Document 7R8ZD9MmdrDLLVdRVOVyXG76g

0 I----- 1 Report No. 137 WASTE TREATMENT COSTS by GEORGE E. HADDELAND September 1980 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025 MOD 000012487 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. e ii INTRODUCTION 1 SUMMARY............................................................................................................................................ 3 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 5 5 5 6 8 8 9 9 POLLUTION ABATEMENT LEGISLATION AND EXPENDITURES............................... 13 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 Lav................................................... Expenditures in the United States ..... .............................................. Capital Expenditures....................................................................................................... Operating Costs............................................................................. Expenditures in Japan ....................................................................................................... 13 16 22 24 25 26 33 33 41 13 28 32 32 3 3 WASTEWATER TREATMENT TECHNOLOGY ............................................................................. 43 Pretreatment....................................................................................... Primary Treatment--Chemical ....................................................................................... 46 Objective................................................................................................................................ 46 Ion Exchange................................................................................................... Electrodialysis ................................................................................................................. 56 Reverse Osmosis..................... *........................................ ........................................ 58 Neutralization...................................................................................................................... 58 Oxidation and Reduction ......................................................... ...... 60 Chemical Addition . ....................................................................................................... 63 Hydrolysis............................................................................................... Primary Treatment--Physical ....................................................................................... 67 Sedimentation.................................................... .... -............................................... 67 Hydrocycloning. ................................ ..... ............................................... 67 54 65 iii MCD 000012488 CONTENTS LA 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 ................................................................................................................. Nitrif ication-Denitrif icat ion.................................................................................. Sand Filters .......................................... ............... Tertiary Treatment ............................................................................................................. Foam Fractionation........................................................................................ Chlorination.............................................................................. ..................................... Ozonation........................................................ ........................................................................ Toxic Liquids Disposal.................................................................................................. 70 72 76 77 77 80 82 85 85 87 89 90 90 91 92 95 80 4B GASEOUS WASTE TREATMENT AND DISPOSAL TECHNOLOGY.................................... 97 Precreatment................................................................................... .................................... 97 Dry Systems........................................................................................................................................ 100 Gas-Solid Separation .......................... . . ................................ ..... 100 Adsorption on Activated Carbon.............................................................. ..... . 101 Liquid Systems........................................................................................................ Water and Solvent Scrubbing.............................................................................. Acid or Ammonia Neutralization.........................................................................105 Limestone Desulfurization............................................................................................... 105 Waste Gas Disposal............................................................. 106 Steam Generation and Incineration.............................................. 106 Emergency Flaring....................................................................................................................107 Dispersion by a Stack.............................. 108 105 105 4C SOLID WASTE TREATMENT AND DISPOSAL TECHNOLOGY................................................ Ill Waste Solids Treatment ................................................................................................... Ill Dewatering................................................................................................................................... HI Drying.............................................................................................................................................. H5 Incineration .......................................... ..... ............................................... 116 Combustion................................................................................................................................... H9 Waste Solids Disposal.................................................................................. 121 Land Farming..............................................................................................................................121 Stacking........................................................................................................................................ 122 Sanitary Landfill....................................................................................................................122 Hazardous-Waste Landfill ......................................................................................... 124 Other Disposal Methods .............................................................................................. 125 000012489 MCD iv 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 of 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 3ed Active Carbon Adsorber Capacity ............................... CITED REFERENCES................................................................................................................................. 127 130 133 131 189 190 190 190 193 195 195 195 199 200 200 200 204 205 205 207 207208 211 213 217 223 225 v 000012490 MOD 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....................................................................................... 42 Wastewater Treatment Alternatives..................................................... Multiple-Chamber Alternate-Membrane Electrodialysis Cell ... 57 Settling Curves at Various Suspended Solids Concentrations , . 68 Batch 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............................................................................................................................ 75 Activated Sludge System.................................................................................................. 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 ran 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...................................................................................... Stacking Procedure for Waste Gypsum..........................................................................123 Guthrie Method for Modular Cost Estimates.......................................................... 129 Module Cost: Tanks ........................................................................................................ 136 Module Cost: Thickener, Clarifier ... ..................................................... 137 Module Cost: Settling Lagoon ............................................... . ..................... 138 Module Cost: Oil Separators.......................................... 139 Module Cost: Filters...............................................................................................................140 Module Cost: Centrifuges.....................................................................................................141 Module Cost: Hydraulic Cyclones . * ................................................................ 142 vii MCD 000012491 44 1 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 Cost: 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: IonExchange 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 000012492 ViCV> ILLUSTRATIONS 5.37 Module Cose: Ammonia Neutralizer.................................................................... 171 5.38 Module Cost: Acid Gas Neutralizer............................................................... 172 5.39 Module Cost: Scrubbers* Hydrocarbonor Water........................................ 173 5.40 Module Cost: Active Carbon Adsorberfor Gaseous Stream. . . 174 5.41 Module Cost: Gas Compressor ............................................................................... 175 5.42 Module Cost: Dust Separator ................................................................... 176 s- 5.43 Module Cost: Gas Coolers................................................................................... 177 5.44 Module Cost: Gas Refrigeration System ..................................................... 173 5.45 Module Cost: Rotary Direct Dryer. . . ...................................................... 179 5.46 Module Cost: Dewatering Centrifuge.............................................................. 180 5.47 Module Cost: Solids Incinerator ..................................................................... 181 5.48 Module Cost: Solids Combustor .......................................................................... 182 5.49 Disposal Cost: Land Farming ............................................................................. 183 5.50 Disposal Cost: Gypsum Stacking. , . ..................................................... 184 5.51 Disposal Cost: Sanitary Landfill......................................... 185 5.52 Disposal Cost: Hazardous-Waste Landfill .......................... .... 186 5.53 Transportation Cost.................................................................................................. 187 6.1 Treatment of Methanol Plant Wastes.............................................................. 191 6.2 Treatment of Ethylene Plant Wastes (Ethane/Propane Pyrolysis) .................................................................................. 196 6.3 Treatment of Multiplant Wastes ........................................................................ 201 6.4 Treatment of Process Phosphoric Acid Plant Wastes CDihydrate Wet Process).............. ..................... 206 B.l Probability Plot of BOD Value............................................................................... 214 ( C.l Determination of BOD Removal Rate Coefficient...................................... 218 C.2 Determination of Oxygen Utilization Coefficient.................................. 220 C.3 Determination of Sludge Production Coefficient ....... 221 D.l Breakthrough Curves for Three Columns in Series................................. 224 ( D.2 Service Time as a Function of Bed Depth. ................................................. 224 ix mod 000012493 TABLES 2.1 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 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 A Comparison of Modular Waste Treatment Estimates With Independently Estimated Values................................................................... 11 U.S. National Ambient Air Quality Standards...............................................15 Typical Effluent Limitations Promulgated by U.S. EPA According to the Federal Water Pollution Control Act Amendments of 1972 .................................... ....................................................................... 17 U.S. EPA List of Priority Toxic Pollutants as of December 1978............................................................................................................................ 19 U.S. EPA-Proposed Water (Micrograms/Liter) Quality Criteria for Selected Toxic Pollutants ......................................................... 21 Major Pollution Control Legislation by the U.S.Congress ... 27 U.S. Pollution Abatement Expenditures for Air, Water, and Solids, by Chemical Industry Segment .................................................... 36 U.S. Pollution Abatement Operating Costs for Air, Water, and Solids, by Chemical Industry Segment .................................................... 40 Japanese Pollution Abatement Expenditures.......................................................... 41 Typical Thickener and Clarifier Design Criteria...........................................46 Water Pollutant Treatment Methods ................................................................... 47 Toxic Inorganic and Organic Pollutants and Methods for Their Control. ........................................................................ 43 Materials Rejected by Reverse Osmosis.....................................................................59 Commercial Oxidizing and Reducing Agents and Their Possible Applications to Waste Treatment .................................................. 62 Typical Flocculants and Coagulants and Their Applications. . . 64 Some Typical Filter Applications ......................................................................... 73 Typical Centrifuge Performance Characteristics ... ....................... 74 Activated Sludge Process Characteristics .................................................... 83 Typical Compounds Susceptible to Ozonation ............................................... 93 Applications of Gas-Solid Separation Equipment .................................... 101 Vapors Adsorbed by Activated Carbon................................................................... 10 3 U.S. EPA-Sponsored Waste Incineration Demonstration Plants............................................................................................................ *......................... 11* xl MCD 000012494 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 HCD 000012495 xli 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 multiplane complex for making acrylonitrile, ethylene, propylene, hexamethylenediamine, and methanol. These estimates are compared with similar estimates derived independently elsewhere. 1 MOD 000012496 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. MOD 000012497 2 2 SL22IARY Pollucion Abatement Legislation Much of the motivation for pollucion abatement in the United s'* States stems from legislation enacted by Congress over the past decade. v The Clean Air Act Amendments of 1970 and 1977 define three area classifications: Class I - Virtually no increase in air pollucion 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 pollucion 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 raid-1980 and implemented by 1985, should prevent adverse effects on humans, fish, or wildlife. 3 000012496 MCI) EPA is developing a program requiring industrial plants to pretreat their wastes before discharging theca to a POTV. Technical and financial assistance is available through EPA for implementation of the above leg is lac ion. 