic groups) which tend to concentrate at water-gas interfaces MOD 000016468 90 (447046). Heavy metal ions may also be concentrated in the presence of surface active chelating or complexing agents (447045). Foam fractionation columns operate with countercurrent flows of liquid and foan phases in a manner analogous to that of distillation columns. Similarly, they can be employed in stripping or enriching modes or in a combination of both. The design of foam fractionation columns is derived from the experimentally determined equilibrium curve for impurity concentrations in liquid and foam phases and from the height of a transfer unit (HTU) (B-l, 447047, 447048). In some cases, the separation can be made in a conventional bubble plate column. Possible methods for the coalescence of the foam overflow or reflux include rotating paddles, nylon mesh contactors, or ultrasonic vibration. Foam fractionation is most likely to be economic for the concentra tion of trace amounts of surfactants, dyes, phenolics, and heavy metals (447048). A tenfold concentration of toxic ions is said to be readily obtained by a simple mode fractionation (e.g., no reflux and feed to foam pool) (B-l). The estimated capital investment (adjusted to January 1979) for 70% removal of a few ppm of alkyl benzene sulfonate in 1 mgd of municipal wastes is $72,000. At 10 mgd, the investment is $485,000 (447049). Chlorination Water that is to be recycled for human or animal use must be dis infected. The most common disinfectant is chlorine gas, which is drawn into the aqueous stream as it passes through an ejector. Instruments maintain a constant proportion of chlorine to water to give a residual CI2 content of about 0.5 mg/liter (B-1393). Following mixing, a contact time of 15 to 30 minutes is usually required for disinfection. Typical chlorine dosages for disinfection of wastewater at various stages of treatment are as follows: 91 ;i0016469 mod OC Source of Effluent Untreated water Primary sedimentation Activated sludge Chemical precipitation Multimedia filter following activated sludge Dosage Range (mg/liter) 6-25 5-20 2-8 2-6 1-5 The capital investment required to chlorinate 1 mgd at a dosage of 10 mg/liter is estimated at $90,000; at 10 mgd and the same dosage, this figure is $130,000 (B-13924, adjusted to January 1979) Operating costs are the cost of chlorine plus capital-related charges. Chlorine can also be used to eliminate ammonia from wastewater (B-1393): 2NK3 + 3C12--------- ~Nt2 + 6HC1 Best results are obtained with a reaction tine of 2 hours, a tempera ture of 45 to 48F (7 to 9C), and a pH between 7 and 9. Chlorine requirements are about 10 mg of CI2 per mg of NH3. Chlorination is effective for the removal of small quantities of ammonia (1 mg/liter or less). For higher quantities, the cost of chlorine becomes significant (B-13911). A disadvantage is the generation of by-product hydrogen chloride. Ozonation Ozone is a powerful oxidizing agent capable of destroying various toxic, or otherwise undesirable, organic and inorganic compounds. Table 4.10 lists some of these compounds. Ozone is generated as re quired and, since it is expensive to produce, it is most likely to be economic only for impurity concentrations of 100 ppm or less. MCD 000016470 Table 4.10 .* TYPICAL COMPOUNDS SUSCEPTIBLE TO OZONATION Organic Aromatic hydrocarbons Microorganisms Biphenyl 3.4-Benzpyrene 1,2-Benzanthracene 3.4-Benzfluoranthene Bacteria Vi ruses Algae Protozoa V Detergents Other Alkyl benzene sulfonate Anienic detergent Nonionic detergent Color Odor Disinfection Pesticides Aldrin DDT -BHC Dieldrin Malathion Methyl parathion Ozone Oxidation Combined with UV Radiation^ Acetic acid Ethanol Glycerol Phenols Phenol o-, m-, and Catechol Xylenol p-Cresols Inorganic Potassium cyanide Potassium ferricyanide Sodium thiocyanate Sodium thiosulfate ^Numerous other compounds are more economically handled by biological oxidation. ^Little or no oxidation without UV radiation. Sources: B-1394, 447053, 447054 93 MOD 000016471 Ozone Is produced by passing air or oxygen through an electrical discharge. When air is used, the maximum ozone concentration attained is about 2% or less with an electrical expenditure of 7 to 9 kwh/lb ozone. When oxygen (50-75%) is used, ozone concentrations of 5 to 6% are possible with a power usage of 3.5 to 5 kwh/lb ozone (B-1394). With air, a once-through process is used and the air, following destruc tion of residual ozone by catalytic or thermal means, is discharged to the atmosphere. When oxygen is used, the value of the oxygen necessi tates its being recycled. Union Carbide (447054) suggests that this latter system can be advantageously combined with an oxygen-activated sludge operation. Thus, there is only a single pass of oxygen through the ozone treatment process with the exiting unconverted oxygen stream going to a biological oxidation operation. This eliminates the oxygen treating and recycling. Typically, ozone usage is in the range of 1.5 to 3.0 lb/lb of impurity with liquid residence times of 10 to 15 minutes. However, some hazardous materials nay require retention times up to one hour with stagewise application of the ozone (B-1394). The optimum combina tion of ozone dose and contact tine must be determined experimentally for each application. Currently, ozone is most frequently used in tertiary treatments for disinfection, odor or color removal, and oxidation of residual trace contaminants (B-13912, 447052, 447050). Ozone is effective as a water disinfectant at dosages of 5 rag/liter or less (447050). Its advantage is the absence of any residual impurity. The principal disadvantage is the cost of equipment and operation. Recent evidence of the formation of carcinogenic compounds during chlorination of drinking water could, if verified, greatly expand the use of ozone for disinfection (447101). Increased generator efficiencies (lb ozone/ kwh), lower investment cost, and/or stricter effluent regulation could increase the use of ozone for reduction of cyanides, phenols, metal plating wastes, etc. (B-13912). MCI) :.'<00016472 94 Large volume (6,000 lb ozone/day) ozone generation systems require capital investments of about $350 to $450/lb ozone/day (B-13912). The capital investment for a small volume ozonation process to lower the phenol concentration in 800,000 gpd of refinery effluent water from 0.38 ppm to 0.012 ppm has been estimated at $380,000. Ozone output was 190 lb/day and operating cost was about 53c/1,000 gal (B-1394, adjusted to January 1979). Toxic Liquids Disposal Pumping into the ground at depths of several thousand feet has been used for the disposal of corrosive and toxic liquid wastes. Principal costs are those of well drilling, pumps, and power for pump operation. The capital investment for disposal of 500 gpm at a depth of 3,000 feet is estimated at $2.4 million, including pumps with 900 psi discharge pressure (101272, adjusted to January 1979). However, the areas available for "deep-welling" are being increasingly restricted and, by the early or mid-1980s, this disposal method will probably not be acceptable for toxic wastes in most industrial nations. Incineration is a generally acceptable method of disposal for toxic liquid wastes. For example, a fluidized silica bed operating at 1400 to 1500F (760 to 815C) has been used for the destruction of 4% of mixed organic compounds in 750 gph of aqueous solution (447008). Destruction of the organics was 99.9% efficient and the No. 2 fuel oil consumption was 0.33 to 0.43 gal/gal. Capital investment was $6.0 million and operating costs-principally fuel and capital related items--was $530 per 1,000 gallons of liquid wastes. The Zimpro system of wet air oxidation, at elevated temperatures and pressures, of liquid chemical wastes has the lowest operating costs (447008). However, at 536F (280C), the destruction efficiency of some organics is less than 85%. A more recent paper on the Zimpro process (447074) shows that pentachlorophenol is 82% consumed at 527F (275C) and almost completely (99.88%) eliminated at 608F (320C). 95 MCI) 000016473 4B GASEOUS WASTE TREATMENT AND DISPOSAL TECHNOLOGY A variety of well established industrial techniques are suitable for the elimination of environmentally objectionable solids and vapors from inert gases. The most used methods are indicated by the block, flow diagram of Figure 4.8. For example, hot combustion gases from a coal fired boiler night pass through the sequence of--spray cooler, cyclone separator, bag filter, SCH scrubber, and stack--before being released to the atmosphere. Pretreatment Waste gases nay need to be compressed before treatment. If the gases are free of suspended solids and are at temperatures below about 200F (100C) they can be compressed directly--otherwise after cooling and separation of the solids from the gases. The required pressure is generally less than 25 psia. Figure 4.9 shows the brake horsepower required by a centrifugal compressor to increase the pressure of air, at various flow rates, to 17, 20 and 25 psig. Compressor costs are available from the literature (B-13927) or from the PEPCOST relation: Cost $ - 3,894 x 290 x (bhp/4,500)0*76 Feed gases can be precooled by either indirect or direct heat exchange to water. Typical values of U for heat transfer from gases to water are in the range of 10 to 50 (B-l). For a counter current spray cooler, empirical equations for maxi mum allowable gas velocity and unit heat transfer rate are as follows (447060): 00 Oo q4?. 97 Figure 4.8 WASTE GAS TREATMENT ALTERNATIVES PR ETREATMNT t WASTE GASES Process. Comoustion. Vent Dry r Cyclone separation SEPARATION r Liquid---------------- -------------Cl Water scrubber r (S] Bag filter m. Electrostatic precipitation Cl Solvent scrubber I Acid or ammonia neutralisation 1 r (L! Vapor aosorption --r~'active carbon) STEAM --J r*- [SI SO2 scruDber (limestone) INERT GASES TO ATMOSPHERE . .oV cP 98 Figure 4.9 COMPRESSOR HORSEPOWER FOR VARIOUS AIR FLOW RATES V C Source: B-T3944. AIR FLOW RATE, scfh 99 7/0 17> V.max . 0.0146 G0**82 L0*47 ZT0.38 ' where Vmax = max gas velocity, ft/sec C = a constant = 20 0^, Dg = liquid and gas densities, lb/cu ft hga = volumetric heat transfer coefficient, Btu/hr/cu ft/F G, L * gas and liquid mass velocities, lb/hr/ft^ Z- = height of contacting zone, ft. Knowing Vmax and hga, one can readily calculate the cross-section and the height of the column. The cost can then be estimated convention ally. Dry Systems Gas-5olid Separation The principal types of equipment for gas-solid separations are: Cyclones Bag filters Electrostatic precipitators. The choice among these depends primarily on the particle size of the solid, the concentration of the solid in the gas, and the degree of separation desired, as indicated in Table 4.11. Electrostatic precipi tators are the most efficient at particle sizes smaller than 2 microns. 100 Table 4.11 APPLICATIONS OF CAS-SOLID SEPARATION EQUIPMENT Characteristic Cvclone Bag Filter Electrostatic Precipitator r Minimum size particle (microns) 10 0.2 2 (max) Minimum solid particle loading (grains/cu ft) 10 0. 1 0. 1 Maximum collection efficiency (wtZ) Typical gas velocity (fpm) 85 2.000 to 4.000 99 1 to 20 99 100 to 600 Approx, pressure drop (inches H2O) 1/2 to 3 2 to 6 0.2 to 1 Approx, upper size limit (1,000 cfm) 50 200 10 to 2,000 Installed cost ($1,000)* Power cost ($/yr)^ 125 9,040 420 7,480 600 4,000 Maintenance (%/yr of installed cost) 1.0 6.0 0.6 *January 1979 cose for typical systems handling 60,000 cfm of gas at 68F with a loading of 5 grains per cubic foot, 30% smaller than 10 microns. ^ Electricity at 20 mills/kwh. Sources: B-l, B-13928, 447059. They also have the lowest operating costs--largely for maintenance and power. However, the installed cost for an electrostatic precipita tor treating 60,000 cfm of gas is $600,000, compared with $125,000 for a similar capacity cyclone and $420,000 for a bag filter. Adsorption on Activated Carbon The removal of objectionable or valuable vapors from inert gases such as air is a well developed and widely used technology (447069, 447063). Vapors are attracted to the surface of the carbon by forces 101 MCI) 000016478 believed co be similar to those of chemical combination. The amount of a particular vapor adsorbed by a specific sample of active carbon at a given temperature can be represented by a Langmuir isotherm (B--13929): k*K*p X/M = 1 + Kp where X/M = vt of vapor per unit vt of carbon k and K = constants p partial pressure of vapor over carbon. The constants "kM and "K" must be determined experimentally for each adsorption system. Table 4.12 shows the approximate amounts of various chemicals adsorbed by active carbon from air saturated at 20C and 760 mra Hg. Generally, adsorbability varies directly with vaporization tem perature. Typically, solvent recovery systems are designed for solvent capacities of 10 to 20 lb solvent/ICO lb active carbon (B-12930). Adsorption heat for various solvents ranges from about 12000 to 15,000 cal/g-mol (21,500 to 27,000 Btu/lb-mol). Where this results in more than a 5 or 10C rise in the temperature of gas stream, cooling of the bed may be necessary. The bed is regenerated by blowing with steam to vaporize the adsorbed solvent. Typical steam usage is 3 to 5 lb/lb of solvent (447058). Typical pressure drops for air flowing through active carbon beds at 70F and 760 mm Hg pressure are shown in Figure 4.10. The installed cost of an active carbon adsorber to treat 1.2 million cfh of air containing 200 ppm of solvent is $530,000 (447064, adjusted to January 1979). Steam requirements for this low solvent concentration can be as high as 30 lb/lb of recovered solvent. MCD 000016479 102 Table 4.12 VAPORS ADSORBED BY ACTIVATED CARBON* High (ZC to 50 wc") Acetic acid Alcohols Anyl acetate Benzene Bromine Butyric acid Caprylic acid Carbon tetrachloride Chloroform Cresol Disinfectants Ethyl acetate Casoline Nercaptans Ozone Phenol Pyridine Toluene Tu rpentine Medium (10 to 25 wc") Acetone Acrolein Acrylic acid Butylether Butyraldehyde Carbon disulphide Chlorine Ethyl chloride Ethyl ether Hexane Hydrogen sulfide Methyl acetate Methyl alcohol Nitrogen dioxide Pentane Pentylene Sulfur dioxide Sulfur trioxide Low (Less than 1070 Acetaldehyde Acetylene Amines Butane Butylene Ethylene Fo rmaldehyde Formic acid Methyl chloride Propane Propylene Very Low (Not suitable at soecified conditions) Carbon dioxide Carbon monoxide Ethylene Ethane Methane *Adsorption from saturated air at 20C and 760 ram Hg. Sources: B-13929, B-1393C. MCI) OOOOicl^aQ i 103 Figure 4.10 PRESSURE DROP FOR AIR FLOW THROUGH ACTIVE CARBON AT 70'F AND 760 mmHg r c PRESSURE D R O P , inches H 2 O m le<l ( 1 10 100 SUPERFICIAL VELOCITY, ft/mm Source: PittsDurgri Activated Cardon MCD O00016481 104 1.000 C Liauid Systems Water and Solvent Scrubbing Water-soluble gases such as hydrogen chloride, methanol, and formaldehyde are readily removed from insoluble gases by scrubbing with water in. a packed or tray column. Similarly, organic vapors (such as benzene, ethane, and styrene) that are insoluble in water are easily removed by scrubbing with a low