Waste Generation in the Organic Chemicals Industry: A Future Perspective The MITRE Corporation ------- Waste Generation in the Organic Chemicals Industry: A Future Perspective John W. Watson AlanS. Goldfarb Vivian R. Aubuchon October 1980 MTR-80W229 Sponsor: Environmental Protection Agency Contract No: EPA 68-01-5064 The MITRE Corporation Metrek Division 1820 Dolley Madison Boulevard McLean, Virginia 22102 ------- ABSTRACT Possible trends in waste generation by the organic chemicals industry are described and the quantities of waste that could be generated are projected to the year 2000. Some chemical process options that could reduce hazardous waste generation are identified. Increased waste generation accompanying a shift from petroleum-based feedstocks to ones based on coal and oil shale is discussed. In addition, research topics for the future are identified. iii ------- PREFACE AND ACKNOWLEDGEMENTS This is one of several documents on environmental trends and future problems produced to support the Environmental Protection Agency's Office of Strategic Assessment and Special Studies (OSASS) in preparing its annual Environmental Outlook report. That report assists the Agency in its long-range research and development role. Last year's Environmental Outlook 1980 was an ambitious project, covering a broad spectrum of issues. This year, studies like this one focus on selected issues, dealing with them in greater depth. This approach was conceived by Dr. Irvin L. (Jack) White, formerly with the Environmental Protection Agency (EPA), and project guidance was provided by John W. Reuss, OSASS director. MITRE staff members who played central roles in the development of this study included: Brian Price, program manager; Beth Borko, project manager; Carol Kuhlman, production support; Tina McDowell, editorial support; and Sharon Hill, typing support. Valuable guidance was provided by Dr. Stephen Lubore and Ernest P. Krajeski, both of MITRE, as well as Dr. Morris Levin and Donald Cook of EPA and Dr. Frank Maslan, a consultant to EPA. iv ------- TABLE OF CONTENTS Page LIST OF FIGURES vii LIST OF TABLES viii EXECUTIVE SUMMARY x 1.0 INTRODUCTION 1 1.1 Purpose 1 1.2 Background 2 1.3 Approach and Structure 3 2.0 CONCLUSIONS 7 2.1 Industry's Options 7 2.2 Topics for Future Research 11 2.3 Regulatory Actions and Institutional Concerns 15 2.4 Summary 18 3.0 CURRENT TRENDS AND POTENTIAL FOR CHANGE 19 3.1 Chemical Industry Output and Production Mix 19 3.2 Potential Changes 25 3.3 Regulatory Factors 27 4.0 FEEDSTOCKS FOR CHEMICAL PRODUCTION 29 4.1 Base Case Projections 29 4.2 Derivation of Alternative Scenario 31 4.3 Comparison of Waste Loads 34 5.0 SELECTED PETROCHEMICAL BASICS AND INTERMEDIATES: 39 BASE CASE PRODUCTION AND POTENTIAL FOR CHANGE 5.1 Derivation of Projections for Year 2000 44 5.2 Alternative Scenarios Affecting Selected 44 Organic Chemicals 6.0 PROJECTIONS FOR SELECTED PETROCHEMICAL BASICS 57 6.1 General Characteristics of the Scenarios 57 6.2 The Petrochemical Basics 59 v ------- TABLE OF CONTENTS (Concluded) Page 7.0 PROJECTIONS FOR INTERMEDIATE ORGANIC CHEMICALS 71 7.1 General Characteristics of the Scenarios 71 7.2 The Intermediate Organic Chemicals 73 APPENDIX A HAZARDOUS WASTE 97 A.I Quantities of Hazardous Waste 97 A. 2 Characteristics and Implications 98 A. 3 Current Laws and Regulations 100 A.4 Management and Disposal Techniques 103 A. 5 Distribution of Chemical Waste 105 APPENDIX B CALCULATIONS OF ESTIMATED PRODUCTION IN YEAR 107 2000 APPENDIX C SIMPLIFIED DIAGRAMS ILLUSTRATING DERIVATION 109 PROCESSES FOR SELECTED CHEMICALS APPENDIX D GLOSSARY 117 REFERENCES 119 vi ------- LIST OF FIGURES Figure Number Page 1 U.S. Production of Benzene 1950-2000 22 2 Sources of Petrochemical Feedstocks 1975 23 3 Actual and Projected U.S. Use of Natural Gas 1965-2000 51 A-l States Producing Selected Petrochemical Basics and Intermediates 106 C-l Production Sources of Cehmicals Selected for Study 110 C-2 Alternative Routes to Propylene Derivatives 111 C-3 Alternative Paths for Producing Ethylene and Ethylene Derivatives 112 C-4 Alternative Routes to Acetic Acid 113 C-5 Ethanol from Plant Sources and Ethanol from Ethylene 114 C-6 Processes and Derivatives of Harvested Wood 115 vii ------- LIST OF TABLES Table Number Page 1 Chemicals Selected for Analysis 4 2 Top 12 Organic Chemicals 20 3 Feedstock Production, Base Case, 30 1975 and 2000 4 Waste Generated from Feedstock Production, 32 Base Case, Year 2000 5 Waste Factors Associated With Alternative 35 Feedstock Sources, Year 2000 6 Wastes Resulting from Feedstock Sources, 36 Alternative Scenario, Year 2000 7 Production of Selected Petrochemical 40 Basics, 1977 8 Production of Selected Intermediate 41 Organic Chemicals 9 Production of Selected Petrochemical Basics, 45 Base Case and Year 2000 10 Production of Selected Intermediate Organic 46 Chemicals, Base Case and Year 2000 11 Effects of Changes in Feedstock Sources on 48 Production of Selected Intermediate Organic Chemicals 12 Waste Generation Factors for Selected Petrochemical Basics 58 13 Ethylene - Production Assumptions, Year 2000 60 14 Ethylene - Waste Projections, Year 2000 62 15 Propylene - Production Assumptions, Year 2000 65 16 Propylene - Waste Projections, Year 2000 66 viii ------- LIST OF TABLES (Concluded) Table Number Page 17 Benzene - Production Assumptions, Year 2000 68 18 Benzene - Waste Projections, Year 2000 69 19 Acetic Acid - Production Assumptions, 75 Year 2000 20 Acetic Acid - Waste Projections, Year 2000 76 21 Acetylene - Production Assumptions, Year 2000 77 22 Acetylene - Waste Projections, Year 2000 78 23 Acrylonitrile - Production Assumptions, Year 2000 80 24 Acrylonitrile - Waste Projections, Year 2000 81 25 Ethanol (Ethyl Alcohol) - Production Assumptions, Year 2000 83 26 Ethanol (Ethyl Alcohol) - Waste Projections, Year 2000 84 27 Methanol - Production Assumptions, Year 2000 86 28 Methanol - Waste Projections, Year 2000 87 29 Phenol - Production Assumptions, Year 2000 89 30 Phenol - Waste Projections, Year 2000 90 31 Vinyl Acetate - Production Assumptions, 92 Year 2000 32 Vinyl Acetate - Waste