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 cons annually) is Co 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 Ilaricie 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 which are more severe than the national ones. MCD 000012499 4 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 S150 million in 1972 to almost one billion in 1977. Most of this cost percains 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 abatement* 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 race 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* 5 MOD 000012500 The operating costs 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, nay 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, pretreatment 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 may 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. MOD 000012501 6 The choice of operations for creating a given aqueous waste is determined by: Quantity and composition of waste scream Existing or impending pollution abatement laws and regulations Nature of surrounding facilities and environment. In some cases, it may be core economic to eliminate a waste stream by modifying the process or raw materials from which it is generated. Gaseous wastes ciay need to be precooled or compressed to facili 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 firming. These methods can require sizable land areas* 7 MCD 000012502 Modular Waste Treatment Costs Fixed Capital Investment The several methods nomally 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, instrumentation (D) Building or enclosure Totals (module factor * f\<) 0.2 0.6 0.2 0.6 0.2 C.6 0.2 0.6 1.8 3.4 1.0 1.0 1.0 1.0 5.0 A centrifuge with "some" foundations and supports; "some" connect ing piping; "little" electrical, insulation, or instrumentation; and complete enclosure in a building would have a nodule factor (fjf) 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 module 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%. 8 mod 000012503 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. Qperacing 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 rate. These 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: 9 MCD 000012504  A 660 million lb/yr methanol plant A 1.0 billion lb/yr ethylene plant A multiplane complex of adiponitrile, ethylene/propylene, hexamethylenediainine, and nethanol with capacities of 210, 900, 200, and 750 million lb/yr respectively. A 50 million lb p205/vr 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 multiplant complex are well within i20 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. MCD 000012505 10 !(6U 2. 1 a ccsmtscN or hoduui hastt -ntZATyisr esttxatts with iomsoe>m.r estimated values* Pep Ccet Index: 290 O.Qleal plant* : I-00 tivr) Waata Traataant Capital Z at *lnt SI.000 [nviiiaanc "odule * iM uni Cparacmi .Oftt Sl.CCC/vr c/lb of Product 11ac ranoi r <1321 .... :-* "uin p aot ; Mplex aaiponitrlla (ICS) ttayiaoa/prepylant (S0) Kexaeatnvlanadlaelna (100) Matnanol ( 37 5) \ I l ) ssa ! ,: 70 12,.00 l.T 0. 1 J.2 ! 61 135 3.210 C.lb 0.2 7 ) / o. 15; ) Wat proeaa* phoapfwrlc acid (3C)f' 4)0 *.3 39* 0.40 Tndeeandant Wait a Lxad Capital 1 idvlAtion s1.000 free Moduli ?reAt sent Est taj t* Cocrac i:-.a Cok i Daviac .an Sl.OOO/yr f rae Mc : ula 7 12 l..0O -17.0 -2.2 116 -23 slO - .6 9, 100 dr 14,100 -b.5** / 1,600 } 1 3,100 -26.8 -26.8** 3(1 -14.4 kCO *1.5 * l.-.dapaMant valia* niv Man adjuatdd wtiara nacaaaary to a ?EP Coat Icdax af 290, eoftaaponding ea a lisa baai* of January, ; 9 79. *7vaaa figure* ineluda only th biological air oxidation of catitaaol aauaaua wattas. Natural gaa raw aatarial la nauoad io p delivered with a low auifur con tan t. Ctnar vaataa ara negligible or ara racurnad to auppUar for recaverv of aatala. 'watt# traataant coaca naa baan ad Juiced to a aaall plant capacity tar tha indapandant aatiaataa to tocraapond to waata s:rt< puantitlaa uiad far tba aodula aatiaataa. Indapandant waata traataant aatiaaca tneludaa ewa tyteana--ana according to the boat available daaonacratad technology ( SA3T) ara alao according :o cna bast availabla technology liAt). The average of thaaa la uaad ::r coapaman. Capital and aparatlr.g coat to puap alurry waata* to the dlapoaal araa ara net Included In dichar lac of figure*. H MCD 00012506 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 13 MCD 000012507 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 neeting these standards--now extended to December L982 (S-13938). The najor sources of pollution (each capable of emitting more than 100 tons of pollutant per year) have been identified in the United States (3-13938). Out of approximately 23,000 caajor sources, 872 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 act also sets up a National Institute for Occupational Safety and Health (NI0SH), 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). 608 14 0000^ 'able 3.1 U.S. NATIONAL AMBIENT AIR QUALITY STANDARDS Pollutant Sulfur dioxide Nitrogen dioxide Total suspended particulates Carbon monoxide Lead Hydrocarbons (other than methane)^ Ozone Tine Period 3 hr* 24 hr Annual Annual 24 hr* Annual 1 hr 5 8 hr* 3 month avg. 3 hr* 1 hr* Units ug/m3 uug/a3 ag/o-5 Ug/n3 Ug/m3 ug/n3 mg/m3 rag/n3 Ug/m3 Ug/ra3 ppm Primary* Standard __ 365 80 100 260 75 40 10 1.5 160 0.12 Secondary* Standard 1,300 -- -- ICC 150 60 40 10 1.5 160 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 (uR/ra3) Class 1 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 to be exceeded more chan once per year. ^Suggested maximum if ozone limits are to be realized. Source: 447094 15 Mod 000i25qq Water Pollution The Federal Water Pollution Control Act Amendments of 1971, 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 standards for wastewater discharges from existing industries to be achieved by July 1, 1977, by the "best practicable control technology currently available" (BPCTCA or 3PT). New plants were required to file for a National Pollution Discharge Elimination System (NPDES) permit 24 months before beginning the discharge and to meet.an effluent concentration according to the "best available demonstrated control technology" (BADC7 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 $25,000 and/or 1 year imprisonment could be imposed for the first conviction of false reporting, negligence, carelessness, or willful violation. Discharges to publicly owned treatment works did not require a permit provided they did not contain pollutants which interfere with normal operation and provided the discharger bore a proportionate share of the POTW capital and operating costs. EPA implementation of this lav separated the chemical and related industries into subcategories ranging from Aj through G^. Each cate gory was allowed a maximum one day and a maximum 30 day discharge of chemical oxygen demand (COD), biological oxygen demand measured over 5 days at a constant temperature (BOD5), total suspended solids (TSS), and pH, as shown in Table 3.2, for the three control levels BPT, 5DT, and BADT. The above law was not sufficiently specific--small quantities of chlorinated organics or heavy metal salts, which can be very damaging to the environment, were not covered by effluent specifications. 16 MCD 000012510 / /-'rV table 3.2 TTFICAL EFf.'.Tyi OSUTATICNS F*O!i.T.CAtt0 SY U.S. EPA ACCORDING TO THE FtOERAL HATER POLLCTtCN CCNTRCl. ACT A/iE.YOKEfTTS Of 1972 Subcaceitrv A ?r?fiuct ird ?rOCC99C4 JTX if.Tii.ci iv `vdratlon of jy r- ; ' m g*o.it.e; JTXeraaatlc by solvent extraction of reforcata; tyelabexane By hvdrogenatioo of beezana; and vinyl chloride b* hCI Addition to acatyien*. Ef f loan t Characteristic* COD ME; TSS pH '-B.11. .TOC of lla* laua for 1 Dev Avn$ of 20 Consecutive Oav* shell \oc Excsed ---- Product Haxlaua for i Z* v ;r kt'l.CCO c of Product 3>0T ___________ |AT Average Average of JO of 30 Consecut lve Days Shall Not Sxeeed tax lu for 3 Con* acut tv# Oav* snail Not Exceed _ >.062 0.0.5 a.c45 c.e: 0.0 j 7 0.01* :. 015 :.;c8* 0.06 7 0.03 0.C34 0-015 0.02: :. a 3 6.0 to 9.0 6.0 to 9.0 0. 0 to 9.0 8i Aetcast by deftvdroganatlon el itoproptnol; butadiene By-product of cy.vln*; ecrvlhentane bv alkylation of ben*ne; ethylene end propyltn* By hydrocarbon COD pyrolyiit: ethylene dlcnlond* by chlorination of echylen*; BOO; ethylcat oxide by catalytic oxi dation of *thyl*n*; forealddhvd* TSS by oxidation of setnanol ; aem- anol bv seaaa rafomng of natural gat; aetnyl MMI By PH addition of aaaonta to Mthant; vinyl ac*c a to !r ethylene and acetic acid: vinyl chloridt By cracking of thyln dlcMorld*. __ Q. 13 0.5a 0.20 0.088 6.3 to 9.0 --_ 0. 1L 0.048 0.10 0.044 6.0 to 9.0 *3 Adlponitrlle bv chlorination of bentaaleaa; btfijoic acid by catalytic oxidation of toluona; and aetnyl chlocida By HCI raaction with aetnane!* COD BOO; TSS PH 0.94 1.11 0.42 0.49 Between 6 and 9 0.78 0.56 0.35 0.25 Batvaan 6 and 8 Source: Federal Raglstar, Vol. 39, Ho. II, pp. 14676-1*685, April 25, 1974. (Alto 1-15934.) 0-80 0. 38 0. C<*4 0.066 C. JvO 6.0 to 9.: 16.6 11.9 0.25 C. 37 0. 14 0. 21 Batwaen 6 and i 17 MCD 000012511 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 CB-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 nondomescic 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 18 Table 3.3 U.S. EPA LIST OF PRIORITY TOXIC POLLUTANTS AS OF DECEMBER 1978* o i a t lie Halogenated Organics (VHC) 6. / 3. 10. 1 1. 12* 13. u. 15. 16. 23. 15. 26. 27 29. 30. 32. 33. 44. -5. 46. 47. *8. 49. 50. 51. 52. 53. 85. 87. 88. Carbon tetrachloride Chlorobenzene 1,2,- -Trichlorobenzene 1 , 2-Dichlorcecnane 1,1,1-Trichloroethane Hexachlo roe thane 1,1-Dichloroethane 1,1,2-Trichloroechane i, 1,2,2-Tecrachloroechane Chlo roethane Chloruroru 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene l, 1-Die hioroethylene 1,2-c-Dichloroechylene 1,2-Dichloropropane 1,3-Dichloropropylene Methylene chloride Mechvl chloride Methyl broni.de 3ronofora Dichloro'oronon ethane Trichlorofluoromethane Dichlorodlfluoromethane Chlorodib ronomethane Hexachlorobutadiene Hexachlo rocyclopentadiene Tet rachloroethylene Trichloroethylene Vinvl chloride Arccatie Hvdrocarbons 4. 38. 39. 55. 72. 73. 74. 75. 76. 77. 73. 79. 80. 81. 32. 33. 34. 86. Acer.aphthene Benzene Ethylbenzene Fluoranthene Naphthalene 1,2-Benzanthacene Benzo [a ] pyrene 3,4-Benzofluoranchene 11,12-Benzofluoranthene Chrysene Acenaph thylene .Anthracene l,12-Benzopecylene Fluorene Phenanthrene L, 2 : 5,6-Dlbenzanthracene Indeno(1,2,3-C,DJpyrene Pyrene Toluene Phthalace Esters 66. 67. 68. 69. 70. 71. Bis(2-ethylhexyi)phthalate Butyl benzyl phthalate Di-n-butyl phthalate Di-n-occyl phthalate Diethyl phthalate Dimethyl phthalate Amines 5. Benzidine 28. 3,3'-Dichlorobenzidlne 37. 1,2-Diphenylhydrazine 19 MCD 000012513 Table 3.3 (Concluded) U.S. E?A LIST OF PRIORITY TOXIC POLLUTANTS AS OF DECEMBER 1973* I h 10 r:.r.a:ed Esters 1'. 5i s(chloronethvl)ether l i 31 s t. 2 -1 h 10 r u e c r.v 1) e t he c 19. 2-Olii ircecnvL vir.yl ether (nixed) 40. i-Chlorconenyi phenyl ether 41. 4-Bronophenyl phenyl ether 3is(2-chlo roisopropyl)ether 43. Sis(2-chloroethoxy)methane Other Aromatic Compounds 9. :o. 35. 36. 56. 106. 107. 108. 1C9. L 10. 1 11. 112. 129. Hexachlo robenzene 2-Chloronaohthalene 2,4-Dinitrotoluene 2,6-Dinittotoluene Sit robenzene PC3-1242 (Aroclor5 PCB-1254 (Aroclor3 1242) 1254) PCB-1221 (Arocior-' 1221) PC3-1232 (Arocior15 1232) PC3-12-8 (Arocior5 1248) PCB-L26C (Arocior3 1260) PC3-1016 (Arocior3 1016) 2,3,7,8-Tetrachlorodtbenzo-p-dioxin. Pesti cides and Metabolites 89. 90. 91. 92. 93. 94. 95. 9b. 97. 93. 99. 100. 101 102. 103. 104. 105. 113. Aldrin Dieidrin Chlordane (technical mixture & net aboiites) 4,4'-DDT 4,4*-DDE (p.p'-DDX) 4,4'-DDD (p,p'-TDE) Alpha-Endosulfan 3eta-Endosuifan Endosulfan sulfate Endrin Er.drin aldehyde Keptachlor Hepcachlor epoxide Alpha-BHC Beta-BHC Camma-BHC (lindane) Delta-BHC Toxaphene Nit rosamines 61. S-Ni tro sod inethyl anir.e 62. N-Nit rosodiphenylaeine 63. S-Ni trosodi-n-propylam Phenols 21. 2,4,6-Trichlorophenol 22. p-Chloro-ra-cresol 24. 2-Chlorophenol 31. 2,4-Dichlorophenol 34. 2,4-Dinetnyl phenol 57. 2-Nitrophenol 58. 4-Nitrophenol 59. 2,4-Dinit rophenol 60. 4,6-Dinitro-o-cresol 64. PentachlorophenoL 65. Pheno1 Miscellaneous Compounds 3. 54. 116. 121. Acrolein Acrylonitrile Isophorone Asbestos (fibrous) Cyanide (total) Elements (total) L14. 115. 117. 118. 119. 120. 122. 123. 124. 125. 126. L27. 128. Antioony Arsenic Beryllium Cadmium Chromium Copper Lead Nickel Me rcury Selenium Silver Thallium Zinc *The categorization of impurities has been done by SRI. Source: B-13938. c e c HCD 000012514 20 :bi 3.* U.S. EFA-P90P0SED WATIH (-ICROCRAHS/UTS*) QUALITY CJUTEIIA FOIl SELECTED TOXIC POLLUTANTS ?:esi'vur Acuatle lit - -r -vrata la ;.;n Saltwacar Acuatlt Lift i -r *ver4t* lailirt Hu*an Haaltli Iffeces Acanaondant 110 2*0 7.3 17 <0.02 /!) Ac r o l* i n Anc t softy i.: 120 2.7 1,000 0.83 2.0 -- 5. 5 1.-3 CiIor-.r.icM phnoi v-'lllaropraro. 2 .. , vT: ;e-l5fap!--no. *3 ;c ISO ---- 30 150 ---- ;;rt )-Cfc.a ropn*r\oi 2, 5-Dicfileropnanol 2. (j-D icr.ioropntnol 2, A, S-Trtenioropnnol -- -- -- -- -- ---- 50 -- ---- 3-0 -- ---- 3.0 -- ---- 10* 2,3,- , o-It radio rop Hanoi -- -- ---- :s3* Coppr ,(C.B5 la(harina) - l.03) ,(0.88 ln(ha rdnata >-l .03) 0.79 18 (1 a^r i 1 "yjaiOa 1.4 33 -- -- (0.2 1) 3, J'-31ehlorobniidInt -- -- ---- 0* CldioropropanaaCana*) V 1,1- Diesla roproB*n l,J-5icnlarapropana *10 920 930 2.2 CO ---- -00 9 30 203 233 l.l-Dldloropropant 1.320 21,000 79 180 203 i, 3-Die hi ora pro pan# 23 2 50 5.5 1* 0,b3 Dim:rocoluo 2,3-Dinittotoiuana 2 ,--Olnitrotoluant Oiplanvllydraatna lidomulfan Endn n oo.lv. Santana Ulsatnari 0-Bropnr\j'Vpnnyl liLonacnana* 'ativl chiortat `lathy! Sroaia* ' r.v .ana chlortd* 3roao(ora 3roBoc11orotriAn Dicilorodif luorauatnana Trichloro:luroaaonjn* Isopnocon* Sapnthaiana Mekal S'lcroBanttna \Z 620 17 0.0*2 :.:c:o -- 27 l,*00 38 0.*9 O. 20 -- 6.: 1* 7 ,C00 1*0 *,000 3*0 -- -- -- 2, 100 -- ,u.c: ln(harnt*a)-l.02) *30 _(0.*7 16,000 320 9.000 1.900 -- -- -- *.700 -- lndardnatt )*-* 19) 1,100 -- -- -- 0.00*7 -- -- 3,700 170 1.900 130 -- -- --* 97 -- -- 33 10 -- --* -- 0.031 -- -- 8.*00 380 *, *00 *20 -- -- -* 220 -- 120 0* 0* A* (o. i oj/n i ( l. 1 3|/U -- 2 2 2 2 2 3,000 3, 2C0 *60 1*3 133 30 Mtrophanoia 2 -Vic ropnanoi *-*iicropnanoi 2,--Otnitroenanol 2, --Dim t roeraol 2, -. 6-Trlnitrophanol 2.700 2*0 79 57 1,500 6,200 530 180 130 3. *00 ---- S3 120 37 84 -- 150 3*0 -- -- 68.6 12.3 10 .'Hanoi 600 3, *00 -- (1-* /l) 1.0* Pltnaiatt attars Cisacivi pr.tnalaca Ciativi pntlaiata CiSutvl pntlalact 2i-i-atnylltxyi phehalata PCS Tolun* Taxjontn* Cue ,(C.6 -- -- -- -- P.CilS 2,300 0.C37 ln(harenaie)*0.6?) -- -- -- -- 6.2 3,200 0,*7 ,(0.6* IMhardnaaa W.*6) -- -- -- -- 0.02* 100 0.19 -- -- -- -- .20 230 0. 12 (160 a/l) (60 a/l) (3 */1> (10 ags 1) 0* (i2.* si/n 0* (5 b*U> `propoiap lavaLi not yat attaSllihad. 