volatility hydrocarbon liquid. The optimum design of scrubbers depends on the kind and composi tion of the gases being treated as well as on the type of solvent and its capacity for the gaseous components. However, for the average operation a scrubbing tower with 20 actual plates is usually adequate. Also the tower diameter is such that the vapor velocity up through the column is below flooding. Maximum solute concentration in water or solvent is 5 wt/>. Knowing the column size and circulation, one can readily estimate the capital and operating costs by the PEPCOST computer program or from published data (B-13927, B-13928). Acid or Ammonia Neutralization Gases containing acid or ammonia vapors are commonly neutralized by scrubbing with an aqueous slurry or solution of lime or sulfuric acid. Column sizing is similar to that of water and solvent scrubbers. However, the materials of construction must be acid- or alkaliresistant and additional facilities are needed for storage and mixing of neutralizing agents. Storage capacity is usually equivalent to 5 days' supply of acid or alkali. Limestone Desulfurization National ambient air quality standards require sulfur oxides concentrations of less than 0.5 ppm (447061). As more power plants convert from hydrocarbons to coal, the capacity requiring flue gas 105 MCD 000016482 desulfurization is expected to skyrocket from 4,000 MW in 1975 to over 130,000 MW by 1985 in the United States (447062). While numerous flue gas desulfurization processes have been pat ented, less than ten are in large scale operation or construction. Of these, the limestone slurry process accounts for more than 50% of the total capacity. Limestone slurry (5 to 15 wt%) is sprayed into towers, where it reacts with sulfur dioxide to form hydrated calcium sulfate and carbon dioxide: CaCO 3 + S02 + 1/2H20--------- ~CaS031/2H20 + C02 In practice, some SO2 is oxidized to SO3 and this combines to give mixed calcium gypsum crystals [Ca(S03)x(S04)y*zl^O] (447061). Sulfur dioxide removal is about 80 to 95%. The most used method of sludge disposal is on-site ponding and landfill. Investment and operating costs for the limestone desulfurization of flue gas were evaluated in PEP Report No. 63B. The fixed capital investment to desulfurize 13 x 10^ scfh of flue gas from 2,500 vppm to 500 vppm is S17.4 million. Limestone (93% CaC03) usage is 8,600 lb/hr and the resultant gypsum sludge output is 28,800 lb/hr. Operating requirements are principally labor (7 operators/shift), steam (21,000 lb/hr), and electricity (1,300 kw). Maintenance labor and materials is taken at 3%/yr of capital investment. Waste Gas Disposal Steam Generation and Incineration When the waste gases contain combustible gases in concentrations greater than 100 Btu/scf, it may be preferable to burn them for steam generation. Thus, 100,000 scfh of low Btu gas (125 Btu/scf) could generate, at 60% efficiency, 8,000 Ib/hr of steam, with a modular investment in burners and steam boiler of about 5155,000. At 500 Btu/scf, the comparable figures are 75% efficiency, 40,000 lb/hr steam, and an investment of $450,000, as of January 1979. OOOO 106 When the waste gases contain a snail quantity of an environmen tally objectionable gas which is not readily eliminated by preceding methods but which is combustible (e.g., acetylenes), incineration may be desirable. In this case, auxiliary fuel would be added to produce combustion temperatures up to 2000F (1100C). Sensible heat in the combustion gases would be used for steam generation as before. Emergency Flaring In industrial nations, the gas flare serves mainly as a means of disposal for flammable gases during a process equipment failure or emergency plant shutdown. The exit velocity of hydrocarbon gases from a flare should not exceed 1/5 of the sonic velocity if a stable flame is to be maintained (447067): V = 1/5 ygkRT/M where V gas exit velocity, ft/sec g = gravity constant = 32.2 k = Cp/Cv = 1.2 R = gas constant, 1,546 T vapor temperature, R M - molecular weight of vapor. Knowing the gas escape velocity and the maximum volume of gas flow, one can calculate the stack diameter. The stack height is obtained from the following relation: 4TT [x2 + h(h + 120 D)1 where q * heat intensity on the ground at X ft from base of stack, w * gas flow rate, lb/hr. h = height of stack, ft. D = stack diameter, ft. M = molecular weight of vapor. Using a heat intensity "q" at the base of the stack (X 0) of 1,500 Btu/hr/sq ft (approx maximum for 20 second human exposure), the stack height can be determined. If steam is injected (0.3 lb/lb HC), carbon particles are converted to carbon oxides and smoke is eliminated (3-13931). Esso Research (447065) have proposed a smokeless multijet flare which does not require steam addition and which does not have to be elevated. Inside diameter of this stack in feet is equal to 0.825 times the square root of the heat release in million Btu/hr. The erected capital cost to flare hydrocarbons (mol wt 40) at a rate of 0.5 million scfh is estimated at $190,000 for the elevated flare and, if steam is employed, an additional $650,000 is required for steam generation. For the Esso multijet flare, the comparable cost is $400,000. Dispersion by a Stack When environmentally objectionable impurities in the waste gases have been reduced to acceptable limits, the gases are discharged to the atmosphere. A study made many years ago by Moyer Thomas et al. (447068) determined the impurity concentrations downstream from dispersion stacks. The maximum concentration was found at a distance ^max ^/2 Cz and the concentration at this distance was expressed by: ^max 4M \/2TT e^uh^ C, MCD 00 001048! 108 where h = stack height, cm. Cz & Cy = vertical and horizontal diffusion coef., 0.05 to 0.07. M = gaseous impurity emission, g/sec. e * natural logarithm base = 2.718. u * mean wind velocity, cm/sec. Some additional guides to dispersion stack design are suggested by Ross CB--13913): Stack height should be 2.1/2 times that of surrounding buildings to minimize turbulence. Gas ejection velocity should be greater than 60 ft./sec so as to escape the turbulent wake of the stack. Ground concentration varies inversely as the square of the effective stack height. The estimated installed cost of 100 foot steel stacks of 24 and 48 inches diameter is $23,000 and $70,000 (447057, adjusted to January 1979). a o.0.'O, 61 109 4C SOLID WASTE TREATMENT AND DISPOSAL TECHNOLOGY Solids generated in liquid and gaseous waste treatment are treated and/or disposed of as described in this section. Solid wastes such as catalyst residues and spent adsorbents are also handled as described here. Potential treatment and disposal means are illustrated by the block diagram of Figure 4.11. The treatment procedures are standard* widely used, industrial methods. This section briefly reviews their application to waste treatment. Waste Solids Treatment Dewatering Dewatering centrifuges are applicable to relatively coarse (+100 mesh) granular, nonsticking materials. The capacity or these centri fuges is very dependent on the particle size of the feed solids, as shown in Figure 4.12. For example, for a KC1 feed with a moisture content of 35 wt% and a top size of 1/8 inch, a 36 inch bowl centrifuge has a capacity of 44 tph of solids with an exit moisture content of less than 6 wt. This exit moisture content increases with solids feed rate and decreases with increasing solids particle size, as illustrated by Figure 4.13. The approximate purchase prices of helical-conveyor centrifuges are as follows (B-l, adjusted to January 1979): Bowl Diameter (Inches) 26 36 Purchase Price, ($) Steel Stainless 316 58.000 85.000 100,000 140,000 111 MCD '-'0001648 Figure 4.1 1 WASTE SOLID TREATMENT ALTERNATIVES WASTE SOLIDS Mci; uooois^as 112 L A P A C I I Y , io n s s o lu li jhm Iidui Figure 4.12 EFFECT OF FEED SIZE ON DRYING CENTRIFUGE CAPACITY A/oVr. OQCu 113 Figure 4.13 EFFECT OF FEED RATE AND SIZE ON DRYING CENTRIFUGE PRODUCT MOISTURE C PRODUCT M O lS T U H t, wt 000016490 HOD 114 r o e In addition to the dewatering centrifuge, the module would also contain a 20 foot screw feed conveyor, 5 hours' solids and water surge capacity, and a water pump. Drying The equipment applicable to the drying of waste solids includes rotary dryers, flash dryers, multiple hearths, and fluidized beds. Only the direct heat rotary dryer will be considered here. The capacity of the dryer can be expressed by a heat transfer equation (B--1): Q -- baV(At )ni where Q - total heat transfer, Btu/hr V = volumetric heat transfer coefficient, Btu/hr/cu ft/F (At)m = mean temperature difference between hot gases and solids. When the solids temperature is not known, the logarithmic mean of the wet bulb depressions of inlet and outlet air can be used. An empir ical relation for the volumetric heat transfer coefficient is Ua = 0.5G67/d and replacing V by ITD^LM changes the heat transfer equation to: Q - 0.4LDC-67(Atm) where L and D = dryer length and diameter, feet G = gases mass velocity, lb/hr/sq ft. Thus, knowing the quantity of heat to be transferred and the inlet and outlet air temperatures, one can calculate the mass of air required and the dryer length and diameter. MCD 000018-4 9 x 115 Typical performance for direct warm air cocurrent rotary dryers is given below (B-l). Solids moisture is reduced from 25 wt% to 0.5 wt% with inlet and outlet air temperatures of 330F and 160F and inlet and outlet solids temperatures of 30F and 150F. Inlet air is heated by indirect heat exchange with steam. Dryer size (D inches x L feet) Heat load, Q (Btu/hr) Steam, 150 psig (lb/hr) Discharge solids (Ib/hr) Exhaust gas (cu ft/min) Water evaporated (lb/hr) Dryer fan and drive (hp) Dryer purchase cost, Jan. 1979 48 x 25 342,000 700 900 2,250 300 8 $63,000 72 x 35 780,000 1,600 2,100 5,100 700 20 $105,000 *-- .t- i --oo 120 x 55 2,160,000 4,500 5,700 1,900 80 $210,000 Incineration Incineration of solid waste is usually costly but, for many toxic organic materials, it may be the only safe method of disposal. Bayer AG in November 1977 commissioned a $13 million incineration plant for chlorine and phosphorus organic compounds (447070). This plant can treat 25,000 metric tons of waste per annum at an average cost (in 1978) of $190 per metric ton. For several years, two ships--Matthias III and Vulcanus--operating from Germany and Holland, have incinerated organic wastes such as vinyl chloride residues and herbicide orange, in selected ocean locations (447071). In the United States, EPA has sponsored several demonstration plants for the destruction of chemical wastes, solid and liquid (447008, 447019). Five different systems have been tested: (1) sudden expansion liquid combustion chamber, (2) rotating hearth pyrolyzer, (3) fluidized bed combustor, (4) tandem autoclaves for decomposition of liquids at elevated pressures and temperatures, and (5) rotary kiln followed by an afterburner for evolved gases. Details of these tests together with estimates for commercial scale operation are summarized in Table 4.13. 116 a: v /* Incmeracor type Incinerator capability Feed rats Ope racing temperature Heat capacity (3tu/hr) ,'astes created (combustion neat) Table 1. 13 U.S. EPA-SPONSOR8D HASTE INCINERATION DEMONSTRATION PLANTS Ihe Marquardt Comsanv, Van Suva, Calif._________ ____ SUC (sudden expansion) liquid combustion chamber followed sy a caustic venturi seruober, a scrub solution separator tans, a wire deolscer vessel, and a stack. Midland Ross Corp. Surface Combustion Division. Toledo. Ohio Rotating hearth pyroiyzer fol lowed by a rich fuse combustion chamber. Exhaust gases mixea with fresh air before exiting through a stack. Liquids onay Solids, sludges, or cars Systems Technology, Inc., franklin, Ihio Fluidised bed combustor followed by a venturi scrubber, ano an exnauic stack. Liquids, slurries, or solids 50-60 gph :00-*QC Ib/hr 3*0 gpn To 30:0F ( 1650C) 5.5 < l:* (I) EchvLene plane wastes at uxisaturated and arcoatic hydro carbons ( 18,000 5tu/lb) :2) Hexaeniorocvclopentadlene plant wastes with ussy partleulaces (-.3CC 8tuylb) To 1*00F (760C) z lo6 (1) API separator bottoms. Unsaturated and aromatic hydro carbons (2,500 Btu/lb) (2) Solid SBR uaitt plus carbon and some sulfur and metals, 301 H-0 (9,800 Btu/lb) 1100- 1500F (600-8l06C) 59 x JO6 (1) Methvl aethacylate waste liquid with gritty sediment (<2,7C0 Btu/lb) Phenol and cresol wastes wich 26t HsO and 51 inorganic solids ( 2.'00 Btu/lb) Incinerator cenaitIons Temperature r i> 185-285 2 : 3 165-38* (1) :-60-:975F > ; 3-9-1751C! il):*58-257:^F ( 1 3-8 - I 3 78C) Residence tlae Inci Aerator performance Scaek particulates mg/a^) C)0. 1--0.19 sec l2) 0.17-0.18 sec (1) :>25* 1 2) 36-i13* Trace oecals, ag/m^ (l) 0.001-0.003 Pb (2) 0.005 Pb 0.05 Mb Oestructisn efficiency <t) Lsciaated cuaerclii plant size (short tons, nr) 1st. capital investment. adjusted to January 1979 (Soil lions ) Operating cost. adjusted to January 1979 (S/short tan) Labor, S12.70 un*hr Auxiliary fuel. $2.60 million Stu Chemicals and utilities :Ulacenmac Capital-related casts , Total operating cost Net cost (!) 99.5 (2) 99. 95 (1) 16.500 (2) 4,950 (:) 1.92 (2) 1.72 (1) 26.2 -- 5.9 1 1.2 25.5 66.8 (2) 82.3 9*.0 201.3 112.9 76.0 566.5 Mo organic waste materials detected La scrubber water, 'fuel credit. *Follow-up treatment Source: w*7C06. .1) 3 2- :6 :;16-;: (1) l-OQOF < 760C) o i*.:of (?60C) (Comb. chaaber, I525F> (1) 12.5 oin (2) 15 sin U> 28-88 (2 ) 9-1* Cl> Zn, Pb-0.05 SOi 30-50 ppm (2) SOs 25 Ppa (1) 96 (2) 80-90 (1) 320 (2) 2.200 U) 0-*7 (2) 0.97 (O (2) **1.8 52.7 5.3 136.5 310.7 9*7.0 -50.7 896.3 185.1 21.5 5.1 -2.8 97.2 351.7 303.6 -.330-**, 830 -, 77C-T, ;:c Cl) 1*23-155OOF (77--S.3C) (2) 1 36*- i o 52 F ( 7-0-900aC) (1) 13 sec (2) 12-1* sec (l) 560-6 30* (2) l.280-l,*30* (1) Pb 0.55-2.2 (2) Pb 0.4A-0.87 (!) 99.93 (2) 99.93 U) 14,800 (2) 26,700 (1) 6. 32 (2) 6.40 (1) (2) 11.0 35.7 34.6 *2.2 95.7 219.* 7.8 35.7 5.7 2*. 8 53.8 127.8 117 000016493 MOD Table 4.11 (Concluded) J.S. EFA-SPONSORED WASTE INCINERATION DEMONSTRATION PLANTS Zlaoro. Inc., Rothehtld. Wise. )M Company. Cot case Grove. Winn. Rollins Environoentii Service nc . . ye e r ?a r k , 7 s * a s Incinerator type Two continuous autoclaves Id scries wild ill bubbled chrougn the liquid -astes at elevated temperatures and pres* sure* k to 1600 psigj in the presence of a copper catalyse. Rocery ktln followed by a acor*3*ry coabuetLon cmabtr, a vaeer guenon cover, a veter scrub cowsr, and an exfuuec s tee*. Rotary *iln followed oy an afcerbutner chamber. venturi and trj/ ctver strutters, end an exnaust scacit. Incinerator capabilities feed race Liquids with low heating values $-100 gph Puapeble liquids and drummed solids 4,000 lb/hr ?uoMbie liquids westes end druand soiius 723 lb/hr ?C3 capacitors In i rims Operating tQperaturc Heat capacity (Btu/hr) Wattes treated (ccebusclon r.eat) qc lie racer tondlclsna feed race i lb/ hr ) Teeperature Residence else Incinerator performance 2tac. particulates ing/a^) Trace oatale, sg/o^ 450-620F ( 230-325C) - (D Case plant aqueous wastes containing phenols, cresols. ammonia, and pa rtleulates; 00 > $.520 ppm (100 Btu/lb) (2) Aqueous wasee solo of dlchloronitrobenaene (20g/1) and b*'T Jlssoivea toe ids c::c Btu/ib) (1) -6 (2) $3.4 (1) $36F ( 28CC) ( 2) 536F CSO^C) Pressure. 