Projections, Year 2000 93 33 Vinyl Chloride - Production Assumptions, 95 Year 2000 34 Vinyl Chloride - Waste Projections, Year 2000 96 ix ------- EXECUTIVE SUMMARY Potentially Hazardous Waste In The Organic Chemicals Industry The organic chemicals industry generates an estimated 12 million tons of potentially hazardous waste each year. If present trends continued, that figure would rise to 32 million tons by the year 2000. Present trends are unlikely to continue, however, because economic factors and technological advances are making it feasible to use feedstocks derived from coal, oil shale and biomass, instead of the petroleum-based feedstocks that have long been staples in the chemical industry. This limited study outlines several paths the industry might follow over the next 20 years, pointing to increases in waste gen- eration that could accompany a shift from petroleum-based feedstocks to fossil-fuel alternatives. It identifies processing options that could reduce hazardous waste, but notes that any reductions may be outweighed by the tremendous increases in potentially hazardous waste generation that would accompany widespread use of non-petroleum-based feedstocks. Forces Affecting the Organic Chemicals Industry Several forces are working to change the industrial climate, perhaps altering chemical products, processes and feedstocks, along with waste by-products. These forces include: o The availability and price of petroleum and related feedstock sources, including natural gas; xi ------- o Technological advances in producing feedstocks from materials other than petroleum; o The way in which available petroleum and alternative mate- rials are distributed between the chemical industry and com- peting uses such as fuel; o Costs associated with alternative processes, including capitalization costs for plant modification or replacement, operating expenditures and energy needs; and o Government regulations that might encourage the use of cer- tain processes, such as recycling materials that would other- wise be disposed of as waste. Industry's Options External influences, including Federal policy, could cause industry to employ any combination of the following actions: o Other energy sources, including coal and oil shale, could be used to supplement natural gas and petroleum for energy needs, freeing petroleum for chemical feedstocks; o Coal and oil shale could be processed into the basic chemical feedstocks; o New processes could be developed (or tested processes could be adopted commercially) for producing chemicals using feed- stocks more simply derived from coal such as acetylene, syn- thesis gas, methane and methanol; o Garbage and other refuse could be used to produce methane; and o Biomass could be employed as a source of chemical feed- stocks. Government's Role EPA's regulatory policies could play a key role in encouraging the use of favored processes or feedstock sources. Government can influence industry actions with regulations that affect the economic xii ------- trade-offs involved in chemical production. Stringent requirements for decontaminating hazardous waste could make it economically at- tractive to recycle or adopt processes that minimize waste generation. Before a comprehensive waste management policy could be devised, research is needed in several areas including: o The amount of hazardous waste generated by different chemical processes. For instance, data could be collected on the make-up of wastewater from given processes to determine what percentage is solid waste and how much is hazardous. o The concentration of hazardous materials present in wastes that remain after refuse is recycled. o The trade-offs involved when waste is transformed from one form to another. An example of this would be the hazardous particulates, sulfur oxides and other atmospheric contami- nants from coal processing, which are removed at the price of additional sludge and solid residues typically disposed of on land. o The relative energy requirements for the most important chem- ical production processes. (For example, an analysis found that the derivation of acetic acid from acetaldehyde is less energy-intensive than the alternative process using methanol by a ratio of 1.2-to-l.) o Much deeper understanding of alternative production routes— and their waste-related implications—that will be available to the industry as it responds to regulatory and other pres- sures in years to come. xiii ------- 1.0 INTRODUCTION The organic chemicals industry is currently a major generator of waste regulated under Subtitle C of the Resource Conservation and Recovery Act (RCRA). Precise figures on waste generation are lacking, but estimates developed when the RCRA regulations were proposed indicated that the organic chemicals industry generates an estimated 12 million tons of hazardous waste each year (Maugh 1979). Maugh (1979) estimated that hazardous waste generation could expand by 3 percent each year. Waste generation by the organic chemicals industry may increase more rapidly because chemical production is increasing at a faster pace than industry as a whole. Despite these estimates, the waste loads by the end of the cen- tury may not be those that would be anticipated from current rates of generation and industrial growth. Nor are they necessarily those which would be estimated using any assumptions based only on recent trends. 