'Data ara liawt(ictant to tat entartoe, but EPA racoooaoda situsizLng axpetufat. *Organolapt ic affacta. iour:<; Tame llatafial -law. Waakly fcialntta Uttar, July 23, 1978, Buaioaaa Pv6iU6*f lac-, P. 0. Bos 1067, SUvtr Spring!, 2ME 21 mcd 0Ql25l5 programs in accordance with the standards issued by EPA. By 1983, this could affect as cany as 38,000 to 55,OOC 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 (B-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 race 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 Che "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 OQq e  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 I 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 dumping of sewage sludge and industrial wastes by December 31, 19?! (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 12Z 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 MCD 000012517 investigated the economics of land-based waste management facilities for hazardous waste disposal (4-7077) 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 microgram 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-ofpipe 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 cake the ocher 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 000l25l8 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, 25 000012519 MCD 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 toxic materials-- review current Washington developments in these areas. Both are published by Business Publishers Inc., P.0. Box 1067, Silver Springs, Maryland, 20910. "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 447002, 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 handled 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 000012520 Table 3.5 :iAJOR POLLUTION CONTROL LEGISLATION BY THE L'.S. CONCRESS ____________ Congressional Ace Public Law Number Congress Statute Date Air Pollution Air Duality Act of 1963 Air Quality Act of .967 Occupational Safety and Health Act of L970 Clean Air Act Amendments of L970 Clean Air Act Aaencoents of 1977 o t 00 00 90-148 91-596 91-604 95-95 77th S 1st 84th 84th 91$t 392 435 596 1676 665 Dec 17, 1963 Nov 71, 196* Dec 31, 1970 Dec 31, 19 7 C Aug * ' 1977 Water Pollution V. Federal Water Pollution Control Act Amendments of 1972 92-500 86th 816 Oct. 18, 1972 Marine Protection. Research, and Sanctuaries Act of 1972 92-532 66th 1052 Oct. 73, 1972 Clean Water Act of 1977 95-217 91st 1566 Dec. 20, 1977 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 79ch 90th 90th 997 2003 2795 Oct, 20, 1965 Occ. 11, 1976 Oct. 21, 1976 Source: Reports of the L'.S. Congress House of Representatives and Senate, issued by Supe rintendent of Docuoents, Government Printing Office, Washington, D.C., 20402* 27 MOD 000012521 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.LO ng/m3 < 0.04-0.06 ppm <0.06 ppm Hourly Value, .lax. <0.1 ppm < 20 ppm for 8 consec* hours < 0. 20 mg/n3 A 1978 amendment to the sulfur dioxide emission standards made the following revisions: The hourly volume of SC^ (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. 000012522 28 Mct> 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 burn ing liquid or gas' has a limit of 0.30 g/Nm^, whereas, for a large scale 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^ Km^/hr) Upper Limit for NO* Cone, (ppm) Boilers Cas 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 29 MOD 00001 2523 These linits apply to new operations installed later than June 1977. Somewhat higher linits are permitted in older facilities. The air pollution amendment of June 1971, also specified emission linits 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 (ng/Nm^ ) 1.0 30 80 1 to 20 1 to 20 Hydrogen chloride emission rates as high as 700 mg/Xm^ are possible for incinerators of waste chlorides. The fluorine and lead range between 1 and 20 ng/Nm^, 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 1970, 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: MCD 000012524 30 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 Colifora groups/cc - daily average 5.8 to 8.6 5.0 to 9.0 160 mg/liter 120 mg/liter 200 mg/liter 150 mg/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 Copper 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 31 MCD 000012525 As in the case of air pollution, local governments have the authority to set and enforce lower limits tor these and other pollutants in water effluents. Such areas include the Seto Inland Sea, Tokyo Bay, and Ise Bay (B -- 13940). In Japan, it is customary for chemical producers to conclude a pollution prevention agreement with Che 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 MCD 000012526 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 as in the case of a polychlorinated biphenyl (PCB), the government can hale ics i-portation 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 1983, 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 33 MCD 000012527 Figure 3.1 ANNUAL CAPITAL EXPENDITURES BY THE U.S. CHEMICAL INDUSTRY FOR POLLUTION ABATEMENT c POL LU TlO N AUATEMENT EXPENDITURES, $ in.ll.on> PtH C LN T OF f O I A l N tW C A P llA L E X P I N O I HJHLS Source: Pollution Abatement Costs and Expenditures Current Industrial Reports. MA-2Q0. 1973 thru 1977, Bureau o* Census, U.S. Deoi of Commerce, Washington. 0 C and Reference 447003. 34 MCI) 000012528 w disposal for the 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 $83C aillion/yr to about $1,300 nillion/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 expenditures, PACE is expected to remain in the range of 10 to- 12%. Presumav 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 5Z respectively between air, water, and land pollutants. For air purification, particulate removal represents the major portion (43%) of its capital investment; NC^ is next at 32%; heavy metals, radioactive materials, toxics, and others represent 19%; and sulfur oxides are last at 6%. In 1977, the esti mated amounts of pollutants removed from air by the U.S. chemical industry were as follows: 35 MCD 000012529 Tab 1 a 3.6 U.S. POLLUTION ABATCtENT IlCPS VO IT'. RES FOR AIR, WATER. M*tl SOL13S, BY CHEMICAL ISDCSTRY SECMOJT 31 Current Dollar*) I '2 - s : r> i* -enc pollution Abt=cnt CApt'-Al Exotnciturs *J* ,4. PACE is I o: Total v*w Taolcal Distribution ot Air Pollution Attateaant Sxpandltura Total . End ot ?:gcss Partic ulates SO- a. *?pnr Irjfjjn.: .e-..j.S, p4gsen;s Plastic =itrlals ra* ms , tuscar , leiljioJf ano orgame : ibtrs Drug* and pf.araacauc ical s ;; p. 3 LSI.i 14.4 . j: 9. 6 -.3 56.0 35.9 51-5 5 30-2 3. 5.9 . p# 3 SB.6 57.4 *7.9 1C. 7 3.3 32-9 3. 1 0.2 48. 7 3.3 37.6 13.0 1.8 3. 3 5 O'. 7 Soaps, iti*rgtncs, isns . :olist ?r*pirationj, #tc. ?a ints And ai 11 ;f -c jct fl Industrial organic meaicals . mtacaaciatts. .cod ohaeicals, guS* and c>e.ic organics Agricultural musicals and rare ill ca rs fiscal lanaau* comi cal. products, adhasivcs, explosives. Industry total i 3.- U?.d U9.3 4 ,, 7 982.4 8.9 40.2 8.5 0.4 2.5 NS NO 3-9 -.5 l. 1 32.4 NO 0. 1 0.8 -- 0.2 0. 1 IS.a 1C.8 i).:s 111.2 25.4 93.6 17.6 22.3 1 NO 59.. 18.4 s:.3 34.9 >5. 3 7.0 26.7 2.4 9.- N. 1 18.6 41.6 340 34.6 16.0 296.9 2.6 43. 1 12.0 US 1.2 20.1 5- 1 109.1 0-2 65.8 c c c 36 MOD 00001253 Table 3.6 ( Concluded) U.S. POLLITIOW AiATEMEVT E.Tj'S.SDITl PIS "OR AIR. WATER. AHD SOLICS, S'! CHEMICAL INBCSTtlf SECHEVT (Millions of Current Hollars) Induscrv 5e*a*nt Total Ctscributicn of Pollution ibateaent Expenditure -*:e r ac .: 4 End :( Process Total . Inorganic ;*cn-- ia s . Alkji its , c" .-r;^e , gists, pl^tncs , a;*c . Plastic aaterlala resins , rubber, cellulose and organic fibers Crugs and p ha maceu t ic a 1 s Soso*. detergent*. polishes. toiler prepa rat ions, etc. Paines and allied products Industrial organic chesicals. lotaracdiates. wood chealcals. guaa. and cyclic organics Agricultural cneaicait and fertilizers Iliac*llaneous chei" cal products, adftasivss. explosives, carbon black, etc. Industry total 3b. - 55.4 62.9 *0. 7 5.9 61.5 11.4 56. 1 1.7 50.0 302.3 69. J 93.1 62.1 25.3 56.6 593 60, A 31.2 55-2 5.7 12.3 1.5 376.0 77.6 17.5 530 5-2 ;3-6 i. 6 7.7 :.9 1.9 0.2 (5.3 0. 1 o.a 3.7 0.2 0.7 17.6 26.3 24.2 5,5 15.5 4.4 3.0 7.5 63.0 0.5 49.4 1.5 5.0 *All figures art for the calendar year 197?, escape the pollution abactnt otpendlture* (PACZ) aa e Z of total oav capital expenditures, which aro for 1976, Source: Currant Industrial Reports, "Pollution Aba ment Costa sf^ Eapendlturea", 1976 and 19??. MA"200(?6W and NA-200( 77 W, U.S. Cepe, o/ Cooaeree, tureau of the Census, L'.S. Covt. Printing Office, Washington, O.C. 37 MCD 000012531 Particulates Nitrogen oxides, hydrocarbons, and CO Heavy netals, radioactive materials, toxics, others Sulfur oxides Total Thousands of Short Tons 3,417 i,815 700 1,033 7,024 Operating Costs The growth of operating costs for pollution abatement by the I'.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 18%, 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 38 000012532 MCD C r V Figure 3.2 ANNUAL OPERATING COSTS OF THE U.S. CHEMICAL INDUSTRY FOR POLLUTION A8ATEMENT annual operating cost for pollution abatement, $ millions a n n u a l o p e r a t in g c o sts AS A % O f VALUE a o d l o Sources: See Figure 3.1. YEAR 39 MOD 000012533 Tibi* 5.7 AIR,J.3. POLLLTION aSaTE.'EkT OPSSATtNC COSTS TOR aTE*. ASO SOLIDS, 3Y CHCllCAi. 'llllons 5t Current Dollars) 7ntr.4uf.oo :r .~:scs ' "il.iors :-.lusc it t_en; Inorganic T14 - c e racIu Cose l'Jl i . ; irs .at^e `cc<3" 9v - n o: Aztr 2G..:s >oreclatlori labor ;]-.i ;. 7 'b.Z .5.* 3 7.: -6.5 q\Jl3 '-; r lai 3y?Ci.* . 5r7i;es . r c.n 44S$, ;iga<nt4. z+sc. res ins . rubber cellulose and organic t ibers Irugs and ;naraaceuc teals ?s*pa , ieter^tnts, -oiisnn, isilcc prep*f4tLona, tec* ; roauccs 155.2 -5. 7 :&. i-.a o. 3.3 :.b 18. 1 58. 7 28.2 27.0 35.2 2. 3 54, 3 8. 7 26.6 12.4 6.5 ?.: 0.7 11 . - 3. 5 0. 3 l-.v :. .1 `.I 1. 1 ) o.: 9.0 Indue trial organic cneaLcals, tntercediace*. wood cneeicals, guas and cvelic organici Agricultural otouaii and fertilisers llscalianaoui chmieal pro ducts, adhesives, explosives. carboa black, acc. Industry Total 550.0 158.8 51. 1 i,:i8. i 1.5 1.7 1.6 1.9 m.u 131.1 35.5 96.6 99. 7 3.5 3H.8 6.9 87. 1 24.a -> * t 21.7 8.9 38.9 8.6 25.8 2.2 91.1 18.7 0. 3 23.2 315.5 485. 3 217.5 219.5 238.9 13.0 723.9 ?i vT*nt 5 :. 5 o. . ;. 3 ;5.. s 2.1 41.5 !;scs :ec over*c .3. . -.3 -.0 5 `4. - 31.8 1-.0 206.4 '.All figures *r :or the calendar year 1977, except she total operating coat* a* a percent of value aadad, which Is tor 197b. Value added Includes all canufsecuring coats ocher than raw aeterlels. 'Recovered costs ere tn* value of salable *sie* such a* scrap and fertiliser or of recyclable aaterial. Source*: Current Industrial Raporce. "Pollution Abateaent Coat* and Expenditure*", 1977, MA-Z00<74)-2.. also Annual Survey of `tanufaccuraa. Central Statistics cor Industry Croup#-i975 and 197b. loth U.S. Cepe, of Coaaerce, Bureau a: the Census, L.S. Covt. Printing Office, Ueahlngtoa, O.C. c r-**- r c c 40 MCD 0000.12534 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 i971 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 pollu tion abatement in 1979, was 4.5 x 10^ yen O $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 Z 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. 41 MCD 000012535 Figure 3.3 ANNUAL CAPITAL EXPENDITURES BY THE JAPANESE CHEMICAL INDUSTRY FOR POLLUTION ABATEMENT AS A PERCENTAGE OF TOTAL NEW CAPITAL INVESTMENT c PfcHCfcN I 2^6 OOOO^ 42 c c 4A WASTEWATER TREATMENT TECHNOLOGY The various levels of wastewater treatment may be defined as foilows (447041): (1) Pretreatment: 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 the 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, rur.off 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* 43 MOD 000012537 WASTEWATER TREATMENT ALTERNATIVES c r c L [ 44 MCD 000012538 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 mg/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 680 mg/Iiter (+13 mg/licer) would require an equalization reservoir of 1.3 million gallons. The flow equalization function can be combined with that of a thickener so that sectleable 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/ton 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. 45 MCD 000012539 Table 4.I TYPICAL THICKENER AND CLARIFIER DESIGN CRITERIA Suspended SoLids Percent Solids Feed Underflow Settling Area* (sq ft/ton solids/dav) Equivalent Solids Flux (lb/sq ft/dav) Asbestos Cement kiln dust Cyanide slimes Iron ore, -325 mesh Lime slurry (acetylene) Manganese sulfide precipitate Power plant flue dust 9-12 9-10 16-33 20-35 12-15 0. 5 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 normally range from 8 to 15 feet for diamete rs from 10 to 150 feet. Source: B-l, page 19-55. Primary Treatment-- Chemical Ob iective 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 pretreatment 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- 46 000012540 MCD Table 4.2 WATER POLLUTANT TREAT! IE NT IIETHODS 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 3--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 (l.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/llter (1 to 100 ppb) Control MCD 000012541 47 (Text continues on page 54) Table fc. } toxic :norca.nic and orcanic pollutants and .methods for their control Ion ic St4t Tjx;c jLtv or Saurd (Huaarit) TV- io. j:. on Mils Thresno id Activacea Si jdxe lore, Innibit 5ry to 9lo Prrceses a*.' liter' AjUifcOic ion sit rltlea1 Antlaony Arsenic* Asbestos !(lbrou*)' ioron (halides) 3*ryUiuaf Oadaiia^ C41 c 1 ua ^rsQiua*,Htiviiinc ' Trlvalenc* C3?p*rr Cyanide1 1 ron Lead* Manganese Magnesium Mercury1 SlckelT Selenium' Silver' Sodluo Sulfate Sulfide Th*iliu*r line' Sb*3 15 ppm 0- 5 sg/'a3 Skin burni Skin Irritation Soae explosive Poisonous liol. salts) 0. 5 ag/a3 Skin irritation Poisonous -- 2 fibers/ea3 -- (carcinogenic) -- S03`3 (1 ppa) Skin burn* (halide*) Very toxic 8-2 Cd"2 (1,-2 0.002 ag/a3 0.05 ag/a3 -- -- Skin irritant (eluli) Poisonous Toxic (soae explosive) -- Or -- Cr-1 Cu*: 0. I ag/a3 CCrOj) -- Toxic (du*t) Skin irritant -- Toxic Toxic (enroeatee) -- Toxic CH-l 10 ppa (HCN) Poisonous Poisonous ?e-J -- Oaeoap to MCI Toxic, skin burnt (FeClj) Pb** IS ag/a3 Toxic Pol *0 nous * *t*2 H-2 - 0.01 ag/a3 (matal) (ffnfj vary rcactlva ) -- Toxic Toxic St*J. Si-- 0.1 ag/a3 Irritating Toxic SeO4*2 0.2 ag/a3 Toxic Poisonous At'1 H.-` 0.01 ag/a3 2 ag/a3 (NaOH) Toxic Skin bum* (SaOH) tox is -- S04*2 S-2 n^J 2q*2 1 ag/a3 (WjSO*) Suras (H3SO*) IS ag/a3 (H;5> 0.1 ag/3 __ Poisonous _ Toxic (tt2S) Polsonoua -- .80 0.1 riori 10-100 2.5CO 1-10 50 1.0 0.1-5.0 1,000 0.1 10 0. 1-5 1.0-2.5 5 3.500 - 0.5 1. 500 1.6 -cn* - -- 5-50 50-500 1.0 4 5 1.000 1,365 2.0 -- 50 __ - nor. c -- -- :.;s -- CG5-0. 5 T.Ji -- 0.5 50 -- 0.53 -- 500 0.08-0.5 c MCI) 000012542 43 `abla *.3 (Caatlnuad) TailC INORGANIC AND ORGANIC POLLUTANTS AND METHODS FC THE 11 CONTROL lutJnt Znop^ipi ;c Aimfin . * Anc iion-y Carbon Ad to roc.on Control Methods ?r*c ipicjcion _____ with CaiOKl > SaS !on Excnanaa (Uvana Oaaoaia' XX XX Art an is r Aabetcoa (fibroua)' boron ihalldae) X X X X StrvllLus' C ad aljo ^ XX X XX Calc i ua Chraoiua-Heaavalanc f Trlvaiaac' Copparf Cyanida* Iron LoadT tlanginaia M|natiua .`Ircuryf Mlckal1 Jalanlua' Silver* SodlM Sul fata Sulfide T^aLllua* Zinc* XX X XX X X X XX X X X X X X X XX X X X X X X X X X X X X Thraanoid Halt valuaa for rapaatte B hour 4*7 axpoaurta ale teat advaraa a(fact, .. .............. Icvirsirta'.Ca. ' A^a.-.i-. fRavaraa oauoala (lvaa a 94 to BBS rojaettM af teat weal tote from (ate aolutlona of up to 12 act corteaotratloo. Slaecrodlalyala eeacaatratoo aoot apuacua loarpaUc aalca tram 1,000 to 3.000 ppm to ateuc 10,000 pp but with .00 to 300 ppu laft la tte purlllat aeraaa, Sourcaai 1-0*4, B-1397, fr-OM, 447021. 49 MCD 000012543 *bie ICantlcuedl TOXIC INORGANIC AND ORCANIC POLLUTANTS AND Ml7H0W FOR TNEIR CONTROL ??.jnt Normal Stats Li c uid . So1i: , Cm 3oil;nj ?oint zr) 30D< Theoretical Oxvgen jeaano , ThOO Tonicity to Goldfish, Concentration and Tlae cor :0S Facility Acen*p"-~i~* Acfcietri' Ac r-< ior.it r il Aliyl zloahol Allyl cUiriCi Jenzene 1 Bentidene' CArson tetrachloride Chlcrot orn 'resol -rocanyl tlcaftol Chrvirvi 1,--0taethy1 phenol' S :?7 _ - 5:.5 0.0 1.72 ' CCC ) o.cb (/1. ;. r.r - 0.72 3.17 11.8 ag/1. 96 nr (Blueglll) 5- 96.9 0.2 2.2 1.0 a|/1, 24 hr L -5.5 C. 23 1.64 20.9 sg/1, 96 hr L 30.1 2.13 3. 10 ` 46 eg/ 1, 24 hr S -c: - -- L 76. 7 0.0 0.21 - 6: 0.C2 1.346 - L 191 1.6 2.52 -9 ng/1, 96 hour L Ul - --- S - --- S 21 l.J -- -- 18 ag/1, 96 hour 2 , .-Oir. itrotoluene Da--(2-echvlhexyl);ncn*l*ie' 31-n-bucyl pr.tnelate* Ethylbenzene n-deptyl alcohol n-Hexyl alcohol s L L L L 3C0 38} 340 136.2 176 L5B 0.41 3CI of ThOO 28X of ThOO 2.24 -- 10 ag/1 94.4, 96 hr -- Iso pho rone 1 Met hy lene chloride' Naphchalene' Nitrobenzene' o-Nitrophenol' ?-NtCropneool' n-Octnoi Phenol' L 213 -- L 42 - S 218 0 L 211 0 S 214-217 - s 279 -- 2.99 1.9} -- -- L 19} 38X ThOO. 2.9} - L 182 W4 2.6 37 MCD 000012544 so r r c c. c Tebie '.1 (Continued) TOXIC tMORGAN 1C AND 0RCANIC POllUTANTS ANO. METHODS PC* THEIR CONTROL Pollutant 'rz4r, it Acccap ncheae Ar;.is* Acrviam tule Aul/i alcohol Alivi chloride Beniene' Bcntidc nt * Carson recrachioride' CSlsraf o ra * Cresol Crotsnyi alcmoL Chryssner 2,i-3loecnyIphenai < 2,*-Dtnitrateluene 51-( 2-etr.ylhyi)phchalate 01-N-bwtyl ?hcnalacer Ethylbenaena n-deptyl alcohol o-Htxyl alcohol I*ophoronar Met `v l n chloride * NaphthaleneNltroOea*eoeJ o-Nicrapneoolf p-NUrophaaol1 oHjesenol Phene 1 ) Threshold lone. Inhibitor* to Vn.imcil Process 'as;liter) AA4 r 0 5 l C 52 j4g * i3n V; : rif icarion Control Methods _ 53 " 92 20 125 n -500 (E. Cell) 57 12 47 IOC -- 10-2C 10- lb 50C -- 500 1,000 _ 19.5 190 -- i-lb -- - -- 1 T 0.