107 ats (2) 1.0 hr (2) 1.0 hr Further water crestoanr needed to remove catalyst and residual organics. (O 99.AS of dlthloronltrobenzane (2) ?9I phenol 6b 1 quinoline 980-1090C (1800-2000?) 2 400-2 700 F (1200-15CCC; 90 x 106 110 x 10* ; 1) Aqueous (72*) slurry of polyvinyl cnlonde solids (231) with craces of vinyl chloride and allpnatlc hydrocarbons (1,300 Btu/lb) (1) 725 Ib/'hr silled ?CB capacitors in fiber drums (<$,000 Btu/ Ih) (2) N'itrachioeooentene i95I) wastes plus $2 .spears (9. 2CC Btu,Ip) Prlaarv rone : IbOCrOF' ( 870C) Secondary zone: :ooof U09$C) (I! 725 (2) 1.025 (1) Kiln, J230F aot used Af terourner. 2- 30F (2) Klin noc used a:terburner, 2430F Solids. 2 hr Cases, 2 sec 71* (HCl, 1$) (1) 2.2 sec (2) 2.3 sec (1) 25* (2) 14* Scrubber water 720 ag HC1/1Iter (1) ?b 2.7 (2) None decected destruction efficiency '.?) 835 of COD (1) 99.99 (2) 99.99 (1) 99.96 (2) 99.99 Eatisaced ccoterclal plant site (snort tons/nr) (1) 770,000 (2) $3,000 74.000 ID $.500 (2) 5.000 Eat. capital investment, adjusted to January 1979 ($ nilllon) (1) U.3 (2) 2.3 8.3 (D 3.9 (2) 3.0 Ope racing cost. adjusted to January 1979 (S/short ton) Labor, $11.70 mai^Kr Auxiliary fuel. $2.60 olllion Btu Chemicals and utilities Maietenance Capital-related coat* US Investaaoc Total operating coat Sec cost Cl) (2) 0.42 1.00 2.95 0.50 0.45 0.64 3.27 jrrr 3.18* 9.36 1.09 1.95 9.23 TTTT3 0.30 16.10 52.5 185-5 31.5 40.7 223.4 533.6 Cl) O 93.6 307.0 54.4 2C.2 96.3 71.6 154.2 72777 18.9 33.8 130.9 I$5U So organic -.aste material# detected In scrubber water. 'fuel credit. *Fol low-up t reatoene . Source; 447GOB. 118 c s C e mod ^0016^94 The rotary kiln followed by a secondary combustion chamber or afterburner offers the greatest flexibility for handling both liquid and solid wastes with destruction efficiences of greater than 99.99%. However, the capital investment for this system ($600 to $ 1,100/annual ton capacity) is the highest of the five systems considered. For those wastes with less chan 5,000 Btu combustion heat per lb, auxiliary fuel costs can be appreciable. The design of direct fired rotary kilns is similar to that for direct heat dryers. Heat efficiencies usually range from 55 to 75% with heat transfer rates of about 2,500 to 6,000 Btu/hr/cu ft (B-l). Heat efficiency can be improved by the use of heat exchangers or recuperators to recover sensible heat from the exhaust gases. Zimmerman (447076) has described the Kelly-Hoskinson batch inciner ator, which ranges from 2 to 12 cu yd capacity. It has a primary combustion chamber that operates at 2200F (1200C) and provides second ary fume combustion in the base of the exhaust stack. It operates without precipitators, scrubbers, or grates on combustible wastes and gases which are noncorrosive and nontoxic. Purchase cost ranges from about $12,000 to $62,000 (January 1979). Natural gas fuel consumption is between 100,000 and 300,000 Btu/hr. Combustion Solid wastes containing less than 2 to 3 lb of water per lb of combustible material can usually be incinerated without auxiliary fuel and possibly with some heat recovery. For example a solid waste con taining 52.3 wt% carbon, 6.2% hydrogen, 40.5% oxygen, and 1.0% ash, has a gross heat of combustion of 9,000 Bcu/lb. The available net heat from burning 1,000 lb/hr of this material, accompanied by 100 lb/hr of moisture, is as follows: MOD 00001649b 119  Gross heat input (9,000 x 1,000) Less evaporation or free water (1,060 x 100) Less evaporation of formed water (0.563 x 1,060 x 1,000) Less losses, assume 80% heat trans. effic. (9.0 x 106 x 0.2) Net heat Btu/hr 9,000,000 106,000 597,000 1,800,000 6,497,000 This is equivalent to 5,700 lb/hr of saturated steam at 125 psig. Detailed considerations of the design of municipal waste treat ment incinerators have been published by the Research and Education Association (B-13933). Capital investment for a multiple chamber batch incinerator is said to be about $15,000 to $40,000 per daily ton of waste capacity. This is exclusive of any combustion gases treatment. By comparison, costs by Babcock, and Wilcox Company (447075, adjusted to January 1979) for a coal fired steam generator are as follows ($ 1,000) : Steam Capacity (lb/hr) 50,000 100,000 200,000 Equipment cost Boiler, furnace, fans, economizer and firing equipment Metering and control inst. Deaerator and water treatment Boiler feed pump Total equipment 675 25 60 ___ 5 765 1,100 30 91 9 1,230 2,000 40 147 13 2,200 Estimated module cost (f^ 3.0) 2,300 3,700 6,600 Assuming a waste sludge feed of 5,000 Btu/lb net heating value (i.e., equivalent to 3.7 lb steam/lb sludge), the above module costs range from $10,000 to $15,000 per daily ton of sludge feed. c\o 120 Waste Solids Disposal Land Faming Land farming has been used in the United States for over 25 years as a neats of disposal of refinery sludges. Over the next several years, the quantity of sludge disposed of by this method could double or triple (447079). Land farming is applicable to biodegradable hydro carbon sludges which are nontoxic, nonreactive, and nonvolatile and have flash points below 140F (60C) (447088). These are principally oil refinery wastes such as API separator bottoms, treating clays, and tank and separator cleanings. Land farming consists of spreading the hydrocarbon waste over bare soil in layers up to several inches. The land is then cultivated at regular intervals to provide closer contact between the waste and the soil. Bacteria convert the waste to humus, wThich may actually improve the original land's ability to sustain vegetation. Typical application rates for oil refinery wastes range from about 200 to 600 barrels/year/ acre (30 to 90 tons/year/acre) (447017). Regulations for the selection and operation of land farming sites (447C88) stipulate that land farms be located on stable, level land at least 5 feet above the historic high water table, with no possibility of migration to livestock, or public water supplies. Wastes must not be applied when the soil is saturated with water or when its temperature is less than freezing. The pH of the soil should be between 7 and 9 to prevent leaching of heavy metals and to encourage bacterial or algae growth. The use of supplemental nitrogen and phosphorus may also be needed to assist the growth of microorganisms. The site must be monitored to detect any migration of waste impurities. A typical cost for land farming operations, exclusive of land, is reported to be about $16.50 per ton of waste (447088, February 1979). *cr> OQr >01 121 Stacking Waste stacking is applicable mainly to gypsum from wet process phosphoric acid plants or from power plant flue gas scrubbers (447091). To start the stack, an area is enclosed by an earthen dike, and the aqueous slurry is pumped inside. The gypsum settles and the water overflows and is recycled or neutralized. As the gypsum settles and consolidates, it is used to raise the retaining wall for the gypsum pond as shown in Figure 4.14. Gypsum has a sedimented density of about 100 lb/cu ft; therefore, one acre foot has a storage capability of 2,000 tons. Thus, a 1,000 tons/day vet process phosphoric acid plant producing 4,500 tons/day of gypsum that is stacked to a depth of 20 ft would require 40 new acres every year. Regulations for stacking as well as those for sanitary disposal (discussed next) are generally similar to those for land farming (447083). Disposal costs are principally land costs. Added to this is the cost of a dragline or mechanical shovel for building dikes and possibly a rubber or plastic liner to prevent contamination of ground water sources. Sanitary Landfill Sanitary landfill is the placing of compacted wastes into earth cells which are later covered with soil. The wastes must be inert to begin with or be capable of microbial conversion to harmless compounds. The landfill should be designed to prevent leaching from the fill and contamination of surrounding streams. This may be accomplished by providing drainage from the fill to a collection and treatment point or by enclosing the fill in an impervious liner (447090). 122 aV Figure 4.14 STACKING PROCEDURE FOR WASTE GYPSUM V FIXED VERTICAL Source: 447091, 123 Cl0, X9& Disposal costs for landfill operations, where cover material is available on site, are estimated to range from about $10/ton at 20 tons per day, to $4*5 at 50 tons and $2.5 at 200 tons per day (383522, adjusted to January 1979). Hazardous-Waste Landfill Hazardous wastes are those materials which pose substantial pre sent or potential hazard to human health or living organisms because they are lethal, nondegradable, persistent in nature, ox cause detri mental cumulative effects (447007). These include toxic, radioactive, flammable, and explosive materials. Numerous restrictions apply to the selection of a hazardous-waste disposal site, permits are necessary for dumping wastes at these sites, and long term monitoring is required to detect any leakage from the containment area (447015). Finally, severe penalties are provided for noncompliance with these regulations. The complexity of regulations and the costs of compliance tend to restrict ownership of hazardous-waste disposal facilities to those com panies with appreciable quantities of hazardous wastes or to companies specializing in services. A 1977 EPA publication (447092) lists over 100 hazardous-waste management facilities across the United States. These include service operations for incineration, deep-welling, and land disposal of hazard ous wastes as well as for solvent reclaiming and metal reprocessing. A resume of the background, capabilities, and service charges for many of these operations is contained in another EPA publication (447078). Secure landfill disposal costs are in the range of $20 to $60/short ton. The estimated costs for a 20 year operation of a hazardous-waste facility (4,000 tons/yr) owned and operated by Union Carbide are as follows (447007, adjusted to January 1979): 0000 rtCt1 >0 124 Study and La nd Equipment Operating design costs (20 years) Tot ai $ 114,000 147.000 367.000 4,242,000 $4,870,000 ($61/ton) c An industry source estimates that pending regulations and infla tion will double hazardous-waste landfill disposal costs by 1985. Other Disposal Methods Ten years ago the oceans were the recipients of large volumes of V solid industrial wastes (447029). However, increasing regulation is gradually reducing the quantity and kind of industrial wastes which may be dumped in the oceans (419299). In the United States, EPA regula tions are expected to terminate the discharge of waste to coastal waters by the end of 1981 (447082). In Western Europe a 95% reduction of ocean dumped wastes by 1985 is proposed. Another alternative for disposing of solid waste is to slurry it in water and inject it deep into the ground where it is isolated from potable-water aquifers by impervious and fracture-resistant strata of shale, limestone, or dolomite (447087). Currently, there are approxi mately 380 deep welling sites in the United States. By the end of 1979, all such sites in the United States are expected to cone under EPA regulations for inspection, monitoring, record keeping, and report ing. Thus, deep-welling is likely to continue for some time as a waste disposal method in suitable locations but with increased control and regulation. The average investment for a deep well--including casing, surface facilities, pumps, etc.--is about $75 to $90 per foot (447087, adjusted to January 1979). Maintenance costs for an injection rate of 6 million gal/ao (140 gal/min) into a 10,000 ft well are reported to run about $60,000/yr and energy at 2c/gal (447087). 125 5 COST CALCULATION'S FOR WASTE TREATMENT MODULES r There are a number of methods for the development of preliminary capital cost estimates for chemical or waste treatment processes. The Hirsch and Glazier method (289) totals the purchase costs of all the major equipment. This total is multiplied by given factors--depending on the amount and type of equipment--to obtain the battery limits investment for the process. This figure represents the capital cost of the complete, ready-to-operate processing unit. It includes founda tions, piping, instruments, housing, erection costs, and contractors fee, but excludes land, utilities, feed and product storage, and start-up costs. This method has been adapted to PEP estimating procedures. The Miller method (10039) for estimating the cost of a chemical plant totals the costs of major equipment items and then adds per centages for the foundation, erection, piping, insulation, electrical work, and building requirements. These percentages are selected on the basis of the type of process and the average value of the major equip ment items. They allow the estimator some leeway in deciding whether each requirement is minimal, moderate, or extensive. This method, has also been adapted to the PEP computer program. A third method (used by Guthrie) estimates the installed or modu lar cost for individual processing operations (distillation, drying, etc.) by multiplying the purchase cost of the equipment by factors for installation labor and materials. The battery limits cost is the sum of the modular values plus a percentage for indirect costs. This method requires slightly more time and effort than the others but it correlates installation costs with specific operations better than the others do. 127 MCI) OC001S502 Waste treatment processing consists of only a few standard chemi cal and physical operations. Thus, the use of process modules is possibly the simplest means for estimating the investment for treating a given waste flow. Guthrie (B--13926, 76481) has applied the modular approach to the evaluation of chemical process capital investments. In Guthrie's method the costs of installation materials (M) and labor (L) are esti mated as fractions of the purchase cost of the equipment (E). Thus, the direct or installed cost of an item of equipment is'E + M + L. This sum is then multiplied by an indirect factor (I) (which depends on the size of the direct cost) to obtain the modular cost of that equip ment item, as illustrated schematically in Figure 5.1# Excluded from the modular cost is the cost of land, site preparation, contractor's fee, and contingencies. Guthrie supplies M and L factors for specific items of chemical equipment in various sizes. Adjustment factors are supplied for alter native materials of construction and for locations other than the U.S. Gulf Coast. The effects of inflation from the base year to the present are handled by applying the appropriate cost indices to both materials cost and labor cost. A disadvantage of the Guthrie method is that L and M factors are not available for all types of process equipment-- particularly some of the equipment used in waste treatment--and the procedure to develop them is complex. Icarus Corporation (447001, 447056, 447057) has applied a modular cost estimating technique to waste treatment systems. The