1.1 Purpose This study explores the future, outlining options open to the chemical industry as it grapples with petroleum shortages and RCRA regulations. Pointing to limitations in the current data base that hamper predictions, the study also suggests an agenda for research and development. Despite those limitations, it sketches a picture of waste generation in the year 2000—or several pictures—indicating what could happen if the chemical industry continued to follow present trends, or if it embarked on any of a number of new trends. ------- 1.2 Background As recently as 1970 a thoughtful study of the organic chemicals industry reported that the latest developments in processing petroleum- and natural gas-based feedstocks had made it possible to almost totally eliminate coal and coal tar as souces of chemical raw materials in the U.S. Calling this trend "irreversible," the study said, "The return to coal...seems unlikely...at least as long as known petroleum reserves continue to increase" (Hahn 1970). That projection has been relegated to the realm of naive opti- mism by soaring oil prices and uncertain pertroleum supplies. The average price of a barrel of oil rose from $1.80 in August 1970 to about $32 by August 1980 (Ross 1980) and the unpredictability of petroleum supplies was demonstrated by the Arab oil embargo of 1973-74 as well as the 1979 gasoline crisis. Industry has turned anew to building plants for the gasification and liquefaction of coal (Van Slambrouck 1980, Abelson 1980). By 1979, experts wrote that, "The manufacturing community must turn away from natural gas and, ultimately, oil" (Anderson and Tillman 1979). One projection holds that by 1985 the output of coal-derived chemi- cals will be more than eight times the 1975 figure of 1.2 million tons (Anderson and Tillman 1979). With an increase in the use of coal, feedstock production pro- cesses may change. Furthermore, regulatory pressures could change production methods, favoring processes which generate less waste and ------- those which recycle intermediate products to cut down on hazardous waste generation. 1.3 Approach and Structure After a preliminary examination of waste generation associated with alternative feedstock sources, five basic petrochemicals and eight intermediate organic chemicals were analyzed to illustrate the effects of various factors on waste generation (see Table 1). The chemicals were selected on the basis of production volume and the variety of methods available for their production. Used to make a variety of products from insecticides, to detergent, to gasoline, they are important in everyday life. A literature search yielded data on the nature and quantity of waste generated during production by each method and the quantity of each chemical produced by each method. Production volumes were pro- jected for the year 2000 and the quantities of waste that would be generated under varying assumptions of possible production process mixes in the year 2000 were calculated. Section 2 of this study summarizes conclusions that can be drawn from data presented in the sections that follow. Section 3 offers background information on chemical production and external forces affecting industry. Sections 4 through 7 provide a detailed analysis of potential future chemical production and waste generation. Infor- mation on feedstock production and resultant wastes is included in Section 4 with two projections for the future—a "base case" scenario ------- TABLE 1 CHEMICALS SELECTED FOR ANALYSIS Petrochemical Basics Representative Products Intermediate Organic Chemicals Representative Products Benzene Ethylene Propylene Toluene Xylene(s) Dyes, detergents, gasoline, plastics Plastics Plastics Solvent, explosives (TNT), gasoline octane booster Gasoline octane booster, solvent, synthetic fibers Acetic acid Acetylene Acrylonitrile Ethanol (ethyl alcohol) Methanol Phenol Vinyl chloride Vinyl acetate Synthetic fibers, safety glass, surface coatings (paint) Plastics, synthetic fibers, solvents Synthetic fibers, plastics, gaskets Solvent, cosmetics, surface coatings, vinegar, drugs Antifreeze, synthetic fibers Plastics, adhesives Plastics (garden hose, pipe) Adhesives, paint, floor tiles, phono- graphic records, safety glass ------- that assumes no change in present production methods and a contrast- ing "alternative scenario." Section 5 provides information on current production quantities and process mixes for each of the 13 chemicals studied, along with baseline production projections through the year 2000 for each chemical. It also discusses conditions that would define alternative scenarios of production volume and process mixes for these chemicals. Chemical-specific alternative scenarios are offered in Section 6 for the selected petrochemical basics and Section 7 for the intermediate organic chemicals. Presented in tabular form, these scenarios give alternative projections of chemical production and waste generation, based on varying assumptions of process mixes. ------- 2.0 CONCLUSIONS 2.1 Industry's Options 2.1.1 Critical Factors A number of forces are acting to shape the future direction of the chemical industry in terms of products made, processes used and wastes generated. Foremost among these forces is the diminishing availability of conventional feedstock sources—natural gas, natural gas liquids and petroleum. The demand for organic chemicals and the feedstocks for chemicals is projected to continue to increase through the end of the century and beyond. If conventional feedstocks prove inadequate to meet the increasing demand for chemicals and fuel, alternative feedstock and energy resources will have to be developed, principally from coal and oil shale. Reliance on such alternatives would probably lead to a larger increase in hazardous waste generation than if present trends continued to the year 2000. In making optimum use of available fossil fuel resources to meet the nation's needs for both chemicals and energy, any combination of the following options might be employed: 1. Coal and oil shale resources can be used to supplement natural gas and petroleum for energy needs, permitting the chemical industry to use an increasing share of the avail- able natural gas and petroleum for feedstock production. 