* t 50 200 -- 100-500 -- 200 -- -- 4-10 , 15 we* retention or. aecive carbon. water scrubomg. <MnO, Biodegradation by autant meroorganitai Activated carbon (retention 0.CI4 it i'i Evaporation 3 25C (90! of 1 ppa after 99 am) Active carbon <0.09 g/g). air stripping, anaerobic lagoon (13 lb/day/1.000 *q ft; 10 ag/1 in, 3 ag/1 cut) Evapotatlon A 25C (90! of 1 ppa after 9' ami Evaporation 7 25C (90! of 1 ppa after 93 am; Ion exchange (LOO! retention on Aabarlice XAD-2) - Ion exchange (100! retention on Aaberlite AJCD-2) Biodegradation in freshwater hydrosail Active carbon (SS! retention at 100 g/1) Activated sludge (27! oxidation at 500 ppa after 12 hr) Activated sludge (29! of ThOD after 24 hr) Active carbon (edeorbebiUcy 0.19 g/g); reverse osnosis (47! rajeetlon Iron 0.01 M solution); Lon exchange an Aaborlltc* XAD-2 ($5! retention at 200 ppa). Anaerobic lagoon (49 lb COD/day 9 140 ag/1 in end 30 ag/1 ouc) Active carbon (0.193 g/g, 97! ratantlon froa I.Q00 ng/1 inf low) Evaporation froa water sc 25C (90! af 1 ppa aftsr 80 din ton atehangt, 100! sbsorption on Aaberlite* XAD-2 Mtlve cetbon 9 .196 g/gC (96! adaorbanca ? 1,02 3 ag/1) biodegradation by soil microflora Ion exchange (100Z retention on aBbarlite7 XaD-2 at 0.2 ppa) Reverse oeaoeis (69! rejection froa 0-01 M Sola) (1) Active carbon O.lblg/g C (91! adaoTptlon froa 1,000 ag/1) (2) Adsorption oa Aaberlite* XAD-7 (86! affac at 0.4 ppa) (3) Solvent extraction with Ugbc oil (95!) (4) Trickling filter (100X raaoval at 20 ppa) 51 MCD 000012545 ?-,; I 7e trac.'... r .--e-8 7r ic ni or; t `y .en 7ilun* vinyl tftloridr 7*&ie TOXIC IS'ORCA-SIC .COD IRCASIC . Core i-uC ) u;D ' ITHC CS FOR 7 K E IR 00 STRCl Norsal 5tat Lo quid. -olid , 0* L L 3oll.r.4 "omi -T~i ..3 !I : .- 50D< 10 77.00 .: B L jft.7 -- L L.0-3 I. ; 5 2 -.3.9 -- '"-00 -- ?.;9 -- Toxicitv to Coid t`v 5n , Coneantracian xnd Tl = ; ;r - ~t Fatality -- -- -- 3.. 3 -- 53 aj; i, 36 nr ^ / MCD 000012546 52 c 0 Table >.3 'Concluded) iscrcasic v.e organic rc'-lltants va ?xthoqs e:r rwtu control 11 jtant_______________ Rrsparj/l alcohol Tet racn. ;r;e cr.v 1 e7 e icn.s rse .ene To Luene .'inyl chloride* Threshold Cone. Inhibitory :a ______ 3 i a 1;: c a 1 ? r o c c s ' ~t o-.;.jik v.rc:L; S. ;; ' :uis~.).~. si t r. : itat ion :-:o Control Nat hods 5 j i*. 1 5C0 Evaporation fcoo water at 35C (9CZ o: ppa a: ter ?C am ; Evaporate :rao water at LSC (9CZ oc pc a: cer 80 am ) Active tarbon 0.3Sg/gC (79S adsorption too 31r ag;.;. mc;v s.udge digestion ' -C og/1- evaporation Jroo water at 15C (90X at ppa alter 96 am i Threshold mnibitory concent ra: ions her* .are determined with bacteria `Pseudcocnae putlda" and biological deeoopo iC ion -i possible n soae case* at nigr-er eoneentrat ion*. 'Luted as priority pollutant* i< t.-.e Er.vt rorcencal Protection Agency. Id 1 .0U ; Tther priority pollutant* not luted anove are as -laloeen Cancai-Unt Compounds Or. 1 o rose men*, i,:,.*cr;en.t*5cen:ene. -.t*ehlcraB*n tene, 1, 1-d ichioroe thane , 1.1, l-trie More thane, 1,1 -dienior se thane . 1 . 1.1-tricMoroethane . 1 . 1. 1.l-tetracr-larsetnane. chioroecrane, bis(enloroaeehy1) ether, bls(chloroechy 1) ether, 1-chlorsetny L -;n - i i t-.er -: >ee ;, 1-c nlcr: hapni r.alete. l.-.s-trtchLocdr'enoi. pa rachlarccecac re* si, 1-chloropnenoi, I . l-c:cni.oroB*n2*r.e , l.l-nir.ioraoenzen*. 1--ai: \orp:ease*.e . 3,3-d isnioroPent nine . 1.1--.icnlaroeth.ylen* , 1. 1-? rans-diehloroetnv i#ne, ] , T-dichloropnenoi, 1.1 -J tch--or irr apasa . ), 3 -a tc 11 a rop ro py aar.e , i luorantneae, .-enoropneny 1 phenyl ether, a-araaophenvl pheny. ether, oisi l-ehloroet no* v ) machine, cetnvl chloride, necnyl bro&ide, jraeofors, d 1c hlo roProaoae c hane , c r ichlarar luereaecnane . J ichlorodi C luormet ha ne . Oh. : ran. : roc see tnane . hexach l pro But ad iene , rex acnio roc''dopant a diene , pantacnloropneno.. , 3.--bento: luotant rene, tluorene a.ir;r, lieldrm, cnioreane, IDT. TIE, COD. naptaenlor, neptachlar epoxide , a.pna-iHC, baca-SHC, ga*ma-4HC, delta*:-!, trsc.cr- 1116. .311. 1131, ;3*2, 11*8. 113, and 1160, and taxaphena Others l.B-Oinicratoluane, 1, ;-d i p.re n vihvdra 2 ma . 1, i-n mi t ro phenol, u, a-d mi t roc re sol, Suit ro sod laetny Learns , S-nitrssodlpneny lantne. r tscoiropy laame . Putyl Bensyl phehaute, dl-s-octal phtnalace. diethyl phcneiate. dioethyl pntnalata, 1,1-benaant h race:*, 3, .-be itopy rene. anthracene. L. ll-bemoperylene . phenanchrina. dlbenio (a. h) anthraceoe, mdo( l. 1.3-cd > pyrene, pyrene, al ;na-'.co*iLi rao, beca-endosuif ur . aoo endoauliaa sulfate. Sources: S-1396. 8-1397. 53 MCI) 00012547 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 CaC03). At higher concentrations, the resin inventory and the regener ant consumption are sufficiently large, that other separation methods, such as solvent extraction or precipitation, are more attractive. Ion exchange resins are divided into three classes (B-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. 54 000012548 MCD (3) Anion exchangers--may 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 annoniun hydroxide. Capacities for anion exchangers average about 5 milli-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 (B-1394) and extrapolated to January 1979 is $430,000. Operating costs, consisting principally of labor (36%) and regenerant (38%), are $73,000/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 (clinoptilolite) 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-13911). 55 MOD 000012549 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 cell until they are contained by an anion-permeable membrane. Similarly, anions diffuse coward 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 $8.0 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 67. of investment. 00001255 56 mc.d Figure 4,2 MULTIPLE-CHAM8EH ALTERNATE-MEMBRANE ELECTROOlALVSIS CELL. A. THE ANION-SELECTIVE MEMBRANE; C, THE CATION-SELECTIVE MEMBRANE DEMINERALIZED WATER FEED Source: B-13910. 57 MCD 00001255^ 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 or by insoluble salts. Cellulose acetate; polysulfones , polyurethane, polyamide, and nylon are suitable membrane or fiber materials. Reverse osnosis equipment developed by Du Pont uses hollow fibers 50 ^o.d. and 25 *ii.d. packed in bundles of 4 to 8 foot lengths (Peraasep3). 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 1,900 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 (B--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 mgd of brackish water are estimated at $850,000 and 108c/1,000 gai 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: 58 MCD 000012552 Table 4.4 MATERIALS REJECTED BY REVERSE OSMOSIS Cations Percent Rejection Ca2+, Mg2+, Fe2+, Mn2+ NaI+, Kl+ ai3+ nh41+ Cu2+, Ni2+, Cd2+ Agl+ 96-98 94-98 99 88-95 95-99 94-96 Anions Cll", N031+, FI", Brl" S032-, S042-i HCO3IP043-f S2032-, Fe(CT063CN1" 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 5-8 8-12 4-12 25 10-20 -- -- * Precipitation possible, depending on presence of other ions. Source: B-1394. 59 MOD 000012553 (1) Storage and handling of neutralizing liquid or solid (2) Mixing of waste screaa 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 relative costs of acid and base neutralizing agents are as follows: Agent H1SO4 (100%) HCI (28%) CaO Ca(OH)2 limestone Soda ash NaOH (50%) Price (S/ton f.o.b. works) 58.00 (tanks) 15.00 (tanks) 32.00 (bulk) 33.50 (bulk) 32.00 (bulk) 61.00 (bulk) 157.50 (tanks) pH Factor 1.00 0. 14 0.941 0-710 0.489 0.507 0.450 $/ton Acidity or Basicity 58.00 322.00 34.00 47.20 65.20 120.40 350.00 Relative Cost 1.0 5.6 1.0 1.4 1.9 3.5 10.3 The design of neutralization systems is discussed by Adams i--1395) - The estimated investment for a lime slurry neutralization 1 mgd waste stream (1% H2SO4 by vol) is $1.15 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 ocher, possibly undesirable, chemicals into the waste stream. 60 MCD 0012554 A typical oxidation reaction is the destruction of sodium cyanide by reaction with chlorine and sodium hydroxide (B-1394): 2NaCN + 5C12 + 12NaOH -Ng + 2Na2C03 + lONaCl + 6H20 Oxidation with hydrogen peroxide converts the cyanide to the less toxic cyanate: NaCN + H2Q2------ -- NaCNO + H20 The reduction of :hromic acid (Cr^+) by sulfur dioxide gives chromic (Cr3+) sulfate, which precipitates readily in alkaline solution: 2H2Cr04+ 3S02 + 3H20---------- Cr2(S04)3 + 5H20 Cotcmercially 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). 61 MCD 000012555 Table 4.5 COMMERCIAL OXIDIZING AND REDUCING AGENTS AND THEIR POSSIBLE APPLICATIONS TO WASTE TREATMENT Acer.t Oxidizing Chlorine gas Calcium hypochlorite Chronic acid Hydrogen peroxide Potassium permanganate Sodium hypochlorite Air Reducing Ferrous sulfate Sodium bisulfate Suflur dioxide Sodium borohvdride Scrap iron List Price* (c/lb) 7.5 47 71 15.5 (352 soln) 68 68 (est) -- 2.6 16 10 15 -- Possible Waste Materials for Treatment Sulfides, aercaptans, cyanide Cyanide Organic compounds Phenol, sulfur compounds, lead, cyanide Trace amounts only of phenol, diquat*-, paraquat', organic sulfur compounds, rotenone, formaldehyde, manganese, cyanide Lead, cyanide Sulfites, sulfides, ferrous iron Chromium Chromium Chromium^"*" Mercury, tetraalkyl lead, silver Ferric iron *January 1979. tInsecticides. Source: B--1394. 62 000012556 MOD 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" + 2N'a+ + S'---------Hgsj + 2N'a+ + 2C1" This addition is `relatively straightforward, requiring only a nixing V 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-L 3914): 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-139L5). A few typical flocculants 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: 63 MCD 000012557 Table -.6 TYPICAL FLGCCOLANTS AND COAGULANTS .AND THEIR APPLICATION'S Fiocculant or Coaeulant Coaaosit ion Alun Ll * l 5C_ ; 3. xK^O Tvpe Coagulant Typical Aoc 1 ication '-'a ter treataer.t Effective Range_____ Approx. Price* Concent ration 'c ' lb 3 5-10 iS ppa 90 Ferric sulfate Fe;( SCt,) 3. xH^O Coagulant Phosp.nate llaxiaua Above 1 ag/L precipita ticn at --6 3.7 Sodiua ClC Sodiua carboxy Fiocculant Ilineral aechylcellulose 6 coagulant se pa ration 3-9 0.03 to 0.05 lb/ ton t- 76 Separan* Ac rylaaide powder Fib ref loc"* Aniaal glue Fiocculant Fiocculant Cheaical processing Waste Treatment 2-10 1-9 0.2 to 10 ppa 60 5 to 30 ppa 55 silica sol Ac t ivaced silica sol Coagulant Aa s t e -6 1 to 20 ppa 1C (as sodiua t rea caer.c silicate) Sodiua aluninace NaAlQ; Coagulant Water treatment 3-12 2 to 10 ppa 27 Cuar gua -- Fiocculant 'line ral processing 2-12 0.02 to 0.03 Ib/ton 55 *Cheaical llaricecirtg Reporter, April 16, 1979, Schciell Publishing Co., 100 Church Street, New York, NY 10007. Source: 8*13915, except for the prices- c e MCD 000012558 64 Seeding Application Loading (gph/fc^) Lime coagulation Alum/iron coagulation Flue dust Secondary biodegradable solids MLSS* = 2,000-5,000 ng/licer SVIr * 50-100 SVI * 200-300 SVI * 350-400 50 40 30-50 30-40 20-30 20 *MLSS--nixed liquor suspended solids. ^SVI--sludge volume index. For clarifiers larger than 125 ft diameter, the suggested loading rates are 15 to 25 lower and, for !fLSS 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 poly electrolyte coagulant (2 mg/liter) are added to the wastewater stream and a sludge (42 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 SI,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 65 MCli 0000125&9 Che hydrolysis of titanyl sulfate to yield titanyl hydroxide and sulfuric, acid: T1OSO4 + 2H20-------- -- TiO(OH)2 + 2H2SO4 and the hydrolysis of ethyl acetate to ethyl alcohol and acetic acid: CH3COOC2H5 + H2O - CH3COQH + C2H5OH If sodium hydroxide is the hydrolyzing agent, sodium acetate replaces acetic acid While hydrolysis is a frequently used reaction in commercial chemical production (B-13910), its application to waste disposal systems is still very limited* Hydrolysis can, in some instances, convert a waste material to more easily recoverable or usable com ponents* The hydrolysis of waste cellulose to glucose, which can be fermented to ethanol, has been investigated by Fagan (447038)* The cellulose is ground, heated to 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 foaat to recover toluene diamines (intermediates in toluene dissocyanate production) has been proposed by Mahoney (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 times and construction materials differ sufficiently so that each design is usually specific to a particular application (B-13916)* 66 mod 000012560 43* Primary Treatment--Physical Sedimentation Settleable solids are defined as those larger chan 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 (2SV) for chat percentage of suspended solids. From this can be calculated the settling velocity (ft/min) and hence the solids flux (Ib/sq ft/day) for the various suspended solids concentrations (B-L395). 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 Che intersection of this line with the "yM 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. 67 000012561 Figure 4 3 SETTLING CURVES AT VARIOUS SUSPENDED SOLIDS CONCENTRATIONS* c M tlG H TO F IN T E R A C T . mi 68 0000 SOLIDS F LU X , flVsq ft/ddy Figure 4.4 BATCH SUSPENDED SOUOS FLUX CURVE FOR DESIGN 69 MCD 000012563 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 (B-139L5): d 50 56. 3 Dc3 ^ Q(es - ei) 0. 5 where d50 Dc *n q e i and es particle diameter with 50% separation efficiency, y, hydrocyclone diameter, inches liquid viscosity, centipoises liquid feed rate, U.S. gal/min density of liquid and solid, lb/ft3 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 gpo but night not separate particles smaller than 50g,. A 10 mm cyclone would separate particles down to 5y> 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 cm 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 70 00 00 I O O o o & o' O' Figure 4.5 inches PRESEPARATION Flow Rat* < 200 gpm 36-50 gpm/ll^ 30-40 gpm/lt? APPROXIMATE SOLID SIZE RANGE FOR SOLID LIQUID SEPARATION EQUIPMENT - 00 II 8 oeo oo a | Bar racks eh 00 - - OD U> > -l 1 1 00 10 --o o o -Li. J___ L f- IN J____L _J___L. .88 3 0o o o 1 J--L | [ Pium screens | Bell screens, hydiotiev*ffe> I Tyler mesh .88 3 o6 o o OD o o -L-L-l___ l_ SEDIMENTATION Approximate Settling Reie 60-0.1 li/hr *10 ft/hr 1 - 0 06 ll/hr JJ Thickeners, clarifiers J Hydraulic classrhers 1 Hydraulic cyclones J CENTRIFUGATION Densely Dependent No No Lower Solids Cone. Lt. IS wt% 0 wi% Yes FILTRATION Solids Concentration, wt% *20 10 to 20 1 to 10 0 wt\ Filter Rate, g/m/lt* 6 5 to 0.2 0.2 to 0 02 -5 0 2 to 0 01 Solids Loss in Filtrate 50% solids below 100 m Small above 60 p Negligible Reciprocating pusher | High speed, automatic batch | | Solid bowl, scroll discharge | Rotary vacuum drum 1 | Tilting pan. scroll discharge | | Rotary vacuum disc | | Continuous precoal or pldle and frame (447035). Typi^il 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 gpd of metal plating wastewater by vacuum filtra tion on a rotary drum is estimated at $240,000 (B-I394, adjusted to January 1979). Operating costs, principally labor and capital-related charges, including straight-line depreciation over 10 years, are $43.00/ton of dry solids. The corresponding costs for centrifuging are placed at $168,000 and $385t'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 the 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 Cube, 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 72 2566 0000^- Table <*. 7 SOME TYPICAL FILTER APPLICATIONS T-^icai Material C/amde slime, flotation concentrates Cement slurry Pulp and paper Crystals, salt, etc. Pigments Sewage sludge Garnish Mineral oil Material Character Finely ground uinerals Approx. Filter Capacity lb.sc ft /dav ) 100-2,000 Finely ground limestone, shale and clay Free filtering fibers Granular, crystalline Sneary, sticky, finely dlvided Colloidal, slin'/ Cloudy, viscous liquid filtered hot with filter a id Removal of 1 to 20% bleaching clay from oil 4QC-20C 200-1,200 ( l'i to 20 gpm/ f c ^) 3,000-12,000 200-500 23-250 (5 gal/sq ft/hr) (3-30 gal/sq ft/hr) Filter Type Continuous vacuum Continuous vacuum Continuous vacuum Continuous vacuum Plate and frame or pressure tank Continuous vacuum Plate and frame Pressure tank Sources: 3-1, --7034, 73 MCD 000012567 Ta b1e 4.8 TYPICAL CENTRIFUGE PERFORIAKCE CHARACTERISTICS Cer.trif use Tvpe Bowl Qia. (inches) Tubular 1-3/4 4-1/8 5 Disc 7 13 24 Helical conveyor 6 18 32 54 Motor Horse power 2 3 1/3 6 7-1/2 5 15 60 150 Throughout Liquid (2pn) Solids (tons/hr) 0.05-0.25 0. 