Icarus method is much more detailed than the Guthrie method. Equipment costs are obtained, together with the cost of materials for installation. Allowance is then made for labor cost and productivity, to obtain a direct cost. Adding construction overhead and engineering costs results in a base module cost comparable with that for chemical equip ment by the Guthrie procedure. Icarus also provides location, design, 000016603 MOD 128 V C/5 < C/5 ID oC/5 O IX < _J Q O X oLL Q O X UJ LD X X H D (3 V 129 0^66^ 4 O0^ and material factors for adjusting the module costs. It has also been adapted to a computer program. However, this program has several disadvantages: The amount of detail and effort necessary to estimate module costs is more appropriate to an engineering design than to a preliminary estimate. There is no separation of the modular cost components to permit user modifications or to enable users to derive their own module costs for special equipment. We have developed a simple and quick procedure for estimating nodular costs for waste treatment operations which is independent of both Guthrie and Icarus modules. Capital Cost Methods Used in this Study The nodular costs developed by both Icarus and Guthrie are gener ally 1.8 to 5.0 times the purchase price of the equipment. This is also true for the PEPCOST estimates of battery limits investment. Equipment items with "little" requirement for (A) foundations and support, (B) connecting piping, (C) electrical connections, insulation, and instrumentation, and (D) enclosure are close to the lower limit, while those with "extensive" amounts of these additions tend toward the upper limit. If, as shown in Table 5.1, we arbitrarily assign values of 0.2, 0.6, and 1.0 to represent "little", "some", and "extensive" needs for each of the four categories of installation activity, we have a quick way of estimating modular costs. For example, a tank and pump erected outside on the ground, with only inlet and outlet pipes, would have a module cost factor * 1 + 0.2 + 0.2 + 0.2 + 0.2 * 1.8. A distillation operation erected indoors on steel supports, with inter connecting piping to condensers and reboiler and with extensive instrumentation and insulation, would have anfj^l + l + l + l + l = 5. mod 00001650! 130 Table 5.1 SRI MODULE INVESTMENT ESTIMATION FACTORS Installation Requirement Little Some Extensive factor 1.0 1.0 1.0 (A) Foundations, steel supports, and field labor 0.2 0.6 1.0 V (B) Connecting piping 0.2 0.6 1.0 (C) Insulation, electrical 0.2 connections, and instruments 0.6 1.0 (D) Building or enclosure Totals 0.2 0.6 1.8 3.4 1.0 5.0 Notes: (1) Module cost factor (ftf) " 1+A + B + C + D. (2) Module cost = purchased equipment cost (f.o.b.) x fj^. Table 5.2 compares Icarus and Guthrie module costs with those estimated by SRI's simplified procedure. While considerable variation occurs in the cost of similar equipment items by the three modular estimating procedures, the equipment cost totals are very close. For example, the estimate for a 10,000 gal vertical cylindrical stainless steel tank is $108,000 by the SRI method and $190,000 by the Guthrie. This Is equal to a plus or minus mean deviation of (190 - 108)/(190 + 108) x 100 = 27.5. However, the totals for the nine modules listed show a mean deviation of only (1,872 - 1,703)/(1,872 u 1,703) x 100 = v 4.7X, Thus, for a multimodule treatment system, the individual devia tions appear to counteract one another. Also the modules developed above appear to offer sufficient accuracy for an approximate cost estimation. MOD 000016506 131 Table 5.2 COMPARISON OF CHEMICAL EQUIPMENT MODULE COSTS ESTIMATED BY DIFFERENT METHODS Basis: PEP Cose Index 290 Time January *979 Equipment Description Air cooled exchanger 500 sq ic Steel tubes Icarus Module Cost* rs) 45,000 Equipment Purchase Cast (S) 16,400 Column, valve trays 5 ft dia. x 30 ft high IS trays Carbon steel 165,000 72,000 Oppressor , centrifugal i ,000 hp Turbine drive 70C.COO 320,000 Furnace, cylindrical Carbon steel 10 million 3tu/hr 250,000 82,000 Heat exchanger, 1,COO sq ft LOO psl Carbon steel fixed tube 58,500 14,300 Puap and driver, ICO gpm 70 ft head Iron centrifugal 10,900 1,950 Tank, horizontal, cylindrical 10,000 gal Carbon steel 47,000 15,000 Tank, vertical, cylindrical 10,000 gal Stainless steel 150,000 45,700 Thickener, ICO ft dia. 7 ,8C0 sq. ft. 390,000 -- Totals 1,616,400 Guthrie Module Factor 2.17 Module Cost (S3 3S.500 Equipment Purcnase Cost (S) 14,500 3.05 220,000 48,000 2. 15 690,000 340,000 2. 19 180,000 75.000 3.17' 45,000 9.700 3.30 6,400 2,000 3.05 46,000 14,000 4.16 190,000 60,000 - 290,000* 140,000 1,702,900 SRI Module Factor 2. 2 Module Cost (S) 32,000 + 9 4. 200,000 2.6 3.- 2 890,COG 235,200 40,700 3.8 7,600 2.2 31,000 1.8 108,000 4 307,700 1,872,000 *Equipoenc purchase cost and module factors are not readily sepa rable from the Icarus Corporation module cost *This figure was derived from the Coat Engineering Quarterly in order to complete the comparative column. vo- 0^ c \ r e e 132 i Operating Costs Operating costs for waste treatment--like those for chemical processing--are a function of the following three variables: / Variable Dependent Operating Costs Capital cost Maintenance, taxes, and insurance, amortization, return on investment Feed or production rate Process materials, utilities. Process complexity Labor (operators/shift), control V analysts, overhead, supplies. G&A (administration), sales, and research costs, and working capital interest, which are usually included in chemical plant operating costs, are believed to be small enough to be neglected for most waste treat ment systems. Capital-related charges, maintenance costs excepted, are normally taken as a predetermined fixed percentage of the capital investment. PEPCOST customarily uses 2% for taxes and insurance, 10% for amortiza tion, and 25% for return on investment. The maintenance percentage depends upon the nature of the equipment and the stream being pro cessed. Table 5.3 suggests a procedure for estimating annual module maintenance cost as a percentage of the module investment. Thus, a mixing tank or system handling noncorrosive liquid with some agitation and connected to inlet and outlet pumps would have a percentage main tenance =0+0+1+1+0 2%. A filter or centrifuge processing a sulfuric acid slurry would have a figure of 7 or 8%. Other operating costs which are a function of feed rate or process complexity are specific to each treatment operation and no generalized correlations are possible. Thus, the applicable process materials and utility requirements for each waste treatment operation is listed on the same page as the module cost. Where the labor requirement (operators/shift) is shown as a range (e.g., 0.2 to 0.5 operator/shift), the lower figure at the low end of the waste stream flow rate and the upper figure at the high end. 133 HrD Module Cost Curves We have derived module capital costs and maintenance percentages from published or quoted equipment prices and modular cost factors (f^) as described above. For some specialized equipment--e.g., ozone generators, and electrodialysis or reverse osmosis cells--we used published installed capital and operating cost data directly for the modular costs. These costs apply to a point in time of January 1, 1979 and a PEP Cost Index of 290. Cost curves have, where possible, been based on waste stream flow rates to enable direct reading of the nodular cost. Where these costs are given as a function of equipment size, descriptive information in Section 4 of this study will enable a conversion from size to waste stream flow rate. In instances where the desired nodule cost curve and operation table are not available, the procedures outlined above will enable the interested user to construct them. Table 5.3 SRI MODULE MAINTENANCE COST ESTIMATION FACTORS Conditions Contributing to the Cost of Maintenance (A) Corrosivity, special const, materials (B) Temperature above normal CC) Power usage and moving parts (O Connecting equipment (E) Solids handling, abrasion Totals Annual Maintenance Cost (% of module cost) None Some Appreciable 01 01 01 01 01 05 2 n 2 1 2 10 Note : Annual maintenance cost (M^) (A + B + C + D + E) x module cost MCI) 00001S509 134 s&k. The module capital cost curves and operation tables we developed are shown in Figures 5.2 through 5.53, as follows: Waste Stream Aqueous Gaseous Solid Figures 5.2- 5.31 5.32-5.44 5.45-5.53 The application of these modules to the estimation of capital and operating costs for the treatment of chemical industry wastes is demonstrated in Section 6. /" HCX) 'OOOI65 10 135 Figure 5.2 MODULE COST: TANKS TANK VOLUME, gal M O D U L E C O S T , $ m il....... 10,000 100.000 TANK VOLUME, gal 1,000.000 oO 0 \ 136 10.000,000 M O D U LE C O ST. $ m illii^m Figure 5.3 MODULE COST: THICKENER, CLARIFIER SETTLING AREA, sq ft 137 MCD 000016612 Figure 5.4 MODULE COST: SETTLING LAGOON C M O D U l C O S T. $ im lhonb S' I___ I___L I I I I I 30.000 100.000 ,-NOOOl6 51^ SETTLING AREA, sq ft --i__1 ' 1 1.000.000 SETTLING VOLUME, gal 138 I I II i 10,000.000 1 .......1 30.000,000 L V Figure 5.5 MODULE COST: OIL SEPARATORS PLOATING OIL VOLUME, gph 20 100 300 V. M O D U LE COST. $ n u llio n i 139 mod 0o0165;l4 Figure 5.6 MODULE COST: FILTERS M O D U LE CO ST, $ m illions o>-O s> FILTER AREA, $q ft 140 Figure 5.7 MODULE COST: CENTRIFUGES SOLIDS CONTENT, ip/hr 1.000 10.000 30.000 10 0 c Material F actor Stairness steel 1 0 v 1.0 M O D U LE: COST. $ m ilhuns 0.10 -- - 0.01 1,000 Operation. OO O Maintenance, 3a of moauie cost/yr 5 5 5 Labor, ooerators/snift 0.5 0.5 0.5 Electricity, kw/1,000 gph 3* 1 1 3 kw per 1.000 ifc'hr sohas flow. 10,000 LIQUID FLOW, gph 100.000 1.COO .000 141 MCD 000016516 Figure 5.8 MODULE COST: HYDRAULIC CYCLONES r C MODUl fc LOS 1, $ im 1l1uns .. > <) ' S> LIQUID FLOW, gpn 142 r e M O D U LE COST. $ m illions M O O U LE CO ST, $ m ilium s w Figure 5.9 / MODULE COST: DISTILLATION SYSTEM c LIQUIO FLOW, gph MCI; 000016518 143 Figure 5.10 MODULE COST: EVAPORATORS 200 WATER EVAPORATED, lb/hr 1,000 10 000 M O D U LE C O ST, $ m illio n s CD *0 o WATER EVAPORATED, ib/hr 144 Figure 5.1 1 MODULE COST: STRIPPER, STEAM OR FLUE GAS V M O O U L CO ST, $ imlliDMbt LIQUID FLOW, gph 145 mod 000I(j5. 5^0 M O D U L I COST, $ m ilium s Figure 5.1 2 MODULE COST: LIME NEUTRALIZER LIQUID FLOW, gph V-4 O T. 146 C ( v ( c C Figure 5.13 MODULE COST. SYSTEM FOR CHEMICAL REACTION OR PRECIPITATION 10 0 Material Factor Carbon steel Stainless steei Glass-lined 1.0 16 1.8 c M O D U LE . C O S T . $ finUii.li:> 0.01 1,000 Operation (all curves): Maintenance. % of module cost/y Labor, operators/shift Electricity, kw per 1,000 gpn 4 0.5 3 Note: Add quantities of any reagents required. 110,000 I 1 I I I 11 -- 100.000 LIQUID FLOW, gph I I'll 1.000,000 0000165 o o MCD 147 Figure 5.14 MODULE COST: ION EXCHANGE SYSTEM r c M O D U L I: COS I, $ m ,ih,is /o tvo LIQUID FLOW, gph 148 r c e Figure 5.1 5 MODULE COST: ELECTRODIALYSIS AND REVERSE OSMOSIS CELLS 10.0 i ' v. M O D IJl E COST. $ m illion:, 0.10 0.01 1.000 10,000 LIQUID PLOW, gph 100,000 1.000,000 149 mod 000016524 Figure 5.1 6 MOOULE COST: DISSOLVED-AIR FLOTATION CELL r C M O D U LE COST, Sm illio n s LIQUID FLOW, gph MOD 000016525 150 r C c Figure 5.1 7 MODULE COST: CRYSTALLIZATION SYSTEM M O D U L E A COST . $ in.lin ing 1o r Mooule cost = sum cf Modu e A jnd Moau.e 8. 3 millions 05 0 3 CRYSTAL SEPARATION ibi 1.000 gai f:ow 0.2 CRYSTAL SEPARATION 'MODULE A) 01 -e 5 EVAPORATION (MODULE 3; WATER EVAPORATED '0/1.000 gal Low 10 M O D U LE U COST. $ m illio n s 0.2 1.000 i I llI 10.000 Operation {Module A & B total) Maintenance, % of total mooule cost/yr Labor, ooerators/shift Electricity, Kw/1.000gal l.ouid flow.hr kw/1,000 lb/hr solids seoarated Steam, f ,000 lb/1 000 Ib/br warer evaporated Cooling water, gpm. 1,000 ib.hr water evaporated 4 06 3 1 JA 100 I 1 I 1 I I I_________ I 100,000 LIQUID FLOW, gph 1 I I I I II 1.000.000 151 :>00' Figure 5.1 8 MODULE COST: ACTIVE CARBON ADSORBER FOR LIQUID STREAM 100.0 Material Factor Carbon steel Stainless steel l0 1a Carbon bulk density = 30 itvft^ 100 COO DECREASE Img/liter) c M O D U LE COST, $ m illions Operation: Maintenance. % of module cost/yr Labor, operators/shift Carbon makeuo. ib/hr Steam, lb/hr Natural gas. Stu x lO^/hr Electricity. kv 4 1.0 1 OF * 22.4F 0 08 F 0.22F _ liauid flow Igphl * .i COD 1 ma/nterl 1 015 10.000 i i 1 1 1______________ 1_______ f_____ 1____ 1___ 1__ L 100.000 11,,000.000 LIQUID FLOW, gpn r c .>'1 c 152 Figure 5.19 / MODULE COST; SOLVENT EXTRACTION SYSTEM 100 0 Material Factor: Carbon steel Stainless steel 10 1.8 Basis: Concentration of extractable component = ' .5% M O D U LE COST. $ m illions 10.0 10 0.1 1,000 COUNTERCURRENT SOLVENT EXTRACTION WITH DISTILLATION SEPARATION OF SOLVENT ANO EXTRACT COUNTERCURRENT SOLVENT EXTRACTION WITHOUT SEPARATION OF SOLVENT ANO EXTRACT Operation: Maintenance, % of module cost/yr Labor, operators/shift Electricity. kw/ 1.000 gpn Steam, lb/hr/1.000 gph Cooling water, gpm/1,000 gpn Solvent loss, lb/1.000 gpn Extract recovery approx. 97% O0 44 4 1 1 0.25 54 1 2.800 1,000 - 300 120 - 63 3 J___L i i i 10,000 LIQUID FLOW, gph ii 100.000 1..I ,J. 1,000.000 153 t-ic: UL o0 ,'VH 10 0 10 F:gure 5.20 MODULE COST: BIOLOGICAL OXIDATION SYSTEM INCLUDING SLUDGE SEPARATION Feed * 1,250 oom BOD * 2.500 oom ThOD F*iter depth = 22 ft r c A--A M O D U I L CO ST, $ nullum :, 0.10 -- " -- _ - 50% Material Factor: Carbon steel _ Concrete \.,, ' / 1.0 Rubber-lined ^20 P'ashc construction 1 Operation: O Maintenance, % of module cost/vr Labor, operators/snift Efectricny, 1,000 gph Ammonia reauired, l b /1.000 gpn Phosphoric acid reauired. ib/1,000 gal Lime reauired, 10/1,000 gal Copperas reouired, 0/1.000 gal Land area reouired. acres/10 gpd Filter volume, ft^/gph Sludge* separated, cu ft/1.000 gat 4 1 10 oa 0.4 4,2 o.a 0.2 - 0.2 0 4 1 13 0,8 0.4 5 1.0 0.5 0.3 O 4 0.7 2 0.6 0.3 3 0.6 - 1.25 02 4 05 1 03 0.15 2 0.4 - 0.25 0.15 Sludge moisture * 70%. wt/cu ft * 64 lb. 0.01 1,000 1 I 1 I II 10.000 i f__ i i ml------ 100.000 ii 1,000,000 LIQUID FLOW, gph c ,0s* 154 V Figure 5.21 MODULE COST: FACULTATIVE LAGOON TOO 0 r Materia factor _ Eartn ana poi vetny iene 1 0 Four feet deep vm11n rc agitation Cost distribution = 2S -i excavation. 75% immi Liner life * 4 years 10 0 M O D U L L COST. 4 m .lli.-ns 10 C 30 C Ooeration: Maintenance. % o< module cost.'yr Labor, operators/shift Area, acres 20% ml _ apm @10 = 0 04S x -------- x % SO 0 removal 1.000 qpm @ 3CT - 0.030 x 1 000 x % BOD removal J___ I__ I I 111 10 000 Feea BOD = approx. 1.250 ppm i 1 t l i i I___________ I 100.000 LIQUID FLOW, gph I .-I--I__ ill! 1.000.000 155 wcv c,h0: 00^ Figure 5.22 MODULE COST: FILTERS. DUAL MEDIA AND SAND C M O D U L E CO S , $ n n lJ io mf LIQUID FLOW. gcr> MOD 000016531 156 C c M O D U LE CO ST, $ nnlliuiib Figure 5.23 MODULE COST: FOAM FRACTIONATOR V f LIQUID FLOW, gph MOD 30 Qq o.'