2. Coal and oil shale resources can be processed into the basic chemical feedstock categories—olefins, aromatics, and syn- thesis gas. 3. New processes may be developed for producing desired chemi- cals using feedstocks that are more simply derived from coal, such as acetylene, synthesis gas, methane, and methanol. ------- With the first two options, there would be little or no change in processing techniques used by the chemical industry to produce products. The types of waste generated by the industry would be similar to those produced today, but the quantity of waste would be considerably greater because of increased production. Although there would be little change within the chemical industry, option 2 could lead to an increase in hazardous waste generated outside the indus- try. In the derivation of feedstocks from coal, heavy metals and radioactive isotopes find their way into the large volumes of ash requiring disposal. Because of these same hazardous constituents in coal, option 3 could lead to an increase in hazardous waste generated by the chemi- cal industry itself. It is difficult to generalize about the quanti- ties involved because coals vary in composition, but studies of hazardous constituents are underway (Koppenaal and Manahan 1976). The implications for waste generation during the manufacture of chanicals from these alternative feedstocks is not clear. It is likely that the quantity and type of waste generated will differ from one chemical to another. In addition to fossil fuels, other resources such as biomass and refuse probably will be used to a greater extent for chemicals and fuel. Fermentation of biomass yields high volumes of by-products and solid residues, although available literature offers little indica- tion that such waste would be hazardous. Use of refuse and other ------- discarded materials to produce methane and the chemicals derived from it is likely to result in residues and liquid effluents with toxic or corrosive properties. 2.1.2 Some Specific Options and Their Waste Implications By the choice of raw materials and processes used to derive specific chemicals, significant reductions can be achieved in quantities of solid and semi-solid waste requiring disposal. Some chemical production routes could eliminate residues with hazardous properties and/or provide opportunities for recycling. However, a shift away from the use of petroleum-derived feed- stocks could lead to the use of alternatives that would yield hazardous waste. The large volume of waste associated with shale oil processing could become a consideration in manufacturing the olefinic feedstocks, including ethylene and propylene. Lately, a decline in the volume of waste generated in manufacturing such feedstocks, has accompanied a trend toward using heavier petroleum feedstocks.* The chemical industry could instead use a shale oil-based feedstock that is essentially the same as petroleum. Its use would not alter the nature or quantity of waste generated in the production of olefins; however, indirect waste from shale oil processing must be considered. fci.e., the heavier parts of petroleum. ------- Obviously a reduction in the demand for olefins as feedstocks would reduce the quantity of waste generated during olefin produc- tion. However, substitution of coal-based materials (such as tar oils and acetylene) for olefins seems likely to result in increased residues requiring disposal. Processes using tar oils and acetylene tend to generate more solid waste than other, currently more widely- used, routes. There is another consideration: the larger volume of waste generated with coal-based materials may sometimes contain a smaller portion of hazardous components than the waste generated by today's popular processes. The trade-offs involved differ from one chemical to another. Commercialization of demonstrated technology for deriving products from coal by plasma pyrolysis could reduce solid waste. An increased use of coal tar to derive the BTX aromatics (benzene, toluene and xylene), would result in a greater increase in the volume of waste generated than if they were to continue to be derived from refinery reformate and pyrolysis gasoline. The use of heavier petroleum feedstocks to produce olefins results in the production of pyrolysis gasoline so the current trend toward using heavier feedstocks for olefins would assure an increasing supply of pyrolysis gasoline for aromatics. An increased use of toluene to make chemicals now derived from benzene would reduce the volume of waste generated in producing aro- matics, particularly benzene. However, processes using toluene 10 ------- rather than benzene in the further manufacture of chemicals may generate more waste. Finally, the greatest potential for increased hazardous waste generation lies in a possible shift from feedstocks based on petro- leum and natural gas to ones produced from coal or oil shale. Vari- ations possible from alternative production routes to intermediate organic chemicals seem modest by comparison. In general it would be reasonable to conclude that, while the chemical industry will generate an increasing quantity of waste as a result of the increased demand for chemical products, changes in technology could reduce this volume to a lower level than it would otherwise have been. However, these improvements must be viewed in light of the potentially greater quantities of waste associated with feedstock production from coal and oil shale. 2.2 Topics for Future Research 2.2.1 Extension of the Data Base Only a small segment of the chemical industry has been analyzed in this study (13 out of a potential universe of more than 500). It would be interesting to extend this analysis to consider more chemicals, such as those described in "Industrial Process Profile for Environmental Use" (Liepins et al. 1977, Chapter 6).* *This reference document is part of the extensive data base being developed by EPA which will increasingly facilitate analysis of forces affecting future waste generation in the chemical industry. 