1-10 0.2-20 0.L-LO 5-50 2C-200 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. 74 00001^68 *ct> Figure 4.6 SCHEMATIC DIAGRAM OF DISSOLVED-AIR FLOTATION TANK WITH RECYCLE CHEMICALS CHEMICAL MIX TANK PRESSURE * REOUCING VALVE Source 8-1393 75 mcd 00I2569 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 thicken 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 $35 to $65/cu ft for cell sizes from 400 to 60 cu ft (B-l, adjusted to January 1979). Solvent Extraction Solvent extraction is not competitive with biological oxidation and thus it should be considered only for nonbiodegradable 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 ethylenediaminetetraacetlc 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. 76 0000125^ MCD Crystallization 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 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 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 nonblodegradable (refractory) organics or the residual organics remaining after biological treatment (B-1395). 77 MOD 000012571 Active carbon adsorption of impurities in aqueous screams may be carried ouc by various methods: Down-flow alternating fixed beds Cp-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 t'reundlich isotnera : 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, and 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, Che carbon can be regenerated with steam (about 1 lb stean/lb carbon). Inorganics are removed by washing the activiated carbon with a suitable solvent, acid or base. >6^ 0 OOOV78 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, includ ing 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/1,000 gallons at a 10 million gal/day rate. Recent research as been directed toward the combining of carbon adsorption with biologically activated sludge treatment (447044, 357789). The addition of powdered activated carbon to biologically activated sludge systens 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. 79 MCD 000012573 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 poly-ethacrylate 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 $5.30 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 + CO2 + H2O + energy This is a widely used method for the destruction of organic wastes (5-13913). 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 0000125^4 MCP Wastewater Influent Figure 4.7 ACTIVATES SLUDGE SYSTEM Air Air Source: 8-1394 81 MCD 000012575 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, 447040). 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, B-13922, 417055). 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 SI.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). Hie capital investment to treat 1 mgd of wastewater containing 10,000 ppta COD, and 4,000 ppm BOD was estimated at $2.1 million (1979 dollars) (B-1394). This included primary clarification, equalization, aeration, and sludge separation. Operating costs, including depreciation (10%) and taxes and insurance were $2.20/1,000 gal. Oxygen-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 MCD 000012576 Tabla 4.9 activated sludci process CHARACTERISTICS Characteristic Convent ionj* Process Troe Complete Mix Step Aeration Flow type r Aeratloa Plug flow Diffused air Completely mixed Diffused air Plug flow Diffused air Agitation Mechanical Mechanical Non* BOD; removal efficiency (*) 85-95 85-95 85-95 BOD5 removal (lb/day) per lb microorganism* 0.2-0.4 0.2-0.8 0.2-0.4 Volumetric loading (lb BOD;/1,000 fc^> 20-40 50-120 40-60 V MLSS (mg liter) 1,500-3,000 3,000-6,000 2,000-3,500 Aeration voluae/hourly feed rate 4-8 3-5 3-5 Application Low strength. domestic wastes General application, resistant to shock loads General application to many wastas Nuerlents (total) a p l lb per 50 lb 300; 0.2 lb per 50 lb BOD; Air required when BOD; removal la lb/day per lb of microorganisms is Greater than 0.3 500-900 fc3 of air per lb BOD; removed Less than 0.3 z' Agitation horsepower 1,200-1,800 ft^1 of air per lb BOD; removed 1 hp for 45 lb 800; removel/day or 100 hp/10* gal aerecor volume Sources: B-i393. 8-1395, B-I3922. V 83 MOD 000012577 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 (mg/Liter) Biomass loading (mg BOD5 per mg MLVSS/day) Clarifier overflow rate (m^/day-m^) Sludge production (mg TSS/mg BODe 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 lb/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 raicrodiffusers, 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 10 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. 84 tfCD 0000 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 acidforming 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 BOD^/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 000012579 MCD media can be flooded with wastewacer occasionally to eliminate stagnant volumes and to control fly larvae. Recirculation of the effluent wastes allows a higher loading (1,0C0 to 5,000 lb BODs/acre-ft-day) than a one-pass noncirculating operation (300 to 1,000 lb BODc./ac re-f t-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 BODy'l,OQQ cu ft (low rate) and 25 to 300 lb BODj/ljOOO cu ft (high rate) ]. BOD removal efficiencies usually in the range of 50-85L. 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): i + 0.0C85t/W/VF MOD 0012580 86 where Ei 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 * +R (1 + R/10)2 R Recirculation ratio, i.e., slurry recirculated slurry drawn off Thus, for 2 tngd of industrial wastewater having a BODg 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 B0D5 loading - 600 X 8-34 X 2 * 10,000 lb BOD/day. Then, from the formula above, 0.71 -________________ 1 1 + 0.0085 yiO,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/l000 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): 87 MCD 000012581 NH^"*" + 3/2 O2 Nitrosomonas --------------------------- N02~ + 2H+ + H20 bacteria Nitrobacter NO2" + 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: NO3- + 1.08 CH3OH + H+ * 0-065 C5H7O2N + 0.47 N2 + 0-76 C02 + 2-44 H20 The methanol requirement, mg/liter, is equal to: Cjq - 2.47 N0 + 1.53 Nl + 0.37 D0 whe re N0, 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 mg/llter with 90Z removal in a single stage and 972 in two stages. It is most efficient at temperatures of 28 to 32C and a pH range of 7.8 to 8.3 (6-1395). 88 MOD 000012582 / Denitrification has been applied to nitrate levels as high as 10,000 mg/liter at pH of 6.5 to 7.0. Holding times are in the range of 1 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). 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: Feed Comoosition Total organic carbon (TOC) BOD NO3-N N02-N \ NH3-N (' Organic N ) % Removal 80-90 90-95 I60-80 r The system consisted of an anaerobic reactor with 36 hr retention and an oxygen concentration less than 0.2 mg/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 MCD 000012583 sand aids in the separation of particles as small as 0.5 a. 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/ft2) uses a larger sand particle (0.50 to 0.60 am). The addition of polyelectrolytes to promote agglomeration enables even larger sand particle sizes and faster filtration races. 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 solidliquid feed is concentrated (by backwashing) rather chan separated. In some instances, using air together with Che backwash to expand the 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 (l.e., molecules with both hydrophobic and hydrophilic groups) which tend to concentrate at water-gas interfaces 90 MOD 000012584 (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 foam 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 MCD 000012585 Source of Effluent Uncreated 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----------N2 + 6HC1 Best results are obtained with a reaction time 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. 92 MCD 000012586 Table 4.10 TYPICAL COMPOUNDS SUSCEPTIBLE TO OZONATION* Organic r \ Aromatic hydrocarbons Microorganisms Biphenyl 3.4- Benzpyrene 1,2-Benzanthracene 3.4- Benzfluoranthene Bacteria Viruses Algae Protozoa 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 p-Cresols Catechol Xylenol Inorganic Potassium cyanide Potassium ferricyanide Sodiua 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 000012587 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 ozcr.e. 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-chrough process is used and Che 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 may require retention times up to one hour with stagewise application of the ozone (B-1394). The optimum combina tion of ozone dose and contact time 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 mg/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 placing wastes, etc. (B-13912). 94 MOD 000012588 Large volume (6,000 lb ozone/day) ozone generation systems require capital investments of about S350 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 Ib/day and operating cost was about 53c/1,000 gal (B-139^, 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 Mdeep-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) 000012589 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 might pass through the sequence of--spray cooler, cyclone separator, bag filter, SO2 scrubber, and stack--before being released to the atmosphere. Pretreatment Waste gases may need to be compressed before treatment. If the gases are free of suspended solids and are at temperatures below about 200F (1000 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): 97 MCD 000012590 Figure 4 3 WASTE GAS TREATMENT ALTERNATIVES PRETREATMENT SEPARATION LiQUiO c / <L L 98 MCD 000012591 Figure 4.9 r' \ COMPRESSOR HORSEPOWER FOR VARIOUS AIR FLOW RATES g VI VI UJ cac. 2 /" Ou IT O tr UJ S o a. UJ XV) o X UJ < 5 C Source: B-13944 AIR FLOW RATE, scfh 99 MCD 000012592 Vaax c 1/2 h,,a - 0**01^6 G0*82 L0*47 8 ^5738 where Vmax C pt * s hga G, L ZT max gas velocity, fc/sec a constant 20 liquid and gas densities, lb/cu ft volumetric heat transfer coefficient, Btu/hr/cu ft/F gas and liquid mass velocities, lb/hr/ft^ 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-Solid 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. 0000 100 HCI) Table 4.11 APPLICATION'S OF CAS-SOLID SEPARATION EQUIPMENT Characteristic Cyclone Bag Filter Electrostatic Precipitator Minimum size particle (microns) Minimum solid particle loading (grains/cu ft) Maximum collection efficiency (wt%) Typical gas velocity (fptn) Approx, pressure drop (inches H2O) Approx, upper size limit (1,000 cfm) Installed cost ($1,000)* Power cost ($/yr)* Maintenance (%/yr of installed cos t) 10 0.2 10 0.1 85 2,000 to 4,000 99 1 to 20 1/2 to 3 2 to 6 50 125 9,040 200 420 7,480 1.0 6.0 2 (max) 0.1 99 100 to 600 0.2 to 1 10 to 2,000 600 4,000 0.6 *January 1979 cost for typical systems handling 60,000 cfra of gas at 68F with a loading of 5 grains per cubic foot, 30% smaller than 10 microns* t 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 precipitator 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 (447C69, 447063). Vapors are attracted to the surface of the carbon by forces 101 MCD 000012594 believed to 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 CB--13929): where X/M * wt of vapor per unit vt of carbon k and K * constants p * partial pressure of vapor over carbon. The constants "k" 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 mm Hg. Generally, adsorbability varies directly with vaporization tem perature. Typically, solvent recovery systems are designed for solvent capacities of 10 to 20 lb solvent/100 lb active carbon (B-12930). Adsorption heat for various solvents ranges from about 12,000 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. C ^ f x 102 f 0* r table L2 VAPORS ADSORBED BY ACTIVATED CARBON* High (2~ to 50 vc") Acetic acid Alcohols Anyl acetate Benzene Brcr.ine Butyric acid Caprylic acid Carbon tetrachloride Chloroform Cresol Disinfectants Ethyl acetate Gasoline Mercaptans Ozone Phenol Pyridine Toluene Turpentine Med iura (10 to 25 wt'O Acetone Acrolein Acrylic acid Butylether Butyraldenyde 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 10*0 Ace taldehyde Acetylene Amines Butane Butylene Ethylene Eo maldehyde Formic acid Methyl chloride Propane Propylene Very Low (Not suitable at soecified conditions' Carbon dioxide Carbon monoxide Ethylene Ethane Methane *Adsorpcion from saturated air at 20C and 760 ram Hg. Sources: B-13929, B-13930. / / 103 MOD 000012596 P R E S S U R E D R O P , inches H 20 / H bed Figure 4 1 0 PRESSURE DROP FOR AIR FLOW THROUGH ACTIVE CARBON AT 70'F AND 760 mmHg Source: Pittsburgh Activated Carbon MCI) 000012597 104 Liquid 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 colunn size and circulation, one can readily estimate the capital and operating costs by the PEPCOST computer program or from published data (B-13927, B-1392S). Acid or Ammonia Neutralization Cases 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 MOD 000012598 desulfurizacion is expected to skyrocket from 4,000 MW in 1975 to over 130,000 MW by 1985 in the Cnited 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: CaC03 + S02 + 1/2H20--------- -CaS03'1/2H20 + C02 In practice, some S02 is oxidized to SO3 and this combines to give mixed calcium gypsum crystals [Ca(S03)x(S04)y*zh20] (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 $17.4 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 lb/hr of steam, with a modular investment in burners and steam boiler of about $155,000. 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. 106 000(^99 When the waste gases contain a snail quantity of an environnentally 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: 4ft [x2 + h(h + 120 D)] where q * heat intensity on the ground at X ft from base of stack, w * gas flow rate, Ib/hr. h * height of stack, ft. D * stack diameter, ft. M - molecular weight of vapor. 107 MCD 000012600 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 con verted to carbon oxides and smoke is eliminated (B-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 5190,000 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 and the concentration at this distance was expressed by: r- Cz '-max -------- - -- v2TT e^uh^ Cy 108 MOD 000012601 where h * stack height, cm. C2 & Cy * vertical and horizontal diffusion coef. , 0.05 to 0.07. M * gaseous impurity emission, g/sec. e natural logarithm base 2.718. c u mean wind velocity, cm/sec. Some additional guides to dispersion stack design are suggested by Ross (B-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 $70,000 (447057, adjusted to January 1979). 