-i.i v 157 Figure 5.24 MODULE COST: OZONATION SYSTEM c M O D U LE LU S T . $ m ilium s LIQUID FLOW, gpn rtco ooooie\53*3 158 / e c Figure 5.25 MODULE COST: DENITRIFICATION SYSTEM S' V M O D U LE COST. $ m ilituns LIQUID FLOW, gph 159 ',1^ b Figure 5.26 MODULE COST: HYDROLYZER M O D U LE COST. $ m illio n s -*0* .o LIQUID FLOW, gph 160 c Figure 5.27 MODULE COST: CHLORINATQR FOR AMMONIA REMOVAL r \ M O D U L I; COST. $ m ill.u .i* ( \ LIQUID FLOW, gph 161 vV' Figure 5.28 MODULE COST: CHIORINATOR FOR DISINFECTION AND EQUIPMENT FOR WATER QUALITY CONTROL c \ r M O D U LE COST. $ riiifiiu n LIQUID FLOW, gpn :* y 162 e ( Figure 5.29 MODULE COST: PUMPING SYSTEM AND DEEP-WELLING SYSTEM c K LIQUID FLOW, gph F igure 5.30 MODULE COST: LIQUID INCINERATOR M O D U LE COST, $ m illions 0 O4-- 3- 164 1.000 10.0 |-- Figure 5.31 MODULE COST: STEAM AND COOLING WATER UTILITIES STEAM GENERATION RATE, iD/hr 1250 osigl 10.000 100.000 1.000.000 M O D U LE COST. $ m iliu m * 0.5 I 1 11 100 1,000 10,000 100.000 COOLING WATER FLOW RATE, gpm MCD 00001654Q 165 Figure 5.32 MODULE COST: GAS COMBUSTOR FOR STEAM GENERATION c v r M O D U LI'. C O S T, $ im lliu m .'O" vO & GAS FLOW, scfh 166 c 10.o c 0* 10 Jt c a o / 0.10 /' 0.01 1-- I 10.000 V Figure 5.33 MODULE COST: GAS INCINERATOR Steam generation, ie/hr/1,000 scfh Fuel requirement, Btu/1,000 scfh 3 0.5 0.2 0 02 80 0 1x1 06 -till 100,000 1 '___ 1 I I I I I I ,1 000,000 GAS FLOW, scfh i i i ti 10,000,000 MCB OOOOl 6542 167 100.0 Figure 5.34 MODULE COST: FLUE GAS DESULFURIZATION SYSTEM to.o C M O D U L E CO ST. $ m ill..m s i0 0.1 10,000 Operation. Maintenance, a'o of module cost/yr Operating labor, operators/snitt Limestone, ib/hrper KOQOscfh Electricity, kw per 1,000 seth Steam, ib/hr per 1,000 seth Solid waste, i&.-hr per 1.000 scfh Note: SO2 content reduced from 2.500 ppm to 250 ppm 3 2-3 0.674 0.10 163 2.25 J___L 100.000 GAS FLOW, scfh 1,000.000 r 1 1l 10,000.000 e vU'.T', 0\'C e 168 M G O U L E COST. $ m illio n ') Figure 5.35 MODULE COST: HYDROCARBONGAS FLARE GAS FLOW, scfh 169 MOD 000016544 Figure 5.36 MODULE COST: GAS DISPERSION STACK c r M O D U l fc C O S T . $ m illio n s GAS FLOW, scrn :,'c 0'i'nJ o 170 e M O D U LE COST, $ m illions Figure 5.37 MODULE COST: AMMONIA NEUTRALIZER GAS FLOW, scfh MCD 000016546 171 M O D U L fc C O S T, $ m iliu m s Figure 5.38 MODULE COST: ACID GAS NEUTRALIZER 10 0 10 0.1 0.01 10.000 ACID EQUIVALENTS PER 1,000 scfb Matenai Factor Carbon steel Rubcer-nnea i0 I4 Operation Maintenance, % ot module cost'yr Operating Labor, operators, snitt Electricity, kwr 1.000 scth Process water, gpm Calcined lime or NaOH, ib/hr scfh A= 1.000 acid equivalent 1.000 sc f O 6 1.0 0 3 * 0 302A 2.5 A 66A ;96-=l i ' _L_L 100.000 --1 i t 1,000,000 GAS F LOW, seth O <1 0.7 0 3 - Q 0Q1A 0 7A 88A iSO'b) t ii 10.000.000 O*' kO 0.`0" vy- 172 Figure 5.39 MODULE COST: SCRUB8ERS. HYOROCARBON OR WATER Material Factor: Carbon steel 10 Seamless steel 16 Giass-imed, titanium 4.0 HYDROCARBON SOLUBLE VAPOR Hb/1.000 scfi M O D U L I COST, $ million-. 000 Operation: Maintenance. % of module cost vr Operating labor, operators/shirt Electricity. kw/l.QQQ scfh Fuel. Btu/1,000 scfh Cooling water, gpm/1.000 scfh Makeuo water (oil) o 3 0.3 03 - o0 4 0.5 0.3 700 0.03 444 05 05 0.35 0.4 0.5 0.5 1,300 3.300 6.500 0.06 0 15 0.30 Small t i i i i t ii! 100,000 1i t i i i i , , 1.000,000 l l i lilt 10.000 GAS FLOW, scfh >dCD '.100016548 173 Figure 5.40 MODULE COST: ACTIVE CARBON ADSORBER FOR GASEOUS STREAM :o o VAPOR CONTENT lb/7.000 sen t.o M O D U LE COST, $ m illio n s 0 10 - - 0.01 000 1 1. 1 100.000 Operation: Maintenance. of module ccst/yr Ooeratmg laoor, ooerators/snift Electricity, kw/1.000 scfb Steam, lb/1,000 scfh Cooling water, gpm/1,000 scfb o 4 0.5 0 08 5 0.6 4 0.5 0 09 10 12 4 05 0 70 20 24 1i i i i i i , i 1.000.000 GAS FLOW, scfh i 1 r fill 10,000. ooov6b AS 174 M O D U L I COST. $ m illion* Figure 5.41 MODULE COST: G AS COMPRESSO R c MCD 0rjle55 O 175 M O O U l C C O S T . }, ir 11Mn 11-j, Figure 5.42 MOO U LE COST' DUST SEPARATOR GAS FLOW scfh MCD ! >0001 6551 176 Figure 5.43 MODULE COST: GAS COOLERS r M O D U I l COST. $ i i i i IIi i .iiv i 177 hod Figure 5.44 MODULE COST: GAS REFRIGERATION SYSTEM C r M O O U L COST, $ m illion* fX Vv nOV GAS FLOW, scfh 178 c c v Figure 5.45 MODULE COST: ROTARY DIRECT DRYER 10 0 3aS'S CaCLrre-u drying NonstiCKing reeo mate'iai Feeders nconer. cycierne and Dag Niter .nciudea MOISTURE |wt% of reeai V l0 Material Factor. Carbon steel Stainiess steei !0 5 M O O U l E COST. $ m illions 0.10 ' 0.010 100 Operation: Maintenance. % of module cost/yr Operating labor, ooerators'sfnft Electricity, kw / 1.000 lb solids-nr Steam, i .000 ibi i .000 ib sonos.nr o 6 10 i5 1.00 0 6 10 8 0.78 0 6 10 6 0 42 1 I 11I 1,000 1 1 I I 1 II1 10.000 SOUOS FEED RATE IDRY BASIS!, b hr I I I I I j_U 100.000 mod 0oi554 179 io a io Figure 5.46 MODULE COST: DEWATERING CENTRIFUGE Basis: Feed HjO/solias ratio >''05 Product H2O content = -''6 0 wt" Solids are granular, nonsticking SOLID FEED SIZE Imcnesi C I <W* \ M O D I IL L CO ST, $ m illio n s 0.10 Material Factor: Carbon steei Stainiess steel '.0 1.5 Operation. Maintenance. "o of module cost/vr Operating labor, ooeratorsrsnift Electricitv. kw/1,000 lb sonas/nr o 4 0.5 0.55 4 0.5 0.30 0.01 1,000 * i i -i i 10.000 l- I i.lil 100,000 SOLIOS FEED RATE, Ib/hr fdrv basis) .oV`O' O,0" 180 I III 1.000.000 c e 100.0 10.0 Figure 5.47 MODULE COST: SOLtDS INCINERATOR 8asis: Combustion heat of feed < 1,200 Btu/ib. No process neat recovery or excnange. Water scrubbing of combustion gases. Chlorinated or hazardous wastes. M UDULfc COST. $ m ilhum io o.i 100 Ooeration: o Maintenance. % of module cost/yr Ooerating labor, ooerators/shift Fuel. million Stu /1.000 lb sands Electricity, kw/1,000 ib soiidsvhr Process water, gal/1.000 lb soiids/hr 55 2-4 2-4 0.018 0.01 25 15 20 15 5 2-4 0 006 12 1,000 L l l l li 10,000 SOLIOS FEED RATE (DRV BASIS), ib/hr _L_L 100.000 'fa 7) 'J0,0 181 100 0 10 0 Figure 5.48 MODULE COST: SOLIDS COMBUSTOR Basis Cont nuous solids combustion Hoppers, feeder, water treatment included. Steam generated = saturated ^ 1 25 osig WASTE SOLIDS inet neating value C M O D U LE COST. $ m illm iib 10 O0 Operation: G Maintenance, % of module cost/yr Operating iaOOr, operators-snift Electricity, kw/1.000 lb/Hr feed Makeup water, gal/1.000 11>/Hr reed Steam output, b/lb feed sonds 6 2 7 40 7.4 6 2 4 20 3.7 6 2 3 12 2.2 0. 1,000 J___ 1__L 10.000 t 1 -l i i l 100,000 SOLIDS FEED RATE (ACTUAL BASISI. ib/hr i l 1 l li 1.000.000 c oO s> * 182 1 .000 0 100 0 10.0 Figure 5.49 DISPOSAL COST: LAND FARMING Basu: Land cost not included tone acre reauired'60 short tons cer yearl Aoproximate cost distribution: Laoor-reiated 60% Caouai-reiated 30% Fuei-reiaied 10% r x t <tx , . t <iyI t l1XXXl< ^YV * Xtt DISPO SAL C O S !, 1o 100 I I lI 1.000 l I I I____________I______ I____ I___ I___L I I ' I 10.000 100.000 SOLIDS FEED RATE, lb/hr HCD 000016558 183 D IS P O S A t C O S T , S /ilK H t ...... -1---- 1 I j---- M I I 100.0 - 10 0 Figure 5.50 DISPOSAL COST- GYPSUM STACKING ii Basis Lana cost riot included-20 `t high stacking lone acre reQuired/37,000 short tons gyosum waste) Aporox'rnate cost distribution Labor-related 70% Caoitai-te'ated 25% ruei-reiatea 5% Transportation to Site not induced - L u______ 10 - " 'xv<^vv. -- rX i < x t . t* . \T . ' > -Xt <r r 1 i - i . ` 1 *|`1 ' ^ , ' * J l t t l . c </ < * 0.10 _____________i_ 100 I 1 l 1 1 1 i 1_____________1 1,000 1_____ 1------L 1 1 1 J--l------------------- 1----------- 1- ' 1 0.000 1 1 1 11 100.000 SOLIOS FEED RATE, ib-hr >0^ov Vv 184 1.000.0 V 100 0 Figure 5.51 DISPOSAL COST: SANITARY LANDFILL Basis: LanO cost not included (7.000 short tons-dcre to death of 7 0 fti Cover material available on site Approximate cost distribution: LaOor-retated 65% Caoital-related 25% Fuel-related 10% Working time * 8 hr/day Equipment investment: BuMdozer-snovel <3'i cu vdl = $75,000 Tractor; trailer \60 cu va, 40 ton si = S84 000 i t iiI 1.000 * I I L1 10.000 WET SOLIDS FEED RATE, ib/hr i t iii 100.000 10 20 30 40 60 80 100 150 200 300 400 cu ft/hr 185 MCD 000016560 1 .000.0 100 0 Figure 5.52 DISPOSAL COST: HAZARDOUS-WASTE LAMOFlLL Basis. Gsposai company --mctudes (ana Permanent hazardous wastes Transportation to disposal site not included. Uooer values 'O' nicn rainfall areas of nortneastern j S ana lower values tor and areas of soutnwestem u S. Note. S'ncter regulations and mf'anon are expectsa to aouoie costs Dv 1 985. nt Vi < 'u< xdi in> ri i i i i '..(tU.lui i i i tT IJ I. < 1 t Xr( xI. \K<`\UVlii <X.t XXt'.r u1 <u iX tAtXt I'mI t Xut KX l t<l.unii \ i t < V ' 1 V v.v. 10 0 D IS P O S A L COST. $ /s liu ii u,n 1.0 100 J_____ L l J1l 1,000 l l lll 10.000 SOLIDS FEED RATE, b;hr .o s'C- o,0.0,0 186 i i Iii 100,000 T R U C K IN G C O ST. S /s h u .i ion R A IL W A Y COST. jM io it io n Figure 5.53 TRANSPORTATION COST 6.0 Bulldozer or shovel cost = Si.00--SI.50^'ton 100 200 300 400 DISTANCE, miles lone way! Source: Author estimates based on articles m Chemical Week. Nov. 1, 1978 and Oct. 11.1972. 187 MOD 000016562 B A R G IN G COST, $/>horl io n 6 WASTE TREATMENT COSTS FOR SELECTED CHEMICAL INDUSTRIES The waste treatment (and disposal) investment and operating costs for a specific chemical plant depend on several factors: The composition and quantity of waste streams. The area within which the wastes are generated and disposed of The availability of existing public or licensed disposal facilities. The extent of local or national regulations pertaining to the disposal of waste materials. The nature of the chemical process. The kind and purity of the raw materials. The purpose of this section is to demonstrate the application of the SRI-developed modular costs (see Section 5) to the estimation of capital and operating costs for the treatment of chemical plant wastes To this end, the following chemical plants or complexes will be evaluated: A 1,000 tpd methanol plant. A one billion lb/yr ethylene plant. A multiplant complex for adiponitrile (280 tpd), ethylene propylene (1,200 tpd), hexamethylenediamine (270 tpd), and methanol (1,000 tpd). A 150 tpd phosphoric wet process phosphoric acid plant. So far as possible, these estimates are compared with values derived independently elsewhere. OVf o.0? 6c? 189 Methanol Plant Wastes Treatment Methods The volume and composition of the waste streams from a 1,000 tpd methanol plant (PEP Report No. 43A) are shown on the left hand side of Figure 6.1 and the suggested methods of treatment are indicated by the schematic blocks to the right. Gaseous wastes--consisting of ^S-rich methane purge gases from the active carbon .adsorber, and the light-ends from the methanol purification--are combined and fed to a combustion furnace to generate export steam. Combustion gases are scrubbed to remove sulfur dioxide as calcium sulfite/sulfate solids and are then discharged to the atmo sphere. Liquid wastes, consisting of the bottoms from the methanol dis tillation column, are combined with miscellaneous process washing, leaks, and site runoff for biological oxidation. The resulting sludge is used for landfill, together with the calcium solids from the stack gas scrubber. Spent active carbon, and zinc oxide from the natural gas feed desulfurization are also sent to landfill disposal. The BOD5 content of the 3,000 gph of liquid discharge from the biological oxidation is 50 ppm or 30 lb/day. This compares with the EPA standard for new methanol plants (B-13935) of 0.12 lb/ton of methanol production, or 120 lb/day. Treatment Costs Capital investment and operating costs for the four equipment modules shown in Figure 6.1 are listed in Table 6.1. Module costs were read from the appropriate liquid, gas or solid treatment modules of Section 5. An additional 30% was included in the modular costs to allow for indirect expenses (e.g., contractors fees and overhead) as well as for general facilities (stores, maintenance shops, change rooms, etc.). Thus, the total waste treatment fixed capital is esti mated at $8.2 million, with the stack gas scrubber accounting for 50% OV5 ooo 4 190 Figure 6.1 TREATMENT OF METHANOL PLANT WASTES Methanoi process ntermediate pressure from narura1 gas c Methanol plant capacity: (Ref. PEP Report 'So 43Ai 1.000 too GASES _T ATMOS R ERE (545,000 scfh) GASEOUS WASTES 1. HjS-rich gas from active carcon regeneration mois/hr STEAM (35,000 lb,hr) LIMESTONE (600 ib. hn C02 CH4 c2h6 HfS 2. L ght-enas fror methanoi purification 1 119 6 1 23 mo I si hr COMBUSTION r\ (45 x 1 06 Btu.nr) 900 Btu'scf STACK GAS SCRUBBER CALCIUM SULFITE SULFATE SOLIDS 124 tpal DIS?S = SICN STACK Dimetnyi etner Methanoi LIQUID WASTES 3. Bottoms from methanol purification Water Metnanoi Hiqner axono's Extraneous water washings, eaks. runoff, sanitary 12.300 ib/hr (1.500 gpn SOLID WASTES 5. Spent active carbon 6.600 lb (220 ft3) every 1 6 months 6. Spent ?mc oxide sulfur aasornent 18,000 :b '300 ft3 every 4 months MCD 0<J016565 Reference. PEP Report No. 43A 191 Table 6.I TREATMENT COSTS FOR METHANOL PLANT WASTES Methanol Plant Capacity: 1,000 tpd; 0.9 Annual Stream MethanoL Plant Investment: $50 million PEP Cost Index: 29 0 Time Base: January 1979 Factor Capital Investment (Sl.CCO) Module costs Indirect costs, general facilities, 4 contingencies, 30S Total fixed capical Operating costs ($I,000/yr) Labor (men/snift) 3 S 14.20/man-hr Maintenance* !I module cost) Materials -imescone ' $20/con Lime ; $30/ten Aooonia J $l2C/con Phosonoric acid .? S150/ton Copperas ) 335/con Subtotal, materials CtlUties Electricitv ? 