11 ------- Another desirable extension of the information base would be to obtain quantitative estimates of hazardous waste generated in the production of specific chemicals. For processes that generate large volumes of wastewater, there frequently is no information on how much of the wastewater becomes solid waste, and whether the residual solid waste might be considered hazardous. Information on waste generation is often not available for older, discontinued processes and those using coal tar. With petroleum in short supply, some of these pro- cesses might return to favor. Recycling various forms of refuse to produce methane and some higher molecular-weight hydrocarbons offers a way to reduce solid waste. It will be important to determine the net gain in terms of quantities of refuse consumed per production unit, the resulting residuals, and the concentrations of hazardous components. It has been reported that wastewater from the production process may amount to more than 75 gallons per ton of municipal refuse. Cadmium, mer- cury, and heavy metals are known to be present in some refuse usable as feedstocks, while ammonia, hydrogen cyanide and hydrogen sulfide can be formed in the recycling of some materials (Jones 1978). Information on the resulting concentrations is needed to develop an approach to solid waste management. Another subject for research lies in the fact that some chem- icals are produced from raw materials that are processed to recover other chemicals. For instance, benzene is just one of several 12 ------- chemicals extracted from coal tar. The simultaneous production of several chemicals from a single feedstock has implications that are not addressed in this study. If the market for the different chemicals does not correspond to the production distribution, some of the chemicals may wind up as waste. Yet another area requiring examination relates to the trade-offs made when waste is transformed from one form to another. Regulated removal of hazardous particulates, sulfur oxides, and other atmos- pheric contaminants is achieved at the price of additional sludge and solid residues typically disposed of on land. For example, in coal burning, lime sludge is produced by scrubbers used to desulfurize flue gas. This represents a significant source of solid waste. Similarly, the removal of more solids from wastewater would increase requirements for land disposal. 2.2.2 Commercial Feasibility and Extent of Substitution Alternative methods of deriving chemicals considered in this study are technologically proven on at least a laboratory or pilot- project scale. However, various uncertainties remain which affect the feasibility of commercializing specific processes and, hence, the types and quantities of wastes that would result. A shift away from petroleum would depend on the availability of substitutes and processing costs. Other considerations include capi- talization costs for plant modification or replacement as well as costs of materials and energy. These costs hinge on technology, 13 ------- since process modifications resulting in greater efficiency can reduce long-term costs, even if they are initially expensive. A good example of alternative derivation routes, materially assisted by technological improvements, is provided by the possibili- ty of large-scale industrial production of ethanol and other hydro- carbons with improved fermentation techniques (long 1978). Acetylene and other small-molecule hydrocarbons can be produced by plasma pyrolysis of coal. The process has not been commercially successful, but it would be interesting to determine the likelihood of its becom- ing so. Similar questions remain regarding other alternative deriva- tion routes which affect waste generation. These include production of acrylonitrile from acetylene and from propylene by recycling acetonitrile waste (Gelbein 1979). In the 1990s, energy requirements for different processes may become a more serious constraint on derivation options than capital costs. Information is needed to estimate to what extent such con- straints would apply and how they might affect production of specific chemicals. The derivation of acetic acid from acetaldehyde is less energy-intensive than the methanol route by a ratio of about 1-to- 1.2 (Liepins et al. 1977). The available data base does not gener- ally provide a means for such comparisons, however, and it seems important to determine the relative energy requirements for the most important chemical production processes. In an energy shortage, such 14 ------- requirements are likely to strongly influence the processing routes chosen and the resulting waste loads, so this area is of particular concern. Interaction with other industries must also be considered. Benzene and other aromatic chemicals are obtained as a byproduct of coke production by the steel industry. Processing coal tar generated during coke production to obtain aromatic chemicals results in the production of a relatively high volume of hazardous residual waste per unit of production, compared with other methods of obtaining the aromatics. However, since coke production is essential to steel making, the coal tar will be produced as long as steel is made. Processing this coal tar to produce useful materials is preferable to disposing of the tar entirely. 2.3 Regulatory Actions and Institutional Concerns One of EPA's goals is to minimize the volume of waste—particu- larly hazardous waste—generated by industry. However, forces are acting beyond the control of either industry or EPA to influence the allocation of resources between energy and chemical uses, influencing the quantity of waste generated. To minimize waste generation, EPA should have a role in determining the allocation of resources and chemical processing routes. The Federal Government can use subsidies and tax advantages, as well as regulatory requirements and prohibitions, to encourage the use of feedstock sources and processes that promise minimal hazardous 15 ------- waste generation. The role of regulatory constraints in altering the relative cost-effectiveness of various processes is important. Rigid requirements involving expensive waste control equipment and proce- dures can make processes which generate less waste more cost- effective, in spite of higher expenses in capital, material, and operation. Complex factors must be studied to determine an appropri- ate level of environmental protection that can be attained at an affordable cost to the economy. Here, the classification of waste components and concentrations as "hazardous" plays an important role. Special attention should be devoted to waste streams and resi- dues from producing feedstocks based on coal tar and oil shale be- cause of their potential quantities. On the other hand, policy could be formulated to encourage processes that reduce waste generation. Reclaiming chemicals from refuse would reduce the nation's total waste burden, although the concentration of hazardous substances in the resultant waste would increase. With fermentation—a process that can be used to produce ethanol and several other important chemicals—the resulting waste could often be used as livestock feed. In considering process options, the quantity of waste generated may be less important than the hazardous nature of the waste. The cost of energy must also be considered in evaluating process options. A process producing less waste may require more or less energy to operate. Yet another factor is the energy cost associated with collection and disposal of the waste. 