109 mcd 000i2 602 --\ AC SOLID WASTE TREATMENT AND DISPOSAL TECHNOLOGY Solids generated in liquid and gaseous waste treatment are treated and/or disposed of as described in this section. Solid wastes such as catalyst residues and spent adsorbents are also handled as described here. Potential treatment and disposal means are illustrated by the block diagram of Figure 4.11. The treatment procedures are standard, widely used, industrial methods. This section briefly reviews their application to waste treatment. Waste Solids Treatment Dewatering Dewatering centrifuges are applicable to relatively coarse (+100 mesh) granular, nonsticking materials. The capacity of these centri fuges is very dependent on the particle size of the feed solids, as shown in Figure 4.12. For example, for a KC1 feed with a moisture content of 35 wtZ and a top size of 1/8 inch, a 36 inch bowl centrifuge has a capacity of 44 tph of solids with an exit moisture content of less than 6 wt. This exit moisture content increases with solids feed rate and decreases with increasing solids particle size, as illustrated by Figure 4.13. The approximate purchase prices of helical-conveyor centrifuges are as follows (B-l, adjusted to January 1979): Bowl Diameter (Inches) 26 36 Purchase Price, ($) Steel Stainless 316 58.000 85.000 100,000 140,000 111 MOD 000012603 Figure 4.1 1 WASTE SOLID TREATMENT ALTERNATIVES WASTE SOLIDS MCD 000012604 112 ,fS* Figure 4.12 EFFECT OF FEED SIZE ON DRYING CENTRIFUGE CAPACITY C A P A C U Y, ions solnls pci hour 113 MCD 000012605 Figure 4.13 EFFECT OF FEED RATE AND SIZE ON DRYING CENTRIFUGE PRODUCT MOISTURE MCD 000012606 114 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-l): q- 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 * 0.5gO-67/d and replacing V by TTD2l/4 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* 115 MCI) 000012607 Typical performance for direct warm air cocurrent rotary dryers is given below (B-l). Solids moisture is reduced from 25 wtX to 0.5 wt% with inlet and outlet air temperatures of 330F and 160F and inlet and outlet solids temperatures of 30F and 1 50F. In let 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 (lb/hr) Exhaust gas (cu ft/rain) Water evaporated (Ib/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 $105,000 120 x 55 2,160,000 4,500 5,700 14,100 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 L977 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 $190 per metric ton. For several years, two ships--Matthias III and Vulcanus--operating from Germany and Holland, have incinerated organic wastes such as vinyl chloride residues and herbicide orange, in selected ocean locations (447071). In the United States, EPA has sponsored several demonstration plants for the destruction of chemical wastes, solid and liquid (447008, 447019). Five different systems have been tested: (1) sudden expansion liquid combustion chamber, (2) rotating hearth pyrolyzer, (3) fluidized bed combustor, (4) tandem autoclaves for decomposition of liquids at elevated pressures and temperatures, and (5) rotary kiln followed by an afterburner for evolved gases. Details of these tests together with estimates for commercial scale operation are summarized in Table 4.13. 116 6<b O'.0.'O.' 0 S> 609210000 QOW in fill -tit 6*9Z fS fS6 ft? 8*9t 2`5C t'l f SE 0-tl <2) (1) 9*9 <t) If6 (!) 002*92 ) 00#`?1 (1) 6*66 C) C6*66 (!) 28*0-99*0 94 (t) f2-55*0 44 (t) ,0t?`!-0tr`! 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Mtvijutr,, U1TTH' N> T*sio*u; n>i B7Tn* 09*:s 42*nj <j*TT'*nV ]<!_ o;*zis *ioqn (0J >JOH/S) 6i61 *jno*r os ptjanCpt >*os Jutsajads ( uoiTlie t) 616) <(jTnu.* 05 p*iri,'pT 'JPNllItVT X31flH *5>3 (jy/rue: eut; i;t* 3UFld tfl5J*C35 P3=1 :1; 56*66 C) 5*66 (1) (;) uei :soj j*c W 50* D 4d 50f0 C ) 44 00*0-100*0 Cl) fB/fa `iT>ae iptj; ,cn-9C c> .SZ'C (1) PP* 8' *0-2! *0 (f 5*1 61 *o--i *o (i: (rB/8s) -.--T73Jd >9TJS sucjc;ji jo3*jui3u] IC' 3 3-JpTI^ Oe>83f ! 4o::s2-8s?:c:) ;oa:s:i-6*-f ' 3c5:6:-09*: (i; jnjTjadca^ 98C-54: Ci 591-5 ?! (1; ( jy 'c 1 aarj pa a; roc;31puts jojajauiau; ( 91 /t!>g 0;; ; ) ipnet oiutJjout jc pur otn 298 51* to**jo pur touh4 (91 '*a CiD:'Z>) 3uacip( /33pjS uiln pinbi; >3an *3ri/.9ti(]>c im43;; (1; qOI * 65 (OoOie-009) io0051-0011 (4!/n>8 ooe`6) 0:h 20t 'tlt3N put jnjTn* Dot pur uoqjpp told ntn gfS P7lo$ (.t 1 <4T/n8 OOS'Z) *uobjo -ojpA', 913tojt pur p*3?jn3Tsu,-; 03>0q J03I3HII ( i .1 qCI * OT (0o09f ioOOT! ci (91 'r>18 00C '- ) P3r 1 -n>Tuad i>pi U|3 ua t3>an ]gf; auTp3u0TPA50jeju**H (;) I4!,r'38 000*81) 09Jta -ojpXu PTjaiapJT put pajtjnjvttC'. ;c tajaan 3ur( auaiAU33 qO! * 55 OoOS9) ) 4o00*t Vd? C"i Z JU'CT 00 --00Z Ud? 09-Z5 *3"lo ic "apinbT". J3Ht aa^auxa ur pu 'jaoarijaa 1 jr.}u a Ae p*iA5T'c; JOianqBo: paq paTpmTj >v't 0^ *UTt`,yeji JT3 JO **tp1'l* 'apTTCK Xtuo api^tr: H9T3 r utncju: Sui3TX joj*q jtt ucj; uji pair* aaaat aanpyx; jmbpo ucT3*naoo3 aor; qsu a Xs pane: -TO; jaiATOjXO U334 SuT)T30)j K Pr:s f pur j d r cc* j v f 'iu: 46)tJtfti ucii^^os qnj^s t *iOQnj^s sntTirj v Xq Pao||o; uOT3ncfeo3 pinbr, (uo\furdn u*ppn) c;uj *optc^ *uo%.*iatc Lc:i*rqoc;. *5jjng -cictJ *cb puTp;p, j';f: ' stif, u*.\ Aurooc;. spjrf'CJTu; av^ 5irnd noi:v^isno3c : xisvn anjossod'-vaa *s*o C I > r: (jtau U0T3tnqac3) pi(J3 iilitr (JV-'PJS! X335*d3 >Tfj: 9 33ajnqrjadtta: u Tjado lit; p**i 3a a*.; lerdt; jcjrjaursu; Pd/3 j03ja'JT3-:; Tab la 4.13 (Concluded) V.5. EPA-SFONSOUCO WASTE INC INTSLAT ION OEUONSTIUTION PLANTS (r.ctnsrator ivpe Incinerator capabilities r<M ract Operating temperature Neat capacity (Stu/hr) Wastes traatsd Ucnduscioa neat) Incinerator conditions feed cat a v lb/hr ) Teoparatura Zlaars. Inc.. Aothchlld. Wise. Two continuous autoclaves la sanis vttn air bubbled throvgn tfia liquid aacaa ae alavattd taaparacuraa and prai* presence of a tapper catalyst- )M Coaosnv, Cotzaae Crova. *unn. notary kiln followed by a sacondary combustion chamber, a water quenen tower, a water sc mb iiu*r, sad an exhaust icae k. talLLn* Er'.vlf->i\**ncji L me , , c r ? * r a . ? c a * i Kotarv iiiln followed by an afterburner member. venturi and ten cower scrubber*, and an exhaust stack. Liquids with low hasting values Fuapable Liquids and dcimti solids Puapasl* liquids wastes and druaied solids 5-iOO gph ..000 Ib/hr 723 Ib/hr ?CS capacitors m iriai 450-620F ( 230323C) - (1) Coke plant aqueous wastes containing phenols, creaols, ammonia, am particulates; 00 - 5,520 ppa (ICO Mv/Lb) (2} Aqueous waste aoln of dichloronitrabansane (2Cg/l) and o-'T dissolved solids ( 120 itu/ lb) 9BO-1090C <1800-:000*3 90 * 10* 2400-270Cf (i3co-i:cco 110 x 106 <L> Aqueous (72S) slurry of polyvinyl chloride solids (28?) with tracss of vinyl chlonda and aliphatic hydrocarbons <1.300 Stu/16) (1) 725 Ib/hr aiLled PCS capacitors in tiber druas (.<5.200 Stuv lb) (2) hit roenla roeenzerta (.952 ) wasces :lus il isoaers (9. ICO Stuv lb) o 46 (2) 53.4 ( 1 ) 5J6F < :acc) ( 2) 5)6F 1 280*0 Primary cane: ibC0r (870C) Secondary cone; :ooof ( 1093*0 (1) 723 (2) i.023 (1) Kiln. ::SCF not used Afterburner. 2(.)0*F (2) Kiln not used aftarburner, 2*30F Residence ilia Inciaerator pactoraanci Scaca particulate* (sg/s3) Tree* aatale, sg/3 Instruction efficiency iZ) Estlsated eoaerclel plane alia itnoft ton*/hr) Cat- capital investment, adjuatad to January 1979 ($ Billion) Operating coat, adjuatad to January 1979 (S/shart tan) Labor, S12.70 aav-br Auxiliary fuel, $2.60 ailllea Mu Chemical* *ad utilities Heistenaace Capital-ralatad came* 221 l-tvaataaot Total oparatlof eaat Sat coat <n t-o hr (2) 1.0 hr Further wacar traataaat naadad to reuove catalyat sod residual organics. (1) 99.*1 of dlchloronltrobaotene (21 99? phenol 66Z quinoline 832 of COO (1) 770.000 (2) 53.000 (1) 11.3 (2) 2.3 (1) (2) 0.62 1.00 2.95 0.30 0.43 0.64 3.27 T^r 3.58* 9.38 1.09 1.93 9.23 T7773 0.30 16.10 Solids. 2 hr Gasea, 2 sac 71* (HC1, 15) Scrubber water 720 ag HCl/llter (1> 99.99 (2) 99.99 74,000 8.3 32.3 183.3 31.5 40.7 223.4 533.6 *So organic aiti aatsrlal* datactad in acrubbar tatarrrual cradlt. Vollor-up treatment. Sourca: 647001. (1) 3.2 sec (2) 2.3 sec (D 33* (2) 14" (O Pb 2.7 (2) Nona detected (1) 99.96 (2) 99.99 <1> 5.300 (2) 5.000 (1) 3.9 (2) 3.0 (l) (2) 93.6 307.0 96.3 71.6 154.2 7TTT 54.4 20.2 18.9 33.8 130.9 258.' 118 MCD 000012610 c rZ>- r C c ( 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 3tu 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 races 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 Btu/lb. The available net heat from burning 1,000 lb/hr of this material, accompanied by 100 lb/hr of moisture, is as follows: 119 MCD 000012611  Gross heat input (9,000 x 1,000) Less evaporation of free water (1,060 x 100) Less evaporation of formed water (0.563 x 1,060 x 1,000) Less losses, assume Q0% heat trans. effic. (9.0 x IQ6 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, econo mizer 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 (fM 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 dally ton of sludge feed. C C 120 MCI) 000012612 Waste Solids Disposal Land Faming Land fanning has been used in the United States for over 25 years as a means 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, which 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 Che 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). 121 MCD 000012613 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 ICO lb/cu ft; therefore, one acre foot has a storage capability of 2,000 tons. Thus, a 1,000 tons/day wet 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 (447088). 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 000012614 MCt> Figure 4.14 STACKING PROCEDURE FOR WASTE GYPSUM FIXED VERTICAL Source: 447091. 123 MCD 000012615 Disposal costs for landfill operations, where cover material is available on sice, 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): MCI) 000012616 124 C ST** Study and Land Equipment Operating design costs (20 years) Total S 114,000 147.000 367.000 4,242,000 34,870,000 ($61/ton) 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 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 come 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 race of 6 million gal/mo (140 gal/min) into a 10,000 ft well are reported to run about $60,000/yr and energy at 2c/gal (447087). 125 MCD 000012617 5 COST CALCULATION'S FOR WASTE TREATMENT MODULES There are a number of methods for Che 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 MCD 000012618 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-13925, 76481) has applied the modular approach to the evaluation of chemical process capital investments. In Cuthrie'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, 128 MCD 000012619 ct ol (U-J < 01 01 s n OQ (N scc < H <J - UJ ^ -- 0) 3 -O Q oy UJ O ct O LL a oz UJ -- <r zt-- a V Suuices: 6 ) 3926,76481. 129 MCD 000012620 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 nodular 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 modular costs for waste treatment operations which is independent of both Guthrie and Icarus modules. Capital Cost Methods Used in this Study The modular 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 (fjf) " 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 anf^*l+l+l+l+l*5. 130 MCD 000012621 Table 5.1 SRI MODULE INVESTMENT ESTIMATION FACTORS Installation Requirement Little Some Extensive Base 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 (f%() " 1 + A + B + C + D. (2) Module cost * purchased equipment cost (f.o.b.) x fjj. 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 *> 27.52. However, the totals for the nine modules listed show a mean deviation of only (1,872 - 1,703)/(1,872 * 1,703) x 100 4.72. 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. 131 000012622 MCD Table 5.2 COMPARISON OF CHBllCAC EQUIPMENT MODUU COSTS ESTIMATED 8Y DIFFERENT METHODS Basis: PEP Cose Index - 290 Tine " January 1979 iaulooenc Description Air cooled exchanger 500 sq ft Steel tubes lea rus Moaule Cost* (S) 45,000 Equipment Purchase Oust (S) 16,400 Column, valve trays 5 ft dia. x 30 ft 15 crays Carbon steel high Compressor, centrifugal L,000 hp Turbine drive 165,000 72.000 700.OCO 320,000 Furnace, cylindrical Carbon steel '.C alllion 8tu/hr 250,000 32,000 Heat exchanger, 1 , 000 sq ft 100 psl Carbon steel fixed tube 58,500 14,300 Pump and driver, centrifugal 1 GO gpm 70 ft head Iron 10,900 1,950 Tank, horizontal, cylindrical 10,000 gal Carbon steel 47,000 15,000 Tank, vertical, cylindrical 10,COO gal Stainless steel 150,000 45.700 Thickener, 100 ft dla. 7,3C0 sq. ft. 390,000 -- Totals 1,816,400 Guthrie Module Factor 2.17 3.05 2.15 :. 19 3.17' 3.30 3.05 4.16 -- Module Cost (8) 35,500 Equipment Purchase Cos c (si 14,500 220,000 48,000 690,000 340,000 100,000 75,000 45,000 9,700 6,400 2,000 46,000 14,000 190,000 60,000 290,000* 140,000 1,702,900 SRI Module Factor 2.2 4.2 2.6 3.4 4.2 3.8 2.2 1.8 2.2 Module Cost CS) 32,000 200,000 890,000 255,000 40,700 7,600 31,000 108,000 1,872,000 UOi oo *Equipant purchase cost and module factors are not readily separable from the Icarus Corporation modulo cost TThis figure urns derived from the Cose Engineering Quarterly la order to complete the cooperative column. c r e 132 MOD 000012623 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, 10Z 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+l+l+Q* !% A filter or centrifuge processing a sulfuric acid slurry would have a figure of 7 or 8%* ( v. 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 (opera tors/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 MCD 000012624 Module Cose Curves We have derived nodule capital costs and maintenance percentages from published or quoted equipment prices and nodular 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 nodular costs# These costs apply to a point in tine 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 modular cost. Where these costs are given as a function of equipment size, descrip tive information in Section 4 of this study will enable a conversion from size to waste stream flow rate* In instances where the desired module cost curve and operation cable 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 (C) Power usage and moving parts CD) Connecting equipment (E) Solids handling, abrasion Totals Annual Maintenance Cost (% of module cost) None Some Appreciable 01 01 01 01 0 _1 05 2 2 2 2 __2 10 Note: Annual maintenance cost (M^) (A + B + C + D + E) x module cost 134 MCD 000012625 The module capital cost curves and operation tables we developed are shown in Figures 5.2 through 5.53, as follows: Figures r" Waste Scream Aqueous 5.2- 5.31 Caseous 5.32-5.44 Solid 5.45-5.53 v The application of these modules to Che estimation of capital and operating costs for the treatment of chemical industry wastes is demonstrated in Section 6. /-, 135 MCD 000012626 Figure 5.2 1 30 MODULE COST: TANKS 1,000 TANK VOLUME, gai 10,000 30 000 C V r MODULE. COST. $ m ilium s TANK VOLUME, gal L mod 000012627 136 F;gure 5.3 MODULE COST: THICKENER. CLARIFIER 11J>11^S 0 i .C O S! MODULE SETTLING AREA, sq ft 137 MCD 000012628 Figure 5.4 MODULE COST: SETTLING LAGOON s u o ilim i $ 1S O D 3 1 flO O W 30,000 100,000 SETTLING AREA, sq ft t 1I 1.000,000 1 SETTLING VOLUME, gal 138 mcd 0000 10.000,000 ' 30.000.COO Figure 5.5 MODULE COST- OIL SEPARATORS FLOATING OIL VOLUME, go* 20 100 300 M O D U LE COST. S m illions 139 MCD 000012630 Figure 5.6 MODULE COST: FILTERS C M O D U LE COST, $ m illions r FILTER AREA, jq ft 140 MCD 000i263l C c 1 Figure 5.7 MODULE COST: CENTRIFUGES SOUOS CONTENT. ,o..hr ! coo " 0 0 |-- 10 000 CO 000 c Vi:?-.31 w jc:cr S:a n fss '0 V 0.01 1,000 Ooeracon: OOO Maintenance. * of module coit/yr 5 5 5 Labor. ooerators/$h<ft 0.5 0.5 0.5 Electricity, kw/1,000 gpr> 3* 1 1 3 kw oer 1.000 tb/hr solids flow. I ............................................I 10.000 1-- I L--L I I I 100.000 LIOUIO FLOW, gph 1 It i -J. i--i J1.000. 141 MOD 000012632 Figure 5.8 MODULE COST: HYDRAULIC CYCLON C M O D U LE COST, $ m ilium :, r v. 142 MCI) 000012633 M O D U LE COST, $ m illions Figure 5.9 MODULE COST: DISTILLATION SYSTEM too 0 c Material Factor- Caroon steei 1 0 Sta>nie$s steel 2.0 EASE OF SEPARATION BOILING PT DIFFERENTIAL COOLING WATER USAGE. ^ ' gpm/1.000 gph LIQUID FLOW S V STEAM USAGE. by 1.000 gpn LIQUIO FLOW _ - VOLATILES IN " ACUEOUS so lutiqn _* DIFFICULT 10 to 20 F Ao 20 10 01 See curves for steam and cooling water usage. Operation. O0 Maintenance, % of module cost/yr 4 4 4 Labor, operators/shift 0.5 0.5 05 Electricity, kw/1,000 gph 1.2 1.2 1 2 10.000 LIQUID FLOW, gph 100.000 143 MOD 000012634 Figure 5.10 MODULE COST: EVAPORATORS 2CO WATER EVAPORATED, ib/hr 1.000 10.000 M O D U LE CO ST. $ m illions 144 OOOO12635 MOD ( 0** V. Figure 5.11 MODULE COST: STRIPPER, STEAM OR FLUE GAS M O D U LE COST. $ m ilium :, \. 145 MOD 000012636 Figure 5.1 2 MOOULECOST: LIM E N6UTR ALiZER C M O D U L I COST. $ it........ LIQUID FLOW, gprt 146 MCD 000012637 r c Figure 5.13 / MODULE COST: SYSTEM FOR CHEMICAL REACTION OR PRECIPITATION 10 0 Material Factor CarDori steel Stainless steel Giass-iinea 1.0 16 18 V M O D U L E ('C)ST, $ m illio n s 0 01^1.000 V. Operation lalt curves): Maintenance, % of module cost/yr Labor, operators/shift Electricity. kw per 1,000 gph 4 05 3 Note: Add Quantities of any reagents required. II 10.000 I I 1 i I I 1 I 111 L I 1 I I 100.000 1,000.000 LIQUID FLOW, gph 147 000012638 MCI) M O DULE COST. $ m iliu m Figure 5.14 MODULE COST; ION EXCHANGE SYSTEM 148 MCD 00012639 M O DULE CO S1, $ 'm ililitiu Figure 5.15 r MODULE COST: ELECTRODIALYSIS AND REVERSE OSMOSIS CELLS LIQUID FLOW, gph 149 HCD 000012640 Figure 5.1 6 MODULE COST: OlSSOLVED-AI R FLOTATION CELL M O D U LE COST, %m illions LIQUID FLOW, gph 00 ISO Figure 5.17 MODULE COST: CRYSTALLIZATION SYSTEM c r 151 MeD 0012842 M ODULE COST, $ m illiu m Figure 5.18 MOOULE COST: ACTIVE CARBON ADSORBER FOR LIQUID STREAM LIQUID FLOW, gph 152 MCD 000012643 Figure 5.19 / MOOULECOST: SOLVENT EXTRACTION SYSTEM 100 0 r Material Factor CarDcm steel Stainless steel 10 1S Basis: Concentration of extractaD'e comoonent * 1.5*3 M O D U LE COST. $ m illions 10.0 10 0.1 1.000 COUNTERCURRENT SOLVENT EXTRACTION WITH DISTILLATION SEPARATION Of SOLVENT AND EXTRACT COUNTERCURRENT SOLVENT EXTRACTION WITHOUT SEPARATION OF SOLVENT AND EXTRACT Operation: Maintenance, % of module cost/yf Labor, operators/shift Electricity, kw/1,000 gpn Steam, lb/hr/1,000 gph Cooling water, gpm/1.000 gpn Solvent lost, tb/1,000 gpn Extract recovery - approx. 97% o O 4 0.25 1 2,800 1.000 - 300 120 - 63 3 f 1111 10.000 f -l 100.000 LIQUIO FLOW, gph I 1lI 1,000.000 153 Mod 000012644 M O DULE COST. %m illions 10 0 Figure 5.20 MOOULE COST: BIOLOGICAL OXIDATION SYSTEM INCLUDING SLUDGE SEPARATION Feed * 1.250 DDm BOD * 2,500 com ThQD Fitter deotn = 22 ft r c 10 ICKL1NG FILTER (single pass) o io 0.01 1.000 Material Factor: Carbon steel Concrete } 1.0 Rubber-imeO f 2.0 Plastic construction Operation: O Maintenance, % of module cost/yr 4 Labor, operators/shift 1 Electricity, kw/1.000 gpn 10 Ammonia reauired, lb/1,000 gph 08 Phosphoric aco reauired. ib/1,000 gal 0.4 Lime required, tb/1.000 gal 42 Copperas reauired. ib/1.000 gal. 0.8 Land area required, acres/10 gpd Filter volume, ft^/gph 0.2 - Sludge* separated, cu ft/1.000 gal 0.2 Sludge moisture 70%. wt/cu ft 64 Ib. 0 4 1 13 0.8 0.4 5 1.0 0.5 - 0.3 OO 4 0.7 2 0.6 0.3 3 0.6 - 1.25 02 4 0.5 1 0.3 0.15 2 0.4 - 0.25 0.15 * III! 10,000 * 1111 j_L 100,000 * i i >i 1,000.000 LiQUiO FLOW, gpn f 154 MCD 000012645 M O D U l fc C O S T. $ i m i I I k j iis Figure 5.21 MODULE COST FACULTATIVE LAGOON 100 0 Vater'a1 Factor Ear:r jra DOivetnyiene 10 Four feet deep wun ->c agnation CostOistnDution * 2E > excavation. 75'ij ;mng Liner life * 4 years 10 0 1.000 10 C > 30 C 0 Deration: Maintenance, % of module eoit/yr Labor, operators/sHift Area.acres 20% nil , gpm <> 10 * 0.045 x 1--.-0--0--0- x % BOO removal @ OCT" * 0 030 x --1,0--00 x % 800 removal 10.000 Feed SOD * approx. 1,250 ppm i t i i i t 1_____________L______I------- 1--11111 100.000 ,1 000.000 LIQUID FLOW, gph 155 MCD 000012646 Figure 5.22 MODULE COST; FILTERS. DUAL MEDIA AND SAND 10 0 Matecai - actor Caroon ste-r RuDoer-ime ' Stamiess stee 10 16 13 10 C M O D U Lb COST. $ m illion* 0.10 0.011.000 .v- > I I I L I- 10,000 Ooeranon: Maintenance. % of module eost/yr Labor, operatorsishift Electricity, kvv/1.000 gph 3 0.1--0 25 0.5 Notes: e Maximum sludge solids m feed 200 mg/liter Sludge solids removal * 90% Backwash volume 5% of feed. 1 1 < t iiI 100,000 i_____ |---- 1-----1--L_L ,1 000.000 LlQUlO FLOW, gph e 156 HCD 000012647 Figure 5.23 MODULE COST: FOAM FRACTIONATOR 10 0 r T Matenai Factor Carbcn steel Stainless steel ^ubOeriined ^0 l8 18 V 10 M O D U LE COST, $ m ilium s 0 10 0.01 1,000 4 01 05 Feed impurity concentration < 1000 ppm Foam quantity * appro*. 5% of feed. Typical foam impurity concentration * 10-loid over feed. ` tiL 10.000 in 100.000 LIQUID FLOW, gph 1 1 111! 1,000.000 157 mod 000012648 Figure 5.24 MODULE COST: OZONATION SYSTEM c M O D U LE COST, $ rmUmm LlQUlO FLOW, gph 158 MCD 000012649 r e c ( Figure 5.25 MODULE COST: DENITRIFICATION SYSTEM 0.0 r Matariai cactor Caroon sTeei Ruboef-nned 10 20 i 10 MODULE COST, S n iill.o i^ 0.1 0.01 -- 1,000 Maintenance % of module cost/yr Labor, operacors/shift Electricity, kw/1.000 gph 3 0,2-0.5 0.12 Methanol used, lb/hr 1.75 x Mow Igoh) x ^rem0ved Sludge formed, 10/hr 0.42 x methanol added db/hr) 1 1 1 1I 10,000 I L------ J I I I I I I______ 100.000 LIQUID FLOW, gph 1 i ` 1,000 ooc 159 000012650 MCD Figure 5.26 MODULE COST: HYDROLYZER M O D U LE COST. $ m illions 160 MCD 000012651 C Figure 5.27 MODULE COST: CHL0R1NAT0R FOR AMMONIA REMOVAL l 0.0 r Matena' Factor- RuDDer-lined Stairvess steel 1.0 1.0 V 10 M O D U Lt C O b l, $ n n lliu iii 0 10 r 0.01 '-- 1.000 Chlorine required, tb/dav gpd x 3.34 mg NH3/liter 1.000.000 1 1 1I 10.000 I I___ > i i i i i L 100,000 UQUID FLOW, qph L 1.000.000 161 MCI) 000012652 Figure 5.28 MODULE COST: CHLORINATOR FOR DISINFECTION AND EQUIPMENT FOR WATER QUALITY CONTROL c M O DULE COST. $ m illion* r LIQUID FLOW, go* 162 MCD 000012653 c .33* Figure 5.29 MODULE COST: PUMPING SYSTEM AND DEEP-WELLING SYSTEM 163 000012654 ttCD M O D U LE COST, $ m illions figure 5.30 MODULE COST: LiQU ID I NCI N E R ATO R MCD 0012655 164 1.000 10 0 Figure 5.31 MODULE COST. STEAM AND COOLING WATER UTILITIES STEAM GENERATION RATE. A,'hr -250 os.g> 10 000 100.000 1.000.000 10 M O D U LE COST, $ m illions 0.10 0.01 100 Operation: Maintenance. % of module co*t/yr Labor. operator/hift Electricity, kw/1,000 gpm water or / 1.000 Ib/hr steam Mafceuo water, gpm/1,000 gpm water or / 1,000 lb/hr steam O0 2.5 0.2-10 0.1 -0.5 1.2 45 20 1 I I 1 I I 1.000 t- t I 10.000 COOLING WATER PLOW RATE, gpm I II 100,000 165 MCD 00001 2656 10.0 Figure 5.32 MOOULE COST: GAS COMBUSTOR FOR STEAM GENERATION NET HEAT OF COMBUSTION (BliWscf) 1.0 M O P U L COST. $ niiH ioii jt 0 10 0.01 10.000 Operation: Maintenance. % of module cost/yr Operating laoor/operators/shift Electricity, kw/1,000 scfh Process water, gpm/i ,000 setn Steam generated. lb/hr/1.000 scf h o0 O 3 05 1.0 0.1 720 3 0.5 0.5 0.05 400 3 0.5 0.3 0.03 ISO 3 0.5 0.2 0.02 30 100.000 i i i ii 1,000.000 GAS FLOW, scfh I_1_____ 10,000 MCD 000012657 166 ( 10 i/) Q<J UJ OJ o /s 0 10 0.01 \ 10,000 Figure 5.33 MODULE COST: GAS INCINERATOR Steam generation, ib/hr/t.000 scfh Fuel reauirement. Btu/1.000 scfh 3 O.S 0.2 0.02 80 0.1 * 106 J_U_________ 1 100.000 1 * iiii_________ L 1.000.000 GAS FLOW, scfh i i i iii 10.000 000 167 MCD 000012658 1 00.0 Figure S.34 MODULE COST: FLUE GAS DESULFURIZATION SYSTEM 10.0 c r M O D U LE COST, $ m illiuns 10 -- 0.1 10,000 Operation: Maintenance. % of module cost/yr Operating labor, operators/snift Limestone, ib/hr per 1.000 scfh Electricity. *w per i ,000 scfn Steam, ib/hr per 1.000 scfn Solid waste, ib/hr per 1.000 scfh Note: SOj content reduced from 2.500 oom to 250 ppm. 3 2--3 0.674 0.10 1 63 2.25 r 100.000 GAS FLOW, scfh 1.000.000 10.000.000 c o,oO'.0^ & 168 e ( Figure 5.35 MODULE COST: HYDROCARBON GAS FLARE c ( GAS FLOW, scth 169 MCD 000012660 M O D U LE COST. $ m illions Figure 5.36 MODULE COST: GAS DISPERSION STACK GAS FLOW, scfh 170 000012661 MCD M O D U LE COST, S m illions 10,0 10 Figure 5-37 MODULE COST: AMMONiA NEUTRALIZER Material Factor Caroon steel ana rubber uning t0 AMMONIA VAPOR, 'b/l .000 scf 0.10 0 01 10.000 Process water, gpm Sulfuric acid (100%), Ib/hr 4 0.6 0.3 * 0.002A * A* 54A* A icfh/1,000 x acid equivalent/1.000 scf 1-- 1 I I I I I 100.000 <3A$ FLOW, scfh <'1 1.000.000 I---1 10,000,000 171 MOD 000012662 M O D U LE COST. $ m illiun* 10 0 10 Figure 5.38 MODULE COST: AC!0 GAS NEUTR ALl2E R ACID EQUIVALENTS PER 1.000 scfn C Mjierai Factor Carbon sieet Rubcer-imed 10 14 0.1 : \ 0.01 10.000 1 III Operation: Maintenance. % of module eost'yr Operating Labor, operators/sftrft Electricity, kw/1,000 jefn Procesi water, gpm Calcined lime or NaOH, ib/hr tefh acid equivalent 1.000 1.000 set O 6 1.0 0 3 * 0 002A 2.5 A S6A I96S) 100.000 t *-* 1.000.000 GAS FLOW, scfh 4 0.7 0.3 * 0 001'A 0 7A 88A (50%) 11 10,000.000 r c e 172 0000l2663 tfCt> M ODULE LOST. $ million;. Figure 5.39 MODULE COST: SCRUBBERS. HYDROCARBON OR WATER GAS FLOW, scfh 173 MCE 000012664 Figure 5.40 MODULE COST; ACTIVE CARSON ADSORBER FOR GASEOUS STREAM 10 0 VAPOR CONTENT b' 1.000 scfl 10 C M O D U LE COST. $ m illions 0.10 - _ - 0 01 10.000 Operation: Maintenance. % of module cost/yr Operating labor, operators/snift Electricity, kw/1,000 scfh Steam, ib/i .000 scfh Cooling water, gpm/1,000 scfh O 4 OS 0.08 5 06 4 05 0 09 10 12 4 05 0 10 20 2.4 100,000 GAS FLOW, scfh 1.000.000 10.000,000 C MCD 000012665 174 c 10 0 c 1.0 Figure 5.41 MODULE COST: GAS COMPRESSOR PRESSURE INCREASE PROM 15 osia M O D U LI: COST, $ m illions 0.1 001 '---- 10.000 1.5 OS I I_________ ' 100.000 1,000.000 GAS FLOW, *cfh i II----L 1 1 11 10,000,000 175 MCD 000012666 MOGUL E COi>T. $ m illm ii-. Figure 5.42 MODULE COST: DUST SEPARATOR GAS FLOW ch MCD 000012667 176 r 0K Figure 5.43 MODULE COST: GAS COOLERS 177 MCD 000012668 MODULE COST. $ n n llio iii Figure 5.44 MODULE COST: GAS REFRIGERATION SYSTEM GAS FLOW, cfh MGD 000012669 178 A'' V i0 0 Figure 5.45 MODULE COST: ROTARY Dl RECTDRYER 3dS>S Cocurren; drying NoriJTiCX'ng feeo material Faeoers. ^cpper c^cone and Dag Liter included MOlSTCRE lwt% of leeai 10 Material Factor Carbon steel 10 Stamiess steei i S M O D U LE COST, $ m illions 0.10 " _ 0.010 100 V Operation: Maintenance. % of module cost/yr Operating labor, ooerators/shift Electricity, kw/1.000 lb solids/hr Steam, 1.000 ib/1.000 ib solidt/hr O 6 1.0 15 1.00 6 1.0 3 0.78 6 10 6 0.42 * L L 1,000 J. _L_LX 10,000 SOLIOS FEED RATE {DRY BASIS). ;b/hr J____L 100,000 179 MCD 000012670 M O D U LI; COST, $ in.ll.oa> ICO 1c 0.10 0.01 1,000 Figure 5.46 MODULE COST: DEWATERING CENTRIFUGE Basis. ^eed HjO.-'soi.ds ratio *' 0 5 Product H0 content *<"60 wt*o Solids are granular. nonsncuing. SOUO FEED SIZE (mcnesi Material Factor Carbon steel Stainless steel 10 1.5- C t,-3. \ Operation: O Maintenance. % of module cost/yr Operating labor, operators/shift Electricity, kvw/1.000 lb solids/hr 4 05 0.55 4 0.5 0.30 t, 1 10.000 100.000 SOLIOS FEED RATE, ID/Hr Idry basis) oooo^6T1 180 j__ L 1,000,000 c e TOO 0 l\/- V 10.0 Figure 5.47 MODULE COST: SOLIDS INCINERATOR Satis: Combustion heat of feed < 1,200 9tu/ib. No orocess neat recovery or exchange. Water scruODmg of combustion gases. Chlorinated or hazardous wastes. moisture lwt%l M O D U LI COST. } millions 1.0 f O 55 2-4 2-4 0 018 0.01 25 15 Process water, gal/1,000 lb solids/hr 20 15 5 2-4 0.006 12 10 I I I I I I____________ I 1,000 L J__L l_ l -LLl 10.000 SOLIDS FEED RATE (DRY BASIS!. >b/hr I 1 IIS i i ll 100.000 MCI) 000012672 181 100 0 10 0 Figure 5.48 MODULE COST: SOLIDS COMBUSTOR Basis. Cant.nuous solids compustion Hoppers, feeder, water treatment included. Steam generated * saturated @ 125 psig WASTE SOLIDS (net heanng value C r M ODULE COST, $ m illions 10 O Operation. O Maintenance. %of module cott/yr Operating labor, operators/snift Electricity, kw/1,000 ib/hr feed Makeup Mater, gal/1.000 ib/hr feed Steam output, ib/ib feed solids 6 2 7 40 7.4 0 6 2 4 20 3.7 0 6 2 3 12 2.2 0.1 1,000 t I I t 10.000 I t I 1 11 100.000 SOLIOS FEED RATE (ACTUAL BASIS), lb/hr 1 I 1 t1 1.000.000 c WCD 000012673 182 e .300 0 C 100 0 10.0 DISPOSAL COST. S M iu ii u Figure 5.49 DISPOSAL COST LAND FARMING Sasis Lana cost not included lone acre 'equired 60 snort tons per vearl Approximate cost distribution: Laoorreiated 60% Caoitai-reiated 30% Fuei-reiated 10% niin<u*HxH 'iVti<Hutu i\ -rimiiitiitui"H'.M, AV < * W,V 1.0 I I Ll 1 ill l 1 1 I 1 I 1 III V 100 1,000 10.000 100.000 SOUOS FEED RATE, ib/hr 183 HCD 000012674 100 0 10 0 Figure 5.50 (DISPOSAL COST: GYPSUM STACKING Basu: Land cost not included-20 ft high stac*inq 'one acre required/37.000 snort tons gvpsum waste) Aporommate cost distribution Labor-related 70% Cap'tai-retated 25*4 Fijei-reiatea 5^ transportation to site not included C C DISPO SAL COST. wm 10 0.10 too xi<i . '*V(\VAAt\.<X\<rA/A *> m y It <ii A v i t < I . - r -r * i < < t I I I 1 1,000 I I 1II 10.000 SO Li OS FEED RATE, ib/hr *1 100.000 e MOD 000012675 184 e ( 1 .000 0 Figure 5.5 1 DISPOSAL COST: SANITARY LANOFILL Bans Land cost not included 17.000 short tens- acre to deoth ot 7 0 fti Cover material avaiiaoie on i>te Aooroiimate cost distribution Labor-reiated 65% Cao>t*i-reiatea 25% Fuei-retatea 10% Working time * 8 hndav Eau'Oment investment: Suiidozer-snovei <3''* cu yd) * S75.000 T-actor. trailer (60 cu vd. A0 tons) = S3* 000 DISPOSAL COST, S/shuri ion 10 100 t l-i-i 1 - 1.000 1 I l 11__ 10.000 WET SO LI OS FEED RATE, ib/hr l t t iJ 100.000 10 20 30 40 60 80 100 150 200 300 400 cu ft/hr 185 MCD 000012676 1.000 0 Figure 5.52 DISPOSAL COST. HAZARDOUS-WASTE LANDFILL 100 0 D'Soasal company --includes <ana Permanent naaaraous wastes. Transportation to disposal sue not mctuOed. Upper values for hign rainfall areas of northeastern U S ano io*%er values for arid areas of soutnwestem u S. Note: Stricter regulations ana mf'anon are expected to aounie costs by 1985. VtV<V/VvVrViV'Yi i'i'i i'i 'i I i 11 i (> < , < u i i i i i i i i n i < ' < i </ ` i i i, a.(11 njx umi A ftVt < < t t < < 10 0 DISPO SAL COST. $/shu< I ton 100 1,000 10.000 100.000 SOLIDS FEED RATE. Ito/ht MCD 000012677 186 TRUCKING COS1. $/shu.( ion RAILW AY COST. S M io it ion Figure 5.53 TRANSPORTATION COST 6.0 Bulldozer or shovel cost * SI 00--Si 50/ton Liau'd a Bulk solid x 1 25 100 200 300 400 OISTANCE. mile* lone way) Source: Author estimate* bawd on articles in CAemrca/ Wee*, Nov. 1, 1978 and Oct. 11, 1972. 187 MCD 000012678 BARGING COST. S/shori ton I 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 S) 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), hexamethylenediaalne (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. 189 MCD 000012679 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 l^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 sice 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 BODj 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 $8.2 million, with the stack gas scrubber accounting for 50% 190 MCD 0000J.2680 Figure 6.1 TREATMENT OF METHANOL PLANT WASTES Memanoi process Vetnanoi plant capacity nte'-mediate pressure from ''aturai gas Ref PSP Repcn \a J3A) l .000 toa GASEOUS WASTES H 2$-f icn gas from active carcon regeneration mois/hr C02 Ch4 C2M6 n2 h2S 1 119 1 1 6 128 Light-ends from methanol purification D<methyt ether Me tnanoi mo i s hr 45 20 65 LIQUID WASTES .3. Bottom* from methanol purification STEAM 135.000 ib fir( A LIMESTONE (600 ib<hri COMBUSTION (45 * 10 Btu-hr) 1 900 Btu- scf STACK GAS SCRUBBER CALCIUM SULFITE-SULFATE SOLIDS <24 tpdl 80,.. 1/2 ThOD = 25 000 ppm Water Metnanol H.gner alcohol* GASES "0 ATMQS=h=qg (545 CCO scfni OISP6R5ION STACK Extraneous water washing*, leaks. runoff, sanitary 12,300 ID/hr (1,500 gph) SOLID WASTES 5 Spent active carbon 6.600 ib 1220 ft3) every IS month* Spent zmc Oxide suifur adsorbent 18,000 ib '300 ft3l every 4 months Reference PEP Report No. 43A LIQUID TO SEWER OR RIVER BODg 50 ppm * 30 ib/d 0.000 gpn) 191 SOLIDS TO LANDriL L (12.600 tpyl MCD 000012681 Table 6.1 TREATMENT COSTS TOR METHANOL PLANT WASTES let Hanoi Plane Capacity: l.COC tpd; 0.9 Annual Scream Methanol Plant Investment: $50 million PEP Cost Index : 293 Tice Base: January 1979 Factor Capital Investment ($1,000) Module costs Indirect costs, general facilities, & contingencies, JO* Total fixed capital Operating costs ($l,QQ0/yr) Labor (aen/shife) ? S14.20/man-hr Maintenance (Z oodule coat) Materials Llnestone 'i S20/ton Line $30/ton Ammonia 0 S120/ton Phospnonc acid 3 5150/ ton Copperas 3 $3S/ton Subtotal, aacerlals Utilities Electricity 3 2.6c/kvh Process water 3 60c/1,000 gal Steam 3 $5.00/1,000 lb Subtotal, utilities Overhead, 50* of labor Depreciation, lOZ/yr of fixed capital Solids disposal, 3 $6.SQ/tonf TOTAL OPERATING COST Coabustion Furnace 375 113 -38 Cj) 60 (3) LI -- -- -- -- -- -- 10 n -1,386 -l,362 30 49 -- -1,212 Stack Gas Scrubber 3,100 930 * ,030 (2) 240 (3) 93 47 -- -- -- -- 47 11 -- -- 11 120 403 SO 964 *Labor and aacertals. r5 die round crip S 52.00/ton plue 54.50/toa landfill operation. Dispersal Stack. Biological Oxld. and Sludae Seen. Totals 17 5 22 -- (1) Negl. -- -- -- -- -- -- -- -- -- -- __ 2 -- 2 2,800 340 3.6-0 6.292 1,838 3, 180 (l) 120 (4) 112 -- 37 24 LS 1 33 168 -- -- 168 60 364 32 939 (3*j) -20 21b 47 37 24 15 7 130 189 14 -1.336 -1,183 210 3 13 82 693 c 192 MCD 000012682 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 S6.50/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 $1.36 million/yr for the steam generated by the combustion furnace, is $693,000/yr. This is equal to about 1.0% on a methanol sales price of 70c/gal. 