2.6c/'it-+i Process -ater 3 6Cc/l,CC0 gal Steam 3 S5.00/I,COO lb Subtotal, utilities Overhead, 53T of labor Depreciation, 10/vr of fixed capital Solids disposal, 1 Sb.SO/ton^ TOTAL OPERATING COST Coobuscion Furnace 37 5 113 188 <li) 60 (3) U -- -- -- -- -- -- 10 11 -1.386 -1,362 30 49 -- -1,212 Stack Gas Scrubber 3,100 930 *,030 (2) 210 O) 93 -7 -- -- -- -- -,7 11 -- -- 11 120 403 50 964 `labor and materials. t5 mile rouna trip 3 $2.CO/ton plus S4.50/ton landfill operation. Dls pe rsal Stack 17 5 -- C l) Negi. -- -- -- -- -- -- -- -- -- -- __ 2 -- 2 3iologicai Oxid. and Slucae Seen. 7c taLs 2,300 S40 3,6-0 6,292 1,338 3,180 (1) 120 (4) 112 -- 17 z 15 7 33 168 -- -- 168 60 364 32 9 39 C.3<t) *20 216 -: 37 Oi 15 7 130 189 14 -1.336 -1,133 210 818 82 693 c o^e 0 \A^V o L92 e c of this and biological oxidation for 44%. The combustion furnace and the dispersal stack account for the remaining 6%. The above investment in waste treatment represents about 15% of the methanol plant fixed capital requirement. Labor, material, and utility requirements for each equipment mod ule are read from the table accompanying each module cost curve and entered in Table 6.1 at their current value or list price. Next, over head costs, equal to 50% of operating labor, is added on the assumption that the waste treatment facilities are an integral part of a larger chemical unit or complex. Depreciation, is included at a rate of 10%/yr of fixed capital. Finally, a charge of $6.50/ton is made for disposal of solids on the basis of the assumed hauling distance and disposal method. Thus, total treatment cost, after a credit of Si.36 million/yr for the steam generated by the combustion furnace, is $693,000/yr. 70c/gal. This is equal to about 1.0% on a methanol sales price of Discussion of Costs The BOD5 content of the 3,000 gph liquid feed to the biological oxidation is too high for a direct reading on the cost module curve. Thus, a recycle stream of 59,000 gph is assumed in order to reduce the BOD5 content in the feed to 1,250 ppm. Then the modular cost for biological oxidation and sludge separation of $2.8 million is read from the curve at a flow rate of 62,000 gph and a BOD content of 1,250 ppm. A considerable reduction in these waste treatment costs is possi ble with planning. For example, if desulfurized natural gas is available as the raw material, the first three treatment modules-- combustion furnace, stack gas scrubber, and dispersal stack--would not be required. They could be replaced by a small flare to incinerate the light-ends from the methanol purification. Also, if the plant location is within a reasonable distance of a publicly owned treatment works (POTW) it nay be more economic to treat the small volume of aqueous MOD 000016567 193 organics in the public facility. A typical POTW fee of $250/million gal/yr, 5c/lb BOD, and lOc/lb suspended solids plus a proportionate share of capital depreciation could result in an alternative annual cost in the range of $600,000 to $700,000. An independent estimate (B-13934) of the capital investment to treat 4,200 gal/hr of aqueous methanol waste (BOD5 = 1,2C0 ppm) by the best practicable technology (BPT) adjusted to a January 1979 basis, is $712,000. Operating charges--exclusive of depreciation, overhead, and sludge disposal--are $116,000/yr. Comparative costs for* the same stream read from the biological oxidation (air-activated sludge) curve (Figure 5.20) are $858,000 for capital investment (+17%) and $162,000 annual operating charge (+28%). & .0 194 Ethylene Plant Wastes Treatment Methods The composition and quantity of gaseous and liquid ethylene plant waste streams, together with their proposed treatment sequence, is illustrated by Figure 6.2. The stream quantities and compositions are constructed from published information on ethylene plant wastes (PEP Report No. 29B and references 358765 and 358811). The treatment methods are selected from the available technology described in Section 4 of the current study. Gaseous wastes, consisting of hydrocarbons containing purge and vent gases, are flared. Also in the event of an emergency shutdown, feed gases can be diverted to the flare stack, until their flow can be stopped. Green oil liquid waste from the acetylene converter, together with oil skimmed from the process vaporizer blow-down is burned to generate steam. The combustion gases are discharged through the flare stack. Process vaporizer blow-down following the flow equalization settling-skimming tank is treated by anion exchanger to remove S, Cl, and CN ions. The effluent from the ion exchanger is combined with the condensate from the glycol stripper. This combined stream is then added to neutralized spent caustic wastes and the mixture is subjected to biological oxidation to reduce the organic contaminants. Finally, in accordance with the best available technology (BAT), the aqueous effluent from the biological oxidation is treated with active carbon to eliminate residual phenol, cyanide, and BOD. Runoff water capacity equivalent to 50% of the 2 year maximum one-hour rainfall (U.S. Gulf Coast) is included but not treated. Treatment Costs Capital and operating costs for the eight equipment modules des cribed above are obtained from the modular cost curves and their associated operating tables of Section 5. These are listed in Table 6.2 for each module. Thus, the total module cost is $1.06 million. 195 MOD 000016569 <JM/qi ooii \ shom nvsodsta oi S1N3ATOS SnoaUVZVH 96T E604** `II889C >98Se *N uoissssdv pue 862 'N uodea d3d rsaauajajay 3 3 J \ w 3 jA/QigOL * t .AioeaeD iueid Auig (SlSAlOH Ad 3NVdOtid/3NVH13! S31SVM NV3d 3N31AH13 dO 1N3W1V3U1 Z'9 ajn6ij Table 6.2 TREATMENT COSTS FOR ETHYLENE PLANT WASTES Ethylene Plant Capacity: 1.0 x 1C^ Ib/yr at 0.9 Scream Factor Ethylene Plant Investment: S190 million Pep Cost Index: 290 Time Ease: January L979 c Steam Settler- Filter Anion Flare Scacx Generator 2kinar Press Ixc.'tanzer Capital Investment ($1,000) Module costs Indlrecc casts, general facilities, k contingencies, 30t 34 46 120 30 30 ! 0 14 36 9 9 v Total fixed capital 4. 60 1 56 39 39 Operating cost (Sl.OOO/yr) Labor (oen/shift) 3 $ 14.20/oan-hr Maintenance* (I of module cost) __ (2) 1 (0.5) 60 (4) 2 (0.1) (2) 12 2 (0.2) 24 (3) 1 (0.3) 36 (3) l Materials NaOH (SOT) 3 10c/lb Ammonia (anhydrous) 3 S120/ton Phosphoric acid (LOOS) 3 SL30/ton Lime (CaO) 3 S30/con Copperas ^ $35/ton Sulfuric acid (100Z) 3 S60/ton Active carbon 3 60c/lb Subtotal, materials -- -- ---- 16 -- -- ------ -- -- ------ -- -- -- ---- -- -- ------ -- -- -- -- -- -- -- ------ -- -- -- -- 16 Utilities Electricity 3 2.6c/Wwh Steam 3 55.00/1,000 lb Subtotal, utilities Overhead, 50* of Labor Depreciation, LOS/yr of fixed capital Waste disposal Solids 3 $6.50/ton1 Liquid 3 $25/1,0C0 Lb* TOTAL OPERATING COST --L -146 2 -145 __ 30 46 ---- ---- 7 -47 -- 1-- ---- -- -- 1 - 6 12 IS 16 4 4 ------ -- -- 20 36 42 95 MOD OOOOI6571 197 Table 6.2 (Concluded) TREATMENT COSTS FOR ETHYLENE PLANT WASTES Ethylene Plant Capacicv: L.O x 10^ '.b/yr at 0.9 Stream Ethylene Plant Investment: 5190 million ?E? Cost Index: 290 Time Ease: January 1979 Factor Capital investment (Si,000) Module costs Indirect costs, general facilities, & contingencies, 30% Total fixed capital Operating cost (Sl.COO/yr) Labor (men/shift) 0 S1 -.2H nan hr Maintenance* (X of coaule cost) Materials .`,'auh (out) ? ICc/Ib Ammonia (annvdrousl ? $L20':on Phosphoric acid (110%) J SliC/ton Lime (CaO) 0 S3C/ton Copperas J 535/ton Sulfuric acid (100%) : 56i/ton Active carson 0 60c/lb Subtotal , materials Utilities Electncltv 0 2.6c,'kwh Steam 0 55-00/ 1 ,000 lb Subtotal, utilities Overhead, 50% of labor Depreciation, 10% of fixed Waste disposal Solids ? 56.50/tor. Liquid 0 $25/1.000 lb*5 capital TOTAL 0PERATTSC COST Biel. Oxidn. 5 Sludae Seon. Neutralization Active CarPor. Adsorption Totals 330 157 687 100 30 130 16S 50 215 1,055 315 1,370 ::> HO ;) :i -- i 1 2 t -- -- 5 a -- s 60 69 3 -- 286 (0.5) (*) 60 - -- -- -- -- -- 71 -- 71 1 -- 1 30 13 -- -- 179 (C. 5) 60 (*) 6 -- -- -- -- -- -- !9 19 1 -- 1 30 21 -- -- 137 372 (3.65) 33 16 1 1 2 1 71 ;9 111 i2 -K4 132 186 137 3 20 735 Labor and materials. 5 sile round trip at 52.50/ton plus S*50/ton landfill operation. ^Charge tor disposal to hazardous-waste management facility. --^ 198 c r c e When indirect costs, general facilities, and contingencies are added, the total fixed capital reaches $1.37 million. 0.7% of the investment for an ethylene plant. This represents about Operating costs for the eight equipment modules, including a $146,000 credit for steam generation, totals $735,000/yr. This is an almost insignificant charge of 0.07c/lb of ethylene/propylene product. Discussion of Costs A study sponsored by the U.S. National Commission on Water Quality CB--13934) gives three major sources of ethylene plant wastes, i (1) Water quench tower draw-off (2) Aqueous bleed from the acid gas scrubbing system (3) Condensate from compressor interstage coolers. The combined quantity of these streams is said to be 44,800 gph ,Tii'u a BOD of 1,000 ppm and a COD of 2,360 ppm. The estimated capital investment in equalization, neutralization, biological oxidation, and active carbon facilities to treat fhe auove streams according to the best available demonstrated technology (BADT) was $2.24 million in 1973 or about $4.48 million as of January 1979. < Scaling this down by 85Z to correspond to the major flow stream quanti ties in the preceding modular estimate, gives a comparable capital iny^Ament of 4.48 x 1/(7)^*^ $1.40 million (i.e., a 2% difference). Direct annual operating cost, excluding depreciation, for the Frger flows was reported as $310,000 in 1973^--equivalent to approxi mately $620,000 in 1979. This compares with/a scaled-up modular cost of $694,000/yr (+12%). MOD 000016578 t f i ** * Multiplane Wastes Treatment Methods A treatnent sequence.for the combined wastes from acrylonitrile, H* ethylene/ prepylene, hexamethylenediamine, and methanol plants has been proposed by the US. National Commission on Water Quality (B-13934). This scheme is illustrated^by the block flow diagram of Figure 6.3 along with stream quantities and compositions. The adiponitrile wastes containing appreciable amounts of organics and cyanides are divided between incin6ration and deep-well disposals. Hexamethylenediamine wastes are steam stripped t* remove ammonia, ozonated to reduce cyanide concentration, then treeted to separate an oil phase. The remaining waste stream is combined in an equalization and surge tank with the wastes ftr ethylene and methanol plants. This combined stream, amounting 71,700 gph, is next neutralized with sulfuric acid, treated by activated sludge biological oxidation to reduce BOD, filtered in.a dual media filter, and then passed through activated carbon to remove the Use traces of cyanides* The effluent can be dis charged to an adjacent river or ocean* 2i Treatment Costs Capital investment for the above system was estimated in 1973 at $4.5 million for bes&;available demonstrated technology (BADT) and <*T _ $7.05 for best available technology (ftkT). Converted to January 1979 costs, these figures becoA $9.0 and &4*1 million! respectively. Operating costs, excluding\epreciatioik, in 1973 we\e $0.82 million for BADi and $1.55 million for nT--equivalent in 1979 cellars, to approxi mately $1*6 and $3.1 millio^yr respectively* We have reestimated theMppital an^ operating cLts for the same multiplant waste treatment seEgnce on the basis of waste treatment modufcr cost and qtkntities fl Section'5 of this stfcy. The total modular cost is $9.^million e^Lthe total fixed capiL.1 investment is $i_.4 alllion ^Table 6*3). operating costs are^3.2 million annually--$2.0 million if depre^ion is excluded. o Vr c r c c AOIPONI TRUE PLANT WASTE 130,800 <h>M bO"<n' . Doi.-p WL'II toil HEXAMETHYl ENE 10 o F rhju l` 6 3 TREATMENT OF MULTIPLANT WASTLS HOI) roo TSS O.l ON NHi Tol.il ixiljsMiim jnd oiimi|. ii Ci 1 V/iilnmc!, ||iti o 100 b /u 2b fen 0 ti 8b SIIU AM FI OWS fll./h.) o o 100 too b7H 678 ?b 64 64 0 b || *t ..18.6..H l Hij ".. 1 ' 1 .bii 109 b 78 2 1b [ 17 186 4.068 184 446 y 39 0 Ob 2f> 020 21 27 0 Ob 8 o 02 66. 7 4 7 180 71.700 21 620 29 07 (1 06 180 71.700 94 4 76 29 03 180 7 1,700 -vi Moiii.iiioi i'y> Cr Table 8.3 7RIATTEKT COSTS FOR COMB I S"D "lULTIPLANT WASTES Plant Capacities (Billion Lb/yr at 0.9 stream factor): Ethylene a propylene 90C Aclponitnle 110 Hexaoethyienedlaome ICO Kechanol ?50 Plant Investment: 5',8 5 aillion PE? Cost Index : 1' Tioe Base: January 1979 Capital investment (SI,COO> Module costa Cooling uater utility Indirect costs. ;uZ Tocal fixed capital Operating cost* (Sl.CCO/yr) labor faenvshift) ? S 1-. 2 0/aan-hr Maintenance li of moduie cost) Materialsr Suilunc acic <130!) ? 56C/ton Phosphoric ucia (ICO!) ? 3150,con Liae (CaC ) ? ; 3C/1on Copperas l* ?3$'tan Active carbon 3 60c/lb Utilities Elect ric 1 tv ? 2.6c/kvti Fuel S2-30/Mli Uon Btu Overhead. $0t of labor Depreciation, 131/yr of F.C./yr Solid waste disposal'* Land spreading oi blo-toilds J 2. 50/ton Landfill of carbon b.50/ton TOTAL OPERATING COST Incineration Oeeo-Well Infection ".000 -- i. :c: j. ICO 1.450 -- 435 1.385 (i) i:c (-> [ bO -- -- -- -- -- ?b )6"5 60 520 -- -- 1.300 ; 1) ,, 15 -- -- -- - -- 3C -- - 190 -- -- 235 4caoTi la ICO 20 35 155 :o.5) oo ;*) * 30 15 111 C'son* Lion Oil Separation 150 5* ---- -5 -- 195 5 (C.2) 15) 24 3 ;o.;; ii S) Negl -- < 12 b 20 __ 68 18 Leu* i. i za t ion SO -- [ 6'J :oo s .) ^ b -- '0 91 \_ / e# .0 x> 2D2 c e Tibi* 6*3 (Conclude,!) TREATMENT COSTS FOR .COMBINED MLLIIPLANT WASTES Plant Capacities (alllion Ib/yr at 0.9 stream ethylene a oropylene - 900 Adlponicrlle 210 Hexaneehvlenedtaome 200 Methanol 750 Plant Investment: S385 ollllon PEP Coat Index: 190 Tlae 3aae` January 1979 factor): Capita* lnvestoenc <Sl,CO0) Module coses Doour.g ftater utility Indirect costs. JOS Total fixed capital loeraurg costs > I ,OOC/yr ) labor <=en/snfc) 3 $ 1 4.20/nan-nr ".dincenance ,1 of module coat) Materials' juU-iric act; liCCT) 1 S6C/ton ?"-:ss-oric jc;a ilC'S) 0 S15C-`ejr. Itoe iCdi/i ;3 0/to n 1 joperas 1 3 5. ten Active carbon - 6 Cc ,- 1 b .tllltles Eleecricitv ' I.Sc.'kvh fuei C S 2 . 3.1/ml 1 i ion btu Overhead, ICE of labor Depreciation, .IT.'yr of F.C./.r Solid Waste Disposal Land spreading at blo-sallds J C. Landfill of carbon ) 6.50/ton TOTAL OPERATTSC COST Seucra1iza cion 70 ;2 90 (0.S) 60 (v) 3 ii ; con 43 30 9 137 Activated iiudge 2.000 600 2.600 : i) i:o ( 4 ) 80 8 93 60 260 10 637 Dual Media Filtration Activated Carbon 230 "0 330 1,000 ICO 1,300 (0.5) (5) oO '* (1) 120 (4 ) -O -- - .1 --- 30 60 30 130 __ --- 3 39 44t Totals 9,5u5 20 ait 12,-30 (4.3i (3.3) :-`6 127 12 3 21 5 08 262 285 288 1,244 14 -- 3,210 An all sklmser attached to the cop of the equalization tank. Aooonia tree :.-.e aaaoma stripping is used In the activated sludge section. No cradle Is allowed for excess ammonia. * Inciterable wastes assumed to nave combustible content equal to 3,000 Bcu/lb of waace. "'iicm steaiB from incineration is used for ammonia stripping. No credit taken for steam generation above this amount. `Waste disposal is assumed to be adjacent to plant; therefore hauling change* are Insignificant. Doocarison reierence: 3-1 393.., Generalized Plant No. 18. mod WOOl 65 < ( 203 Discussion of Costs The difference between the above BADT and BAT costs is the addi tion of the activated carbon adsorber to the final waste treatment sequence so as to eliminate residual toxic impurities. The nodular cost estimating procedures in this report do not distinguish among BADT, 3AT, and BPT. Thus, it night be expected that the nodular cost estimated here would occupy an intermediate position, as shown below: Modular costs Comparative costs BPT BADT BAT Estimated Capital Investment (S millions) $ 12.4 Annual Opera ting Cost -- Excl. Deprec. (S millions) $ 2. 0 8.6 9.1 14. 1 1.58 1.63 3. 