16 ------- Finally, government policy could play a role in determining the extent to which various feedstock sources are available for chemical use. Government support in one form or another can expedite produc- tion of gaseous and liquid hydrocarbons from coal. Conversely, restrictions or rigorous controls can delay development of these sources and of shale oil. While the major impact of government policy is sure to be felt in the energy sector, the chemical industry would also be affected. How government might act to influence the distribution of conversion products from fossil fuels to various sectors of the economy represents a significant unknown. Dwindling petroleum stocks might be regulated to ensure an ade- quate supply for chemical purposes, with energy needs met from the synthetic products. If so, there would be relatively small change in chemical waste volumes, since the industry could essentially continue present procedures. Conversely, during a petroleum shortage, a Federal policy which gave high priority to energy needs and agricul- ture could restrict chemical use of synthetics even to the extent of curtailing production of organic chemicals. A similar effect could result from a policy that channeled edible biomass to relieve malnu- trition at the expense of industrial production. Most of these issues, of course, are beyond the domain of EPA alone. But their resolution will influence volumes and types of chemical wastes generated by the year 2000 in the organic chemical industry. In the final analysis, it may be that forces constraining 17 ------- the availability of petroleum will leave industry with no alternative but to resort to coal and oil shale, with attendant large increases in waste loads. 2.4 Summary In summary; the prospect is for larger quantities of solid and semi-solid wastes by the year 2000 from the organic chemicals industry. This increase, if it occurs, is likely to be due to the necessity to rely to a larger extent on substitutes for petroleum and natural gas as feedstock sources. In this situation, increases attributable to the chemical industry will be small compared to those resulting from energy production, but they will be significant compared to changes in quantities of waste generated from downstream chemical production. The questions addressed here are among those which will deter- mine the extent to which waste generation may increase. A thorough exploration of these questions will require a comprehensive informa- tion base. Regulatory concerns and institutional incentives offer an opportunity to reduce overall waste by favoring selection of those processes that maximize recycling and minimize residuals requiring ultimate disposal, especially residuals with potentially hazardous components. 18 ------- 3.0 CURRENT TRENDS AND POTENTIAL FOR CHANGE 3.1 Chemical Industry Output and Production Mix Industry is churning out enormous quantities of chemicals to satisfy a growing demand for an array of products—from auto parts to stockings, and from pipe fittings to synthetic coats. Production of synthetic organic chemicals in 1977 amounted to more than 87 million tons, up nearly 10 percent from the 79.6 million tons produced in 1976 (U.S. International Trade Commission 1978). Production of the top 50 organic chemicals totaled 86 million tons in 1978 compared with 80.3 million in 1977 (American Chemical Society 1979). Outputs of the 12 organic chemicals produced in the greatest quantities in 1978 are listed in Table 2. The chemical industry relies heavily on petroleum and associated products for feedstocks, yet it consumes a small share of available refined crude oil. Petrochemical feedstocks produced from petroleum, including liquid refinery gas, totaled about 145 million barrels in 1976 (Bureau of Mines 1976)—a figure that amounted to only about 3 percent of refined petroleum products used in the U.S. (American Petroleum Institute 1976). Natural gas consumption in 1976 for petrochemical feedstocks came to more than 630 billion standard cubic feet—again representing about 3 percent of all U.S. usage. Sales of liquefied petroleum gases and ethane in this country for feed- stocks amounted to more than 140 million barrels (Bureau of Mines 1976). 19 ------- TABLE 2 TOP 12 ORGANIC CHEMICALS Chemicals Ethylene Propylene Benzene Ethylene Dichloride Toluene (All Grades) Ethylbenzene Vinyl Chloride Styrene Formaldehyde (37% by Weight) Methanol Xylene Terephthalic Acid Production (106 Tons) 1978 14.1 7.7 5.7 5.2 4.6 4.2 3.5 3.4 3.2 3.2 3.1 3.0 1977 12.7 6.7 5.6 5.5 3.9 4.2 3.0 3.4 3.0 3.2 3.0 2.7 Average Annual Growth 1968-78 (Percentage) 7.9 7.4 4.1 8.1 6.2 7.6 8.9 6.4 4.1 5.2 4.1 14.4 Source: American Chemical Society 1979. 