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 (P0TU) it may be more economic to treat the small volume of aqueous 193 MCI) 000012683 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 * 1,200 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 foe- 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%). MCD 000012684 194 Ethylene Plant Wastes Treatment Methods The composition and quantity of gaseous and liquid ethylene plant waste screams, 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 50Z of the 2 year maximum one-hour rainfall (U.S. Gulf Coast) is included but not created. 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 MCD 000012685 Figure 6.2 TREATMENT OF ETHYLENE PLANT WASTES (ETHANE/PROPANE PYROLYSIS) Ethyieoe plant capacity 1*10 ip/yf c r References: PEP Report No. 298 end Accession Nos. 358764, 358811, 447093 196 MCD 000012686 HAZARDOUS SOLVENTS TO DISPOSAL WORKS HOOlb/hr) Table 6.2 TREATMENT COSTS FOR ETHYLENE PLANT WASTES Ethylene Plane Capacltv: 1.0 x 10^ lb/yr at 0.9 Stream Facto r Ethylene Plant Investment : $190 million Pep Cost Index: 290 Time Base: January 1979 c Steam Settler- Filter .An:: Flare Scack Generator Sklruter Press Lxz/d- ser Capital Investment ($1,000) Module coscs Indirect coses, general facilities, 6 contingencies, 302 34 -6 120 30 30 10 14 36 9 9 K Total fixed capital 44 60 156 39 39 Operating cost ($l,000/yr) Labor (aen/sblfc) 3 $14.20/man-hr Maintenance* (2 of module coat) -- (2) 1 (C'.5) 60 (4 ) 2 (0.1) (2) 12 2 (0.2) *>4 (3) (0.3) 36 (3) 1 Materials NaOH (502) 3 lOc/lb Ammonia (anhydrous) 3 $120/ton Phosphoric acid (1002) 3 5150/ton Lime (CaO) 0 $30/ton Copperas a $35/ton Sulfuric acid (1002) 3 $60/con .ycclve carbon ? 60c/lb Subtotal, materials -- -- ---- 16 -- -- ------ -- -- ------ -- -- ------ -- -- ------ -- -- ------ -- -- ------ -- -- ---- 16 L't llltles Electricity 3 2.6c/kwh s' Steam 3 $$.00/1,000 lb Subtotal, utilities --1 2 -146 2 -145 -- i-- ---- -- -- i-- Overhead, SOX of labor depreciation, 102/yr of fixed capital Waste disposal Solids 3 Sfe.SO/ton* Liquid 3 $25/1,000 lb* TOTAL OPERATING COST __ 30 46 ---- ---- 7 -47 6 12 18 16 4 4 ------ -- -- 20 36 42 95 197 mcd 00126S7 Table 6.2 (Concluded) TREATMENT COSTS FOR ETHYLENE PLANT WASTES Ethylene Plane Capaeitv: 1,0 x 10^ Ib/yr ac 0.9 Scream Factor Etnylene Plane Investment: $190 million PSP Cost Index: 290 Tine 3ase: January 1979 Capital mvestmenc ($1,000) Module costs Indirect costs, general facilities, 4 contingencies, JOT Total fixed capital Operating cost (Sl,300/yr) Labor (oen/shlft) ? sli.IO/aan hr Maincenance* (t of module cost) Materials NaOH (50t) 9 tOe/ib Ammonia (annvdrous) 3 $120/ton Phosphoric acid (ICCT) >3 $l5G/ton Line (CaO) ? SJO/ton Copperas >3 $35/ton Suifuclc acid (IC0T) 2 $60/con .Active carbon {? 6Ge/lb Subtotal, materials Jell it les Electrlcitv 0 2.6c/kwh Steam 0 $5.00/1,000 lb Subtotal, utilities Overhead, 50X of labor depreciation. 102 of fixed capital Waste disposal Solids J $6.50/ton' Liquid 0 S25/1.000 lb* TOTAL OPERATING COST Slol. Oxidn. 6 Slucae Seen. Neut ra11ration Active Carbon Adsorociof! Totals 530 157 687 100 30 130 165 t ,055 50 315 215 1,370 (1) i 20 (i) 21 -- 1 1 4 I -- -- 5 8 -- 8 60 69 3 -- 286 (C.5) (> bO 4 -- -- -- -- -- 71 -- 71 1 -- 1 30 13 -- -- 179 (0.5) 60 <<0 6 -- -- -- -- -- -- 19 19 372 (3.65) 38 16 1 1 2 1 71 19 111 l 12 -- -144 1 -132 30 186 21 237 --3 -- 20 137 735 'Labor and materials. TJ mile round trip at $2.50/ton plu S6.50/con landfill operation. ^Charge for disposal to hazardous-vast# management facility. 198 OOOO^688 c r C C ( 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 bn Water Quality (B-13934) gives three major sources of ethylene plant wastes; (1) Water quench cower 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 vriUi 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 the 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 85X to correspond to the major flow stream quanti ties in the preceding modular estimate, gives a comparable capital iny^ment of 4.48 x I/(7)0*6 - $1.40 million (i*e., a 2Z difference). Direct annual operating cost, excluding depredation, for the Frger flows was reported as $310,000 in 197^-equivalent to approxi mately $620,000 in 1979. This compares withfa scaled-up modular cost of $694,000/yr (+12Z). / MCD 000012689 * * Treatment Methods A creataenc sequence.for the combined wastes from acrylonitrile, ethylene/prcpylene, hexamethylenediamine, and methanol plants has been proposed by the lr.S. National Commission on Water Quality (B-13934). This scheme is illustrated;.by the block flow diagram of Figure 6.3 along with scream quantities and compositions. The adiponitrile wastes containing appreciable amounts of organics and cyanides are divided between incineration and deejp"well disposals. Hexamethylenediamine wastes are steam stripped to remove ammonia, ozonated to reduce cyanide concentration, and then treated to separate an oil phase. The remaining waste vtream is combined in an equalization and surge tank, with the wastes ft<*a ethylene and methanol plants. This combined stream, amounting ta 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 USt traqes 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 beajjs available demonstrated technology (8ADT) and $7.05 for best available technology (MT). Converted to January 1979 costs, these figures been* $9,0 and 4.1 million! respectively. Operating costs, excludingVepreciatioa, in 1973 vele $0.82 million for BADT and $1.55 million for kl--equiva&nt in 1979 ^llars, to approxi mately $l*b aod $3.i ailllo&rr respectively* We have reeetimated thel-pital an^ operating c multiplant waste keatment ssMnce on basis of moduipr cost and qkntities ftB Section 5 of this s modular cost is $9.\million a^kche tota\, fixed capi $12*^ million (Table 6.3). Tot^aoperating costs are annually--$2.0 milliou if devre^lotl is occluded. 2690 000-^ 00 V < r 201 000012691 MOD Table 6. 1 TREATMENT COSTS FOB COMB INED MLXTIPLANT WASTES Flint Capacities 'aiilion Ifi/yr a; 3.9 strata Ethylene & propylene 900 A4ison 11n1* ;:o Hexanet!v/ienedlan.Lne - 200 Methanol 7)0 Plane Investaent: >18) aillion PEP Celt Index: 290 Tlae Base: Uanuary ; (actor): Capital Investaent (SI.COO) Module costa Cooling water utllicy Indirect cases, 302 Total fixed capital Operating cosea (Sl.COG/yr) Labor (oen/shift) ? $ 1. 20/a*ft-hr Maintenance i S of nodule coat) Materials* Sultunc acid (100Z) 3 S60/toa Phoapnonc acia (1005) ? $150/Con Line <C0) ) 530/ton Copperas ? S35/con Active carbon ? bOe/lb Utilities Electricity 0 2.be,'kwh Fuel ' 52.30/Mil Lion Btu Overhead, 502 of labor Depreciation, 102/yr of F.C./yr Solid weete dlspoaal** Land spreading of blo-sollde C 2.50/ton LaMflll of carbon H 5.50/ton TOTAL OPERATING COST Incineration a.000 -- 1.200 5.300 (1) 120 (-) IbO -- -- -- -- -- 76 364 60 520 -- -- 1,300 Deep-Well In -action leaoma Sir-F;--j Ozonation Oil Seearaeion 1,450 -- D5 100 20 35 150 -- -5 L .365 155 195 5* -- -- 5 _ (0.5) 60 (0.2) 29 (0.1) 12 (1) 15 (-) < (5) 8 (9) Negl -- -- -- -- --- - 30 4 -- ** -- -- - 30 12 6 190 IS 20 - -- ---- 233 Ill M IS Edua. l tat ion 4 no ijret SO by___ : 00 (: > s 6 -- ?0 81 c r MCD 000012692 202 c e Tabls 6.3 (Concluded) treatment costs for combines miltiplant wastes Flint Capacities (alilion Lb/yr it 3.9 icr<u fietor): Ethylene a propylene Adlponitnle (exaaet r.v i e nedl aal n 900 110 100 "etnenol 7S0 Flint Investment: s385 aililon PEP Cost Index: .190 Tlse Base: January 1979 sut ra 11cat ion Capital investnenc ($1,000) !'oduis costs Cooling .itsr utility Indirect casts. JOS Total fixed capital Ipe r at ing costa (Sl.OOQ/yt) :: -- :o 90 labor (aen/shift) 0 StA.IC/oan-nr Maintenance (.1 of annuls cost) Materials* Juiiurie aetd (iCC*) ? SbO/tan '"'asjroric acid HCOt) 7 3:5C.;ton Line iCaO) ? 3 30/con Copperas ? S33 / ton Activs caroon 7 6Cc/lb (O.J) 60 (-) 3 12 -- -- --> -- .tlllctes Electricity ? 2.6c>*'.h Fuel 7 ;2.30/aillion Btu overhead, SC* of labor i3 -- 30 Depreciation, iGS/yr of f.C.,yr Solid Waste Disposal'* land spreading of blo-sollds 0 2.50/ton landfill of carbon 3 6.50/ton TOTAL OPERATTSC COST 9 -- 137 Activ*ta Dual Media Filtration 2,000 -- 600 2,600 230 -- '3 300 U> 120 (C.J) 60 (i> SO (5) 12 ---- s-- -- 5-- ---- 93 -- 60 260 7 -- 30 30 10 -- 637 -- -- 13* Activated Carbon Totals i, cco -- 3C0 1,300 9.543 ;o :,S6S 3o Cl> 120 {4.3) J'b (A) >0 (3.3) 327 -- 12 --9 -- :i --5 68 68 i 262 21 393 60 298 no l *i44 -- A AAA 1A -- 3,210 An all ski seer iccichtd to the cop of the eduelitatinn tank. 7 iBaoni* Iran the laaonn stripping is used la the activated sludge section. Mo credit la allowed for excess avonls. * Inemsrable teste* attuned to have eoebusclble content egual to 3.000 Btu/'lb of teste, "Excess stem free incineration is used for -------- '- stripping, No credit taken for scene feneration above this seounc. waste disposal is assuaed to be adjacent to plant; therefore hauling changes are ioaifaifleant. Coepanson reference: >'1 3936, Generalised Plant Ms. 16. 203 000012693 tfCD Discussion of Coses 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 modular cost estimating procedures in this report do not distinguish among BADT, BAT, and 3PT. Thus, it might be expected that the modular cost estinated here would occupy an intermediate position, as shown below: Modular costs Comparative costs BPT BADT BAT Estimated Capital Investment ($ millions) $ 12.4 Annual Opera ting Cost-- Excl. Deprec. ($ 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 $12 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 0.16c/lb on the combined product outputs of two billion lb/yr. MCD 000012694 204 Phosphoric 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 C- 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 frcm the phosphate dissolver off-gases scrubber. In addition, an allowance is made for 15,000 gph 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. SB 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 MCD 000012695 Figure 64 TREATMENT OF PROCESS PHOSPHORIC ACIO PLANT WASTES (DI HYDRATE WET PROCESS) Phcspnonc aod otant caoacity: 150 tod LIQUID WASTES 1 Aaueous fiuonoe SCruD solution (9.000 gphl H2SP6 <*st.) HF S1O2 COj h20 (H2S04 EQUIVALENT = 2.700 lb/hr) LIME <CaOl 11,540 lb/hrl lb/hr no 900 470 165 75.005 76.650 NEUTRALIZATION 2 Rainwater runoff 115.000 gph> avg SOLI 0 WASTES 3. Gypsum filter cake <1.100 ft3l lb/hr CaS04-2H20 H3P04 HF Ai2'Sld)3 Pe2<S)4l3 H2S.03 S1O2 h2Q 57.300 700 375 360 600 135 2.960 25.200 87.650 (90.000 gphi CD 4. Settled sludge <7.5 ft3) P205 Mixed oxides h20 lb/hr 202 256 42 500 im % SETTLING LAGOON SOLIDS TO LAND STOCKPILE (180 f(3/davl AQUEOUS OVERFLOW TO RIVER OR SEWER 127.000 gph) Reference: PEP Reoort No. 36. B-13936. LEGEND Module numbers MCD 000012696 206 r ... c v 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 C.i ft/hr. Other costs are read directly from the appropriate graphs and tables . Thus, the total module costs are $510,000. When indirect costs and service facilities are included, the fixed investment for waste treatment reaches $664,0C0. 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 $8.60/con (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%). 207 MCI) 000012697 Comparative operating costs were estimated at $343,000/yr in 1975 (B-13936), or about $400,000 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. MCD 000012698 Table 4*4 TREATMENT COSTS FOR PHOSPHORIC acid PLAHT Wastes (DIHTDRaTT ."T PROCESS) Phosphoric Acid Plane Capacity: 150 tpd ?2^5 ac 0.9 .Anneal Stress Factor Phosphoric Acid Plane Investment: 510 Billion PEP Cost Ir.dex: 190 Time Ease: January 1979 Neutralization Cypsua Scacicina Puaoln* Settline Laaoon Total Capital investment nodule cost Indirect coats & facilities 301 ($1,000) service Total fixed capital Operating cost* (SJ.OOO/yr) labor (oen/shift) 9 SI 4.20/aan-hr Maintenance (I of module cost) Materials, Line >3 S30/ton Electricity 3 Z*6Z/kvh Overhead 3 SOZ of Labor Depreciation, 105 of F.C./vr Sludge to stockpile ? 2.SO/ton Cypsua stacking 3 185/ton^ TOTAL OPERATING COST 260 78 338 (0.5) (4) 60 10 183 4 30 34 -- -- 321 -- 180 54 0 2 34 __ __ -- (1) 2 ---- -- 10 ---- -- 24 ---- 45 -- -5 36 70 22 92 __ (20) 14* -- -- -- 9 5 -- 26 510 154 664 (0.5) 60 26 183 14 30 67 5 45 $4 30 'Polyethylene Lagoon liner replaced every 4 years* rTwo mile haul (one way) at $i.5Q/ta n plus leveling at 51.00/too. ^Stackcing cost for 32 ton/hr solids* Including labor, material, overhead, and dapreclaltioa* 209 HCD 000012699 Appendix A COST 3ASIS The Qodule costs 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 corresponding 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 veil as quoted cost information, are also adjusted to a PEP Cost Index of 290. 211 000012700 mod Appendix B CALCULATION'S FOR THE EQUALIZATION' OF A WASTE STREAM FLOW VARIABLE (Reference B--1395) Samples of the wascewacer scream 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 lower value to occur (see Figure B.l). Now, the standard deviation in the feed "tff" is equal to one-half of the difference of the values occurring at probability percentages of 15.9% and 84.1%. That is: <yf - BQD 84,1% -30P 15.9% 2 980 - 380 . 300. 2 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 cummulative normal distribution "Y" 1.65 (Table B.l), the standard effluent deviation: "<?e" - 895 - 680 130 mg/liter 1.65 The required residence time in the equalization vessel is: C - 1 X m * 32 hr or 1.33 days 213 MCD 000012701 where: At cycle time of the variable from a mean value <7f and <je feed and effluent standard deviation, mg/ liter t equalization 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 Figure B.1 PROBABILITY PLOT OF BOD VALUE Source: B-1398. o'* 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 P(X)* .9946 . 99 53 .9960 .9965 ,9970 .9974 .9978 .9981 .9984 .9987 .9989 .9990 .9992 .9993 .9994 .9996 .9997 .9998 .9999 1.0000 215 MCD 000012703 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-SA) Xvt where S0 * influent BOD, COD, or total oxygen demand (TOD), mg/liter Se - effluent soluble BOD, COD, or TOD, mg/liter Xy * average MLVSS concentration--mg/liter (for conventional biological oxidation, Xy 5*1,500 to 3,500) t * aeration time, day"^ K * organic removal rate coefficient, day-* y * concentration of nonbiodegradable organics, mg/liter. 2. The variation of the removal rate coefficient with temperature is given by the equation: K2 - Ki e <T2-Ti) where: * coefficient at temp. Tj, C K2 * coefficient at temp T2, C 9 temperature coefficient (ad.03 to 1.09) 217 MCD 000012704 Figure C.1 DETERMINATION OF SOD REMOVAL RATE COEFFICIENT c A*p/ l ' r Source: 8-1395. 218 MCD 000012705 c L 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 * a1 Sr+b' xXv where: Rr a' & b' Sr x t total oxygen usage, lb/02/day oxygen utilization coefficients BOD (COD or TOC) removed, lb/day average MLVSS concentration, mg/liter biodegradable fraction of MLVSS aeration tiQe, days* A. Constants in the equation for sludge- production are determined from a graph of sludge formation (AXy/xXv) against BOD removal per day (Sj./xXyt) as shown in Figure C.3. aXy * a Sr - bxXy where: Xy * 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 + bXy- y(aSr+bXy)2 -(AbXy) 0.77aSr x* 11 2bXv 219 MCD 000012706 Figure C-2 DETERMINATION OF OXYGEN UTILIZATION COEFFICIENT lb hio<k'i)( jild ljlt: V S S -iljy Source: 9-1395 WCD 012707 220 Figure C.3 DETERMINATION OF SLUDGE PRODUCTION COEFFICIENT lb VSS produced III broduyr jiJulilt.- VSS ddy Source 0-139S. 221 MCD 000012708 6. Nutrient requirements are estimated from the following two equations: 0.123 x Xv + 0.07 (0.77-x) Xv, lb/day 0.77 0.77 0.026 x Xv + 0.01 (0.77-x) Xv, lb/day 0.77 0.77 7. Aerator horsepower is approximated from the relation: lb BOD removed per day hp 45 8. Finally, the clarifier size is determined as indicated for sedimentation separation under ''Primary Treatment" (page 67) C t / 222 MOD 000012709 C c r Appendix D c FIXED BED ACTIVE CARBON1 ADSORBER CAPACITY The design of fixed bed adsorbers requires experimental data for the adsorbabilicy 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 time 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. 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