1 Thus, the BADT investment is 26% below the modular investment while the BAT figure is 14% above. The same comparative percentages for operat ing costs are -23% and +55% respectively. The 512 million investment in waste treatment facilities represents about 3% of the capital investment required for the four production units. The waste treatment operating costs of $3.2 million/yr is equiv alent to a charge of 016c/lb on the combined product outputs of two billion Ib/yr. :-V OO'<v0O.V 204 Phosohoric Acid Plant Wastes Treatment Methods The wet process phosphoric acid industry, unlike the organic chemi cal industries above, has very sizable volumes of wastes for treatment and disposal. Also, it is difficult to make a sharp separation between processing operations and waste treatment functions. Figure 6.4 illustrates a four stage system for handling the liquid and solid wastes after their separation from the process* streams of a 150 tpd dihydrate wet process phosphoric acid plant. Aqueous wastes consist of the fluoride- and silica-rich solution from the phosphate dissolver off-gases scrubber. In addition, an allowance is .made for 15,000 gp'n of runoff water consisting of the average rate of rainfall over the gypsum stack and the settling lagoon areas. An arbitrary allowance of 1,000 gph is also included for plant washings, spills, and leaks. Solid wastes consist of the gypsum filter cake from the phos phoric acid filtration plus sludge which settles out of the acid product following concentration before shipment. The quantities and compositions of liquid and solid wastes correspond to those in PEP Report No. 8B on wet process phosphoric acid, except for the settled sludge, which is derived from a paper by Kealy (432007). The aqueous fluoride scrub solution is neutralized with lime, and the neutral solution is combined with aqueous runoff and washings for disposal to river or sewer by way of a settling lagoon. The gypsum solids are entrained in a circulating aqueous slurry and carried 1/4 mile to the gypsum stacking area. Circulating liquor volume is kept constant by bleeding the excess to the settling lagoon. Settled solids are periodically removed from the lagoon and, together with the settled sludge from phosphoric acid, is stockpiled pending future use or recovery of contained fertilizer values. 205 llCb Figure 6.4 TREATMENT OF PROCESS PHOSPHORIC ACID PLANT WASTES (DiHYDRATE WET PROCESS) Phosphoric acid plant capacity 1 50 tpd LIQUID WASTES 1 Aaueous fluonae scruo solution (9.000 gphl h2S'Fb (est ) HF S1O2 co2 H20 <H2S04 EQUIVALENT = 2700 'b/hrl LIME <CaO) (1,540 Ib/hrl \__p lb/hr 110 900 470 165 75.005 76,650 NEUTRALIZATION Reference: PEP Report No. SB, B-13936. LEGEND Module numpers m 206 Treatment Costs Capital and operating costs for the above waste treatment scheme are tabulated in Table 6.4. These were read from the appropriate liquid and solid treatment module curves and tables of Section 5. The 4 foot deep settling lagoon is sized for a 40 hour holding time to correspond to the minimum thickener settling rate in Figure 4.5 of 0.1 ft/hr. Other costs are read directly from the appropriate graphs and tables. Thus, the total nodule costs are $510,000. When indirect costs and service facilities are included, the fixed investment for waste treatment reaches $664,CC0. This is divided 50/. to neutralization, 35% to pumping, and 15% to the settling lagoon. It represents about 5% of the investment, exclusive of land, for the dihydrate wet process phosphoric acid plant. Land requirement, excluding that for process plant and utilities, is about 100 acres. Operating costs are estimated at $430,000/yr, with neutralization taking the lion's share (75%) of this. At a capacity phosphoric acid output of 50,000 tons/yr P2O5, worth $300/ton, this represents a charge of $8.6C/ton (3%) against the acid product. Discussion of Costs The capital investment for treatment of wastes from a 50,000 ton/yr P2O5 wet process phosphoric acid plant was independently esti mated at $292,000 in 1975 (B-13936)--equivalent to about $368,000 in 1979. Treatment consisted of (a) sulfuric acid plant leakage containment, (b) gypsum pond seepage control, and (c) lime treatment and clarification of gypsum pond overflow. Since no pumping costs were included, this cost probably compares more closely with the modular total fixed capital for neutralization, gypsum stacking, and settling lagoon--$430,000 (-15%). MCI) 000016581 207 Comparative operating costs were estimated at $343,000/yr in 1975 (B-13936), or about 3400,000 in 1979. This compares well with the modu lar estimates in Table 6.4, excluding pumping--$394,000/yr (+1.5%). Conclusion The modular values developed in this report appear capable of providing an easy first rapid approximation of chemical plant waste treatment costs. 00 208 Table 6.4 TREATMENT COSTS FOR PHOSPHORIC ACID PLANT WASTES (DIHYDRATE VET PROCESS) Phosphoric Acid Plant Capacity: ISO cpd Pj^S at Q>9 Annual Stress factor Phosphoric Acid Plant Ir.veetaent: $10 nillioa PEP Cost Indexi 190 Time Base: January 1979 Neutralization Gypsum Stack-ins Pumping Settllns Laaoon Total Capital lnvestneac ($1,000) Module cose Indirect costs & service facilities 30* Total fixed capital Operating costs (Sl,000/yr) Labor (men/shift) 9 Sl4.20/oan-hr Maintenance (% of aodule cost) Materials, line 3 $30/ton Electricity 5 2.6*/lcvh Overhead 3 505 of labor Depreciation, 1QZ of F.C./'yr Sludge to stockpile 3 2.50/ton' Cypsua stacking i? 185/con^ TOTAL OPERATING COST 260 79 3 38 (0.5) 60 (4) 10 183 30 34 -- -- 321 -- 180 -- 54 0 234 -- __ -- U) 2 ---- -- 10 ---- -- ---- 45 -- -5 36 70 22 92 __ (20) 14* -- -- -- 9 5 -- 28 510 154 664 (0.5) 60 26 183 14 30 67 5 45 S4 30 `polyethylene lagoon liner replaced every 4 years. *Tvo aile haul (one way) at $1.50/to n plus leveling at il.00/too. s ^caching cost for 32 ton/hr solids. Including labor, caterial, overhead, and depreciation. 3 209 Appendix A COST 3ASIS The nodule coses developed in this report are based on the equip ment purchase price data used by the Process Economics Program (PEP) to estimate chemical plant investments- These apply to a U-S- Gulf Coast location near Houston, Texas, and to a PEP Cost Index of 290 correspond- * ing to a time base of January 1, 1979. Specialized operations such as electrodialysis, reverse osmosis, and biological oxidation are derived from published costs of installa tion within the United States. These, as well as quoted cost information, are also adjusted to a PEP Cost Index of 290. MCD 000016584 V. ' U 211 3*s / Appendix B CALCULATIONS FOR THE EQUALIZATION OF A WASTE STREAM FLOW VARIABLE (Reference B- 1395) Samples of the wastewater stream are taken at regular intervals over a complete cycle of the variable to be controlled--in this case BOD content. The concentrations in each sample are plotted against the probability for a given or lover value to occur (see Figure B.l). Now, the standard deviation in the feed "Cf" is equal to one-half of the difference of the values occurring at probability percentages of 15.9% and 84. 1%. That is: Cf = BQD 84. 1% -BOD 15.9% . 980 380 = 300. 22 The mean BOD value at 50% probability is 680 mg/liter. If the maximum BOD leaving the equalization pond or vessel is to be 895 mg/liter at a probability of 95%--corresponding to a curamulative normal distribution "Y" 1.65 (Table B.l), the standard effluent deviation: The required residence time in the equalization vessel is: . x (crf) 2 fe)2 n12 (300)2 --2 Xx (130)2 * 32 hr or 1.33 days 213 where: &t = cycle time of the variable from a mean value cf and Ce = feed and effluent standard deviation, mg/liter t = equalisation residence time, hr. For a waste flow of one million gallons per day, the equalization capacity 10^ x 1.33 gallons or 177,000 ft^. This is equivalent to a container 137 ft in diameter with a liquid depth of 12 ft. 'c 't o Figure 8.1 PROBABILITY PLOT OF BOD VALUE Source: B-1395. 214 Table B.l CUMULATIVE NORMAL PROBABILITY DISTRIBUTION Y .00 .05 . 10 .15 .20 .25 .30 . 35 .40 .45 .50 . 55 .60 .65 .70 .75 .80 .85 .90 .95 1.00 1.05 1. 10 1.15 1.20 1.25 P(X)* .5000 .5199 .5398 .5596 .5793 .5987 .6179 .6368 .6554 .6736 .6915 . 7088 . 7257 .7422 .7580 .7734 .7881 .8023 .8159 .8289 .8413 .8531 .8643 .8749 .8849 .8944 Y 1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90 1.95 2.00 2.05 2. 10 2. 15 2.20 2.25 2.30 2.35 2.40 2.45 2.50 P(X)* .9032 .9115 .9192 .9265 .9332 .9394 .9452 .9505 .9554 .9599 .9641 . 9678 .9713 .9744 .9772 .9798 .9821 .9842 .9861 .9878 .9893 .9906 .9918 .9929 .9938 *P(X) = confidence level. Y 2.55 2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05 3. 10 3.15 3.20 3.25 3.35 3.45 3.55 3.75 4.00 PCX)* .9946 0 99 53 .9960 .9965 .9970 .9974 .9978 .9981 .9984 .9987 .9989 .9990 .9992 .9993 .9994 .9996 .9997 .9998 .9999 1.0000 MCI) 00 `0016587 215 Appendix C DESIGN STEPS FOR A COMPLETELY MIXED ACTIVATED SLUDGE SYSTEM (References B--1393 and B-1395) 1. BOD (or COD) removal rate is determined in the laboratory for various feed rates and mixed liquor volatile suspended solids (MLVSS) concentrations. The slope of the graph of SQ (SQ-Se) x vt versus Se (Figure C.l) gives the removal rate coefficient "K". K (Se-y) = Sn(Sn"Sp) `V where: S0 Se *v c K y influent BOD, COD, or total oxygen demand (TOD), mg/liter effluent soluble BOD, COD, or TOD, mg/liter average MLVSS concentration--mg/liter (for conventional biological oxidation, Xv --1,500 to 3,500) aeration time, day"l organic removal rate coefficient, day"* concentration of nonbiodegradable organics, mg/liter. 2. The variation of the removal rate coefficient with temperature is given by the equation: K2 K[ 0 (T2"Tl) where: Kj coefficient at temp. T^, C K2 coefficient at temp T2 C 9 * temperature coefficient (si.03 to 1.09) OOO' v,V. B 217 Figure C.1 DETERMINATION OF BOD REMOVAL RATE COEFFICIENT -V Source: 8-1395. 218 3. Plotting the oxygen usage per day for a known quantity of biode gradable matter (Rr/xXvt) versus the amount of BOD removal per day (Sr/xXvt), as shown in Figure C.2, gives the a' and b* constants for the equation: Rr = a' Sr + b' x Xv whe re: Rr = total oxygen usage, lb/02/day a' & b' =.oxygen utilization coefficients Sr = BOD (COD or TOC) removed, lb/day Xv - average MLVSS concentration, mg/liter x = biodegradable fraction of MLVSS t * aeration time, days. 4. Constants in the equation for sludge production are determined from a graph of sludge formation (AXv/xXv) against BOD removal per day (Sr/xXvt) as shown in Figure C.3. r AXV a Sr - bxXv where: Xv = excess biological sludge production, lb/day a & b = sludge production coefficients. 5. The biodegradable fraction (x) of MLVSS is calculated from the following equation: aSr 4- bXy- \/(aSr+bXv)2 -(AbXy) 0.77aSr c x a ------------------------------------------------------------------- * 2bXv WCT) UOQiq bpi'i 219 V. Figure C.2 DETERMINATION OF OXYGEN UTILIZATION COEFFiCIEN c lb b io ilt'ijr jil.ib li; V S S -tljy o .V' 220 r Figure C.3 c DETERMINATION OF SLUDGE PRODUCTION COEFFICIENT V.. ( 0.2 Source: B-1395. 0.4 Sr xX t 0.6 0.7 lb organics removed \ lb biodegradable VSS-day / 0.8 1.0 221 MOD 000016592 6. Nutrient requirements are estimated from the following two equations: 0.123 x N= 0.77 Xv + 0.07 (0.77-x) 0.77 Xv, lb/day 0.026 x P= 0.77 Xv + 0.01 (0.77-x) 0.77 Xv, lb/day 7. Aerator horsepower is approximated from the relation; , lb BOD removed per day hp - -------------------- 45------------------------- 8. Finally, the clarifier si2e is determined as indicated for sedimentation separation under "Primary Treatment" (page 67). >c 222 r Appendix D C FIXED BED ACTIVE CARBON ADSORBER CAPACITY The design of fixed bed adsorbers requires experimental data for the adsorbability of the component or components to be removed (B-1395). Figure D.l shows the breakthrough curves for 'three 7.5 foot columns in series. When the third column reaches 10% effluent concen* tration, the first column is removed from the series and the fourth column is added. From these curves service tine can be plotted as a function of bed depth, as shown in Figure D.2. Thus, for three 7.5 foot beds in series and for 10% breakthrough, the service time is 14.5 days. Four beds are required, with one bed being replaced every 5 days. r C 223 Figure 0.1 BREAKTHROUGH CURVES FOR THREE COLUMNS IN SERIES I It A C I K IN !)( A lJ S U H U A H I l I 1 4 ) U lM A lN lN '.) C Ml StH VIC fc T lW t.il.iy i Source S ' S9S Figure D 2 SERVICE TIME ASA FUNCTION OF BED DEPTH Source B 139S 224 r c c CITED REFERENCES :S9 Hirsch, J. H., et al., "Estimating Plane Investment Coses," Cham. Eng. Progr., 56, 12 (1960), 37-43 LC039 Millar, C. A., "New Cose Factors Give Quick Accurate Estimates," Chem. Eng., September 1 3 , 1965, 226-36 10242 Hughart, R. , "Debrining Potash and Salt," Chem. Er.g. Progr., 61 (May 1965), 73-32 7 643 L Guthrie, K. M., "Capital Cost Estimating," Chem. Eng., March 24, i969, 114-142 101272 "Projected Wastewater Treatment Costs in the Organic Chemicals Industry (Updated)," study for Environmental Protection Agency, Wacer Pollution Control Research Series, Program 12020 GND, (July 1971) 3-9136 Eckenfelder, W, W. , Jr., et al., "Economics ot Wastewacer Treatment," Chem. Ena., 76, 13 Aug. 25, 1969, 109-113 35773- Eckenfelder, W. W., Jr., "Oxygen Activated Sludge Considerations ror Industrial Appli cations," paper presented at the American Institute of Chemical Engineers. 73th Annual Meeting, Sew fork, November 13-17, 1977 357735 Gitchei, W, C., et al., "Characteristits of Active Carbon Regenerated by Wet Oxidation," paper presented at the American Institute at Chemicai Engineers, 70th Annual Meeting, New fork, November 13-17, 1977 257736 Vaseleski, R. C-, "The UNOX Process--Effective Wastewater Treatment Practice," paper presented at the .American Institute of Chemical Engineers, 70th Annual Meeting, New York, November 13-17, 1977 357737 D'Anconi, J. M., et al., "Effects of Dissolved Oxygen in the Oxygenation Activated Sludge Process," paper presented at the American Institute of Chemical Engineers, 70th Annual Meeting, New York, November 13-17, 1977 3577S8 Stetzer, R. H.t "FMC Pure Oxygen--An Effective Solution to Wastewater Treatment and Process Applications," paper presented at the American Institute of Chemical Engineers, 70th Annual Meecing, New York, November 13-17, 1977 327739 Scadmit, J. G., et al. , "State of the Art: Powdered Activated Carbon Addition to Acti vated Sludge." paper presented at the American Institute of Chemical Engineers, 70th Annual Meeting, New York, November 13-17, 1977 358765 Thompson, R. G., et al., "The Cost of Clean Water in Ammonia, Chlor-Alkali and Ethylene Production," Natl. Tech. Inf. Service No. PB-264 508/3WP. 1976 35881L Linde A. G. and Linde Nissan, "Prohlems of Proteccion of the Environment (When Operating) Ethylene Planes," Chem. Econ. and Eng. Rev., 6, 2 (February 1974), 42-45, 59 383522 Witt, P. A., Jr., "Solid Waste Disposal," Chem. Eng./Deskbook Issue, May 8, 1972, 109-113 -19299 "To Sea or Not to Sea with TiOgWastes," Chem. Week, December 8, 1976, 65-67 -32007 Kealy, J. P., "Phosphacic Granulating Liquid," Chem. Eng. Progr., 64, 5 (May 1968), 71-74 -43053 Oak Ridge Nacional Laboratory, "Desalting Seawater and Brackish Water: Cost Update 1979, for the Dept, of Energy, Contract No. W-7405-eng-26, Subcontract No. 0RNL-11Y-13545V(A), ORNL/TM-6912, (August 1979) -47001 Sleeker, H. C., et al., "Capital and Operating Costs of Pollution Control Equipment Modules. Volume I. User Guide," Natl. Tech. Inf. Service No. PB-227 3Q4/2GA 447002 Hoffnagle, C. F., at aL., "Industrial Expansion and the 1977 Clean Air Act Amendments, 1 Pollution Eng. Yearbook 4 Product Reference Guide, 10, 12 (December 1978), 36-43 -47003 4470C6 De LaRue, R. E., et ai., "the Capital Costs of Industrial Pollution Control," Pollution Eng. Yearbook 4 Product Reference Guide, 10, 12 (Decemoer 1975), 47-32 "OSHA Concentration Limits fcr Gases and Vapors," Pollution Eng. Yearbook 4 Product Reference Guide, .0, 12 (December 1973), 74-75 447007 Fields. T., Jr., et al., "Landfill Disposal of Hazardous Wastes," Natl. Tech. Inf. Service So. PB-26L 079/3GA, i,June 19,3) 447008 4470 15 447017 447019 447028 447029 447033 Ackerman, 0., et al., "Descroving Chemical Wastes in Commercial Scale Incinerators," Natl. Tech. Inf. Service No. P3-273 316/4GA, (1978) Crumpler, E. P., et al., "Siting of Hazardous Waste Landfills," paper presented at the American Institute of Chemical Engineers, 71st Annual Meeting, Miami 3eacn. November 16, 1978 Nnowlton, H. E., et al., "An Overview cf Pecroleum Industry Use of Landfarming, paper presented at the .American Institute o: Chemical Engineers, 7Lsc Annual Meeting, Miami Beach, November 16, 1973 Stevens. J. I., et al., "Thermal Destruction of Chemical Wastes," paper presented at the .American Institute of Chemical Engineers, list Annual Meeting, Miami Seacn. November 14, L97S Lanouecte, K. K., "Heavy Metals Removal." Chea. Eng./Deskbcok Issue, 3-, 22 October 17, 197*. 