20 ------- Feedstocks from sources other than petroleum and natural gas have declined in importance, despite today's renewed interest in them. In 1975 only about 2 million barrels of petrochemical feed- stocks were derived from light oils, coke and coal tar processing (Bureau of Mines 1976). The contribution of this source has declined markedly since the end of World War II—a fact illustrated by the trend in production of benzene, a major building block for synthetic organic chemicals (Liepins et al. 1977). In 1950 only about 5 per- cent of benzene production came from petroleum but by the early 1960s the fraction had climbed to more than 75 percent as shown in Figure 1 (Grayson 1963). By 1977, it exceeded 80 percent (Anderson and Tillman 1979). Sources such as plant derivatives are currently insignificant. Before 1945, however, ethanol was commonly derived from grain, molas- ses, and other plant sources as an important first step in world pro- duction of ethylene (Kochar and Marcell 1980). Now in the U.S., the procedure has been reversed. More than 90 percent of ethanol used to produce organic chemicals is derived from ethylene. As illustrated in Figure 2, the mix of feedstocks used in the production of chemicals is roughly as follows: petroleum and lique- fied refinery gas, 38 percent; natural gas and natural gas liquids produced at gas processing facilities, 61.5 percent; and other sources—chiefly coal oils—less than 1 percent (Bureau of Mines 1976). Tiny amounts of plant derivatives are used to produce 21 ------- — ^ —— Projected Range 1950 1955 1960 1965 1970 1975 1980 1985 1990 2000 Year Source: Adapted from Ayers, G.W. 1964, Debreczeni, £ J. 1977, Purcell, W.P. 1978, and Sherwin and Frank, 1975. FIGURE 1 U.S. PRODUCTION OF BENZENE 1950-2000 22 ------- BIOMASS (Trace) FIGURE2 SOURCES OF PETROCHEMICAL FEEDSTOCKS 1975 23 ------- industrial chemicals. However, somewhat larger quantities are used by the distillery industry and in food processing. Not all of the petrochemical feedstocks reflected in these percentages are used in producing organic chemicals. Nearly 75 percent of the natural gas devoted to feedstock use in 1976 went to produce ammonia (Bureau of Mines 1976). Nevertheless, the breakdown is indicative of the current production mix. The organic chemicals industry has grown at a rate of nearly 6 percent annually as indicated by a growth rate of 5.7 percent per year for the top 50 organic chemicals from 1968 to 1978 (American Chemical Society 1979). Growth through the remainder of the century is projected at more than 6 percent annually until about 1985 (U.S. Environmental Protection Agency 1980b). Thereafter, output of organic chemicals is expected to increase by about 3.5 percent per year, reaching more than three times the 1978 production volume by 2000 (U.S. Environmental Protection Agency 1980b, Bureau of the Census 1978). Hazardous waste generation by the industry could be expected to keep pace with increased chemical production. Details on hazardous waste quantities, characteristics, regulations and disposal methods are provided in Appendix A. Supplies of petroleum-based feedstocks might not keep up with industry's needs, which would force changes in chemical manufacturing. 24 ------- 3.2 Potential Changes 3.2.1 Same Feedstocks from Different Sources One set of possible changes in organic chemical production would involve deriving the same feedstocks from different sources. For example, hydrocarbon liquids produced in the conversion of coal to Solvent Refined Coal (SRC II) could compete with the liquid products of petroleum refining. Synthesis- gas derived from coal gasification could be used in place of that now derived almost exclusively from natural or refinery gas. The implications for waste generation in this situation would not lie directly within the organic chemicals industry but rather in the production of its feedstocks. Once the feedstocks were provided, whatever their source, their conversion into chemicals would be essentially the same. Logically the wastes generated from that point on could be the same as those now asso- ciated with the production process, although that point is arguable. 3.2.2 Input Substitution Input substitutions in organic chemical production processes are possible. Ethanol derived from plant sources can be used to produce ethylene, rather than the reverse. This approach is proving attrac- tive in third world countries lacking petroleum stocks (Kochar and Marcell 1980). There is also interest in using grain to produce ethanol for gasohol. Acetylene can be widely used as an alternative input source for the derivation of several intermediate organic chem- icals although it now contributes only a small fraction. 25 ------- The effect of such substitutions would be less far-reaching than those involving the alternative derivation of basic feedstocks, since each substitution would be chemical-specific. However, when any chemical is produced in enormous volume, the effect of an input change could be great. This could be the case for ethylene, regarded as the most important petrochemical building block in terms of the quantity produced and its dollar value (Lowenheim and Moran 1975). Input substitution depends principally on relative costs of alternatives. A cheaper input material may be associated with a more expensive production route. Moreover, industrial flexibility is limited to some degree. Plants producing a given chemical are likely to be designed for a specific process, or set of related processes, which may require the same input. The cost of redesign to accommo- date different starting materials may be prohibitive, making change desirable only in new plants. 3.2.3 Use of Alternative Processes Starting from the same input, alternative processes can be used to produce a given chemical. Acetylene can be derived directly from coal rather than by today's indirect route and phenol can be produced from benzene by a sulfonation or a caustic (chlorobenzene) process. Some of these alternative processes have important implications for resulting waste loads. Direct production of acetylene from coal by plasma pyrolysis would yield less waste than when calcium carbide 26 ------- is used (although quantitative data are lacking).* Plant flexi- bility and comparative energy requirements are likely to affect industry's willingness to adopt such alternative processes. 