73-80 "Ocean Pollution and Marine Waste Disposal," Chera Eng., 3, 3, February 8, 1971, oQ-6> Ambler, C. M., "How to Select the Optimum Centrifuge," Chera. Eng., 76, 23, October 20. 1969, 96-100. 102-103 447034 Porter, H. F., ec al., "Filter selection," Chem. Eng./Deskbook Issue, 73, 4, February 15, 1971, 39-43 447035 "Wastewater Filtration.' Design Considerations," L'.S. Government Printing Office: 1977-757-056/6410 Region No. 3-11, EPA-625/4-74-007a, Revised Edition, (July 1977) 447036 -47038 Ballew, H. W., et al. (Nuclepore Corporation), "Basics of Filtration and Separation," (1978) Fagan, E. D., ec al., "Kinetics of the Acid Hydrolysis of Cellulose Found in Paper Refuse," Environmental Science 4 Technology, 5, 6 (June 1971), 545-547 447039 447040 Fox, C. R., "Plant Uses Prove Phenol Recovery with Resins," Hydrocarbon Processing, 57, 11 (November 1978), 269-273 ECO-Research, Ltd. (Canada), Technical Bulletin `>L, June 1979, "Deep Shaft Under Con struction at Virden, Manitoba;" Bulletin "2 September 1978, "EPA Approves Deep Shaft Demonstration Plant at Ithaca, New York;" Newsletter, "Duel Shafts Featured at Portage LaPrairie, Manitoba." 447041 447043 446044 "Environmental Pollution Control Alternatives: Municipal Wastewater," L'.S. EPA Tech nology Trans ter, EPA-625/3-76-012 Ford, D. L., ec al., "Removal of Oil and Crease from Industrial Wastewater,' Chem. Eng./ Deskbook Issue, 34, 22, October 17, 1977, 49-36 "Activated Carbon Clears Effluent," Oil and Gas Journal. 74, 22, May 31, 1976, 52-56 447045 Schnepf, R. W., et al., "Foam Fractionation: Metals," Chem. Eng. Progr., 55, 3 (May 1959), 42-46 226 447046 Lemlich, R., "Questions and Answers on Foam fractionation," Chem. Eng., 75, 27 December 16, 1963, 95-102 447047 Brunner, C. A., et al., "Foam Fractionation Standard Separator and Refluxing Columns," Industrial and Eng. Chem, Fundamentals, 2, 4 (November 1963), 297-300 447048 Lemlich, R., "Adsorptive Bubble Separation Methods," Industrial and Eng. Chem,, 60, 10 (October L96S), 16-29 -- 7049 3runner, C. A., "Foam Fractionation," Industrial and Eng. Chem., 57, 5 (May 1965), 40-48 447050 Rosen, H. M. , "State of the Art of Ozonation for Commercial Applications in the U.S.," paper presented at the American Institute of Chemical Engineers, 86ch National Meeting, Houston, April 1-5, 1979 447052 447053 Petherbridge, R. J. S-. "Deodorising Foul Cas Streams with Ozone," Process Eng., (February 1975), 93-99 Garrison, R. L., et al,, "Ozone-Based System Treats Plating Effluents," Metal Progress, (November 1975), 61-62 44*054 PrengLe, H. W., Jr., et al., "Ccone/UV Process Effective Wastewater Treatment," Hydro carbon Processing, 54, 10 (October 1975), 32-87 447055 Raraaiho. R. S., "PrinciDles of Activated Sludge Treatment; Part 1: Fundamental Concepts A New Language is Needed for cr.is New Tool for HPI Plant Operations," Hycrocaroon Processing, 57, 13 (October 1978), 1 12 -- i 18 447056 3iecker, H. C.. ec al., "How to Estimate and Escalate Costs of Wastewater Equipment," Chem. Eng./Deskbook Issue, October 2 1 , 1974, 115-121 4-7057 Sleeker, H. C., et al., "Capital and Operating Costs of Pollution Control Equipment Modules," Vo 1. 11, Data Manual, prepared for Environmental Protection Agency, EPA-R573-023b, Natl. Tech. Inf. Service No. PB-224536 , (July 1973) 447053 Fair, J. R., "Sorption Processes for Cas Separation," Chem. Eng., 76, 15, July 14, 1969 447059 Sargent, G. D., "Cas/SoLid Separations," Chem. Eng./Deskbook Issue, 78, 4, February 15, 1971, 11-22 447060 Fair, J. R., "Designing Direct-Contact Coolers/Condensers," Chem. Eng., 79, 13, June 12, 1972, 91-100 4-7061 "Removal of SO from Industrial Waste Gases," Chem. Eng./Deskbook Issue, 84, 22, October 17, 1977, 127-135 --.7062 Laseke, B. A., ec al., "Status of Flue Gas Desulfurization," Chem. Eng. Progr., 75, 2 (February 1979), 37-50 447063 Lovett, W. D., ec al., "Air Pollution Control by Activated Carbon," Chem. Eng. Progr., 70, 5 (May 1974), 43-47 44706- Mattia, M. M., "Process for Solvent Pollution Jor.trsl," Chem. Eng. Progr., 66, 12 (December 1970), 74-79 447065 Miller, P. D., Jr., et al., "How to Design a New Smokeless Flare," Petroleum Refiner, 37, 5 (May 1958) , 148-152 447067 Tan, S. K., "Flare System Design Simplified," Hydrocarbon Processing, 46, 1 (January L967), 172-176 447068 Thomas, M. D., et al., "Dispersion of Gases from Tail Stacks," Industrial and Eng, Chem. 4L (December 1949), 2409-L7 4-7069 Lewis, W. K., et al., "Adsorption Equilibria Pure Gas Isotherms," Industrial and Eng, Chem., 42, 60 (1950), 1326-1332 447070 Fabian, H. W., ec al., "How Bayer Incinerates Wastes," Hydrocarbon Processing, 58, 4 (1979), 183-192 227 MCB 000016596 MCi> OOOOIBbys < 447071 -47073 -u 70 7 4 Writhe, A., "Marine Incineration-A Clean Answer to Chlorinaced Wastes," Chem. Age, July 22, 1977, 11-15 Berry, R. I., "Sludge Drying--One Way to Waste-Reduction," Chem. Eng., 86, 12 June 4, 1977, 30-34 Wilhelmi, A. R., et al., "Vet Air Oxidation--An Alternative to IncineraCion," Chem. Eng. Progr. {August 1979), -6-52 1-7075 4-7076 Durban. E., "Steam Generation," Chem. Eng. Costs Quarterly, 4, 2 (April 1954), 41-63 Zimmerman, 0. T., "Waste Incinerators," Cost Engineering, L8, 4 (OctoDer 1973), ; -- 1 i -.7 077 44 / 8 "Potential for Capacity Creadon m the Hazardous Waste Management Service Industry," Natl. Tech. Inf. Service No. ?3 -- 257 187, (August 1976) Farb, D. , et al., "Information about Hazardous Waste Management Eac ii it ies," EPA/530/ SV-145, (July 1975) -4707 -47080 Grove, G. V., "Vsa Land Farming tor Oilv Waste Disposal," Hydrocarbon Processing, 57, 5 iMav 19 78) , 1 38- 140 .eng, J., et al., "Industry 3raoes for New Water Cleanup Rules," Chem. and Eng. News, -;v .4, 1979, 3 1- 35 --7081 Scores TSCA Rules." Chem. Week. April 1 1, 1979, 13 -47082 "Dec in Ban Buoys Sludge Processes," Chem. Week, March 3, 1973 , 33 4-7083 "Wast= Disposal bv Burning at Sea," Chem. Weex, April 11, 1979, 44 --7084 Murrav, 7., "Chemical Waste Disposal a Costly Problem," Chem. and Eng. News, March 12, 1579, L2-L6 447085 Glaubinger, R. S., "A Guide to the Resource Conservation and Recovery Act," Chem. Eng., 86, 3, Janu. rv 29, 1979, 79-85 4-7037 -.4 7 038 Smith, M. E.. 'Solid-Waste Disposal: Deepwell Injection," Chem. Eng., 36, S, April 9, L 979, 107-1 12 Huddleston, R. L- , "Solid-Waste Disposal: Land farming," Chem. Eng., 86. 5, February 26, 1979. 119-124 --7G9C "Solid Waste Disposal," Chem. Eng., 73, 14, June 21, 1971, 155-158 --7091 Wissa, A. E. Z., "Err. ronmental Engineering of Gypsum Stacking," paper presented at the .American Institute or -.emicai Engineers, 85th National Meeting, Philadelphia, June 4-8, i978 447092 Straus, M. A., "Hazardous Waste Management Facilities In the I'nited S tates-1977 ," EPA/530/SW-146.3, (January L977) 447093 Baur, K. , "Olefin-Plant Waste Liquor Eyed Closely," Oil and Gas Journal, 75, 43, October L7, L977, S5-57 -47094 447095 447096 -47097 Siegel, R. D., et al.. "The Imi ret of the Clean Air Act Amendments On New and Expanded Plants," Chem. Eng. Progr., 75, i v 19 7 9) , 13-22 "Occupational Safety and Health Act of 1970," Public Law 91-596, 91st Congress, S. 2193, December 29, 1970, Chem. Eng. /Desitcook Issue, 80, 14, June 18, 1973 , 157-158 Moran, R. D.. "Prepare for an OSHA Inspection." Hydrocarbon Processing, 58, 10 (October 1979) , L85-186 "At PVC Plants, Compliance Curbs Capaci:'-'," Chem. Week, 124, 13, March 28, 19/9, 36 228 j f**' ( s f ^ V f 447098 de Never3, N., "Some Alternative PSD Policies," Journal of the Air Pollution Control Assoc., 29, 11 (November 1979), 1139-1144 447099 Perry, R. R., "Backing Away from National Standards," Journal of Water Pollution Control Federation," (April 1979), 659 447 ICO "A Study of the Economic Impact of the Federal Water Pollution Control Act Amendments of 1972," prepared by a major segment of the Chemical Industry. The 10 study sponsors were: Allied Chemical Corp., Dow Chemical Co., Du Pont Co., Exxon Chemical Co., ( Hercules, Inc., Hooker Chemicals S Plastics Corp., Monsanto Co., PPG Industries, Inc., Stauffer Chemical Co., and I'nicn Carbide Corp." 447101 Arguello, M. D., et ai., "Trihalomethanes in Water: A Report on the Occurrence, Seasonal Variation in Concentrations, and Precursors of Trihalomethanes," Journal of the American Water Works Assoc., 71, 9 (September 1979), 504-508 449593 Mahoney, R., "Hydrolysis of Polyurethane Foam Waste." Environmental Science & Tech nology, 3, 2 (February 1974), 135-139 BOOKS 3-1 Perry, R. H,, et al.f eds., "Chemical Engineers' Handbook," 5th ed., McGraw-Hill, New York, 1973 3-2 Bauman. H. C-, "Fundamentals of Cost Engineering m the Chemical Industry," Reir.noid, New York. 1964 3-1393 Clark, B. J., et al-, eds-, "Wastewater Engineering. Collection, Treatment, Disposal. Metcalf and Eddy, Inc.," McGraw-Hill. New York, 1972 3-L 394 De Renzo, D. J., ed., "'.'nit Operations for Treatment of Hazardous Industrial Wastes," Noyes Data Corp., Park Ridge, NJ, 1978 ( 8-1395 Adams, C. E., et al., eds., "Process Design Techniques for Industrial Waste Water Treatment." Associated Water and Air Resources Engineers Inc., Enviro Press, Nashville, Tenn., 1974 B-1396 Verschueren, K., "Handbook of Environmental Data on Organic Chemicals," Van Noscrand Reinhold, New York. 1977 B-i397 Vernick, A. S., et al., "Pretreatraent of Industrial Wastes," EPA Seminar Handout, 1978 San Francisco Seminar, Dec. 7-8, 1978 B-1393 Muir, G. D., "Hazards in the Chemical Laboratory," 2nd ed.. The Chemical Societ;', London, England, Alden Press, Oxford, March, 1977 3-1399 Shreve, R. N., "Chemical Process Industries," 3rd ed., McGraw-Hill, New York, 1967 B-13910 Kirk-Othmer, "Encyclopedia of Chemical Technology," End ed,, Vol. 21, Interscience Publishers, New York, 1970 ^ B--l3911 Culp, R. L., "Advanced Wastewater Treatment," Van Nostrand ReinhoLd Co., New York, 1971 B-13912 Oullette, R. B., et al., "Electrotechnology-Wastewater Treatment and Separation Methods Vol. 1, Ann Arbor Science Publishers, Ann Arbor, Mich., 1978 B-13913 Ross, R. D., "Industrial Waste Disposal," Reinhold Book Corp., New York, 1968 B-13914 Azad, H. S., "Industrial Wastewater Management Handbook," McGraw-Hill, New York, 1976 / V 3-13915 Purchas, D. B., "Industrial Filtration of Liquids," C.R.C. Press, Cleveland, Ohio. 1967 8-L3916 Groggins, P. H., "Unit Processes in Organic Synthesis," 4th ed. , McGraw-Hill, New York, 1952 mcd 000016600 229 B-13917 Bamforch, A. W., "Industrial Crystallization," the MacMillan Co., New York, 1966 3-139LS "Process Design Manual for Carbon Adsorption," prepared for the Environmental Protec tion Agency by Swindler Dressier Co., Pittsburgh, Pa.. Oct., 1971 B-13919 Icarus Corp., "Capital and Operating Costs of Pollution Control Equipment Modules," Vol. 2, Data Manual, prepared cor Environmental Protection Agency. Distributed by Natl. Tech. Inf. Service, U.S. Dept, of Commerce, July, 1973 3-13930 Oliver, E. D.. "Treatment of Petrochemical Wascewacers," Process Economic Report No. SO, SRI-Incernatior.al, Menlo Park, Ca., Sept,, 1972 9-13921 Kurosawa, K., "Deep Aeration tank for Activated Sludge Treatment," First Pacific Chemical Engineering Congress. Parc III, Kyoto International Conference, The Society of Chemical Engineers of Japan, Oct. 10-14, 19*2 5-1 3922 3usch, A. W. , "Aerobic BioLogical Treatment of Waste Water," Principles and Practice, Oligodynamics Press, Houston, Texas, 1971 3-- L 39 2 3 M iddlebrooks. ., "lagoon Information Source 3cick," Ann Arbor Science Publishers Inc.. Ann Arbor, Mich., 1978 3-13934 Weston. R. "Process Design Manual for Upgrading Existing Wastewater Treatment Plants," preoared for Environmental Protection Agency Technology Transfer, Program No. 17090 GNQ, Jet. , 1971 3-1393; Sacks, R. L., "land Treatment and Disposal of Municipal and Industrial Wastewater," Ann Arbor Science Publisher, Ann Arbor, Mich.. 1976 B-l 3936 Cuchrie, K- M., "Process Plant Estimating and Control," Craftsman Book Co., Solano Beach, CA. , 19 74 3-13927 Page, J. S., "Estimators Manual of Equipment and Installation Costs," Gulf Publishing Co., Houston, Texas, 1963 9-1 3928 Popper, H., "Modern Cost Engineering Techniques," McGraw-Hill, New York, 1970 B-13929 Cheremisinotf, P., "Carbon Adsorption Handbook," Ann Arbor Science, Ann Arbor Mich. B-139 30 Riensenfeld. F., "Gas Purification," 2nd ed., Gulf Publishing Co., Houston, Texas, 19*4 3-13931 Evans, F. L., "Equipment Design Handbook for Refineries and Chemical Plants," Vol. 2, Gulf Publishing Co., Houscon, Texas, 1974 3-13932 Rjss, R. 0., "Air Pollution and Industry," Van Noserand Reinhold Co., New York, 1972 3-13933 Staff of Research and Educational Assoc., "Modern PoLlucion Concrol Technology," Vol. 1 and 2, Research and Educational Assoc., Sew York, 1978 B-13934 Catalytic Inc., "Capabilities and Costs of Technology for the Organic Chemical Industry to Achieve the Effluent Limitations of P.L. 92-500," prepared for the National Commission on Water Quality. PB-244-544, distributed by lT.S. Dept, of Commerce, Natl. Tech. Inf. Service B-13935 Sittig, M., "Pollution Control in the Organic Chemical Industry," Noyes Data Corp., Park Ridge, NJ, 1974 B-13936 Sittig, M., "Fertilizer Industry--Processes, Pollution Control and Energy Conservation," Noyes Data Corp-, Park Ridge, NJ, 1979 B-13937 Christensen. H. E., ed., "Registry of Toxic Effects of Chemical Substances, 1975 Edition, available from Supt. of Documents, L'.S. Govt. Printing Office, Washington, D.C., June, 1975 B-13938 "Environmental Quality," the 9th Annual Report of the Council on Environmental Quality, Dec., 1978, available from U.S. Govt. Printing Office, Washington, D.C. r ( c* B-13939 Vernick, A. S-, et al. "Pretreatmenc of Industrial Wastes," Joint Municipal and Indus trial Seminar 197S, U.S. Environmental Protection Agency, Environmental Research Inf. Center, Cincinnati, Ohio 3-13940 "The Quality of the Environment in Japan, 1978," cemDiled by the Environmental Agency, published March 1, 1979 by Printing Sureau, Ministry of Finance, 2-2-4, Toranomon, Minato-ku, Tokyo 107, Japan 3-13941 Arbuckle, J. C., et al. , "Environmental Law Handbook.," 6th ed., Government Institute, Washington, D.C. 3-:3942 "Environmental Statutes Government institute, Washington, D.C. 3-13943 Miiler, L. M., et al., "Toxic Substances Control." Governmental Institute, Washington D.C , 3-13944 "Engineering Data 3ook, " 9th ed.. Gas Processors Suppliers Assoc., Tulsa, OK ( tfoO'l: On, '0 !'6V C 231