3.2.4 Recycling Intermediate Outputs Input requirements and waste generation can both be reduced by recycling by-products now regarded as waste, such as acetonitrile. Such approaches would be attractive to industry if it were cost effective to recycle waste rather than to dispose of it. 3.3 Regulatory Factors Constraints imposed on the organic chemical industry under leg- islative mandates will undoubtedly alter production processes. The manufacture of some toxic substances might be banned entirely under the Toxic Substances Control Act (TSCA). Regulations affecting waste management and disposal can affect the routes chosen to derive chemi- cal products. As costs of complying with environmental regulations mount, the economic trade-offs are likely to shift. Processes that were initially cheaper could become less cost effective when the price of pollution containment is considered. Recycling intermediate waste products could become more attractive economically than manag- ing and ultimately disposing of them as residues, particularly if the problem of decontaminating hazardous constituents is significant. ''This alternative, while technically feasible, has not been demon- strated on a commercial scale. 27 ------- The effect of regulatory factors would be chemical-specific, requir- ing consideration of different variables with each individual product. 28 ------- 4.0 FEEDSTOCKS FOR CHEMICAL PRODUCTION This section demonstrates that higher waste loads could accom- pany a shift to alternative feedstock sources. Such a shift could be expected to result primarily from forces outside the industry itself which would alter the relative availability and cost of feedstocks from different sources—particularly coal, petroleum, and natural gas. Feedstock requirements will reflect production rates of all basic petrochemicals and major intermediate organic chemicals so changes in the waste loads will involve a complicated interrelation- ship between the chemical industry and all other sectors of the econ- omy competing for fuel and energy sources. Waste loads will also be affected by the types of materials used, particularly the kinds of coal, and the conversion processes used to achieve gasification and liquefaction. 4.1 Base Case Projections 4.1.1 Production Table 3 provides 1975 feedstock production data along with a base case estimate of feedstock production in 2000. Designed to serve as a point of reference, these estimates reflect an assumption that feedstocks for petrochemical use from coal, petroleum and natural gas will continue to grow at the average annual rate observed between 1970 and 1978, with no shift in the relative mix among feed- stocks. At that rate, by 2000, production would be 3.4 times the 1975 output. 29 ------- OJ o TABLE 3 FEEDSTOCK PRODUCTION BASE CASE 1975 and 2000 Feedstock 1975 Feedstock Source Production Estimated Feedstock Production in 2000 Petroleum (Including Liquid Petroleum Gas and Liquid Refinery Gas) Tar Oils, Other Oils Natural Gas Plant Derivatives3 Refining Coal Processing plants Distilleries 288.0 x 106 bbl 2.0 x 106 bbl 632.4 x 109 ft3 <1.0 x 106 bbl 980 x 106 bbl 7 x 106 bbl 2,150 x 109 SCF 2-3 x 106 bbl Quantitative data on chemical feedstocks from plant sources and other biological materials not available. Assumptions: 1. No change in percentage distribution of feedstock sources between 1975 and 2000. 2. Chemical industry grows at a rate such that its output in 2000 is 3.4 times output in 1975 (U.S. Environmental Protection Agency 1980b). 3. Feedstock consumption grows correspondingly. Source: Bureau of Mines 1975 and 1976. ------- 4.1.2 Waste Generation Table 4 provides a reference point with regard to wastes asso- ciated with the base case feedstock production. Potentially hazardous waste components are identified, but it would be inappropriate to label particular quantities of waste as hazardous. The definition of that term will depend upon authoritative ruling by EPA under the regulations provided. Specification of hazardous wastes under RCRA and other legislative authority is proceeding. 4.2 Derivation of Alternative Scenario In order to provide a strong contrast with the base case assump- tions about feedstock production, an "alternative scenario" is hy- pothesized in which significant quantities of feedstocks are derived from coal and oil shale. This scenario is separate and distinct from others described later. The underlying assumptions are arbitrary, because no attempt has been made to relate the shifts in feedstock sources to process changes in the production of particular chemicals. The assumptions listed are not necessarily regarded as those most likely to occur by 2000. The purpose is merely to illustrate waste generation resulting from reasonable changes in feedstock sources. Assumed characteristics for the alternative scenario are these: a. A decrease of nearly 35 percent in the quantity of feed- stocks derived in the base case from petroleum and asso- ciated sources. b. A 20 percent decrease in the amount derived from natural gas. 31 ------- TABLE 4 WASTE* GENERATED FROM FEEDSTOCK PRODUCTION BASE CASE 1975 AND 2000 U) Unit Feedstock Source Quantity Petroleum Refining 10 bbl (Including Liquid Petroleum Gas, Liquid Refinery Gas) Tar Oils, Other Oils Coal 103 bbl (140 tons) 9 Natural Gas Processing 10 SCF Plants Plant Material0 Waste Generated Far Unit Of Feedstocks Waste Loads (Tons/Unit) ,,..,„..-,, (103 Tons) reeastocK Liquids Solids Production Liquids Solids 1.8 1.0a 288 x 106 518 288 bbl Unknown 17. 8b 2 x 106 Unknown 35 bbl Negligible, closed 632 x 109 Negligible cycle operations, with liquid dis- charge limited to small quan- tities from leaks and blowdown 2000 Waste Loads „ , .. , (103 Tons) reeostocbc ^ ^ ~^~^~^~^^^~^~ Production Liquids Solids 980 x 106 1,765 980 bbl 7 x 106 Unknown 125 bbl 2,150 x 109 SCF (ft3) * Potentially hazardous components to be considered with petroleum feedstocks are: oil; metals (Cr, Zn, Ni, Cu, Va, Pb, Hg, etc.); phenols; cyanide; and arsenic. With tar oils and other oils they are: trace metals (Zn, Pb, etc.); arsenic; caustic soda; and hydrocarbons. Sources: Rosenberg, et al. 1976. Anderson and Tillman 1979. E comprehensive data available. stimated from application of waste factors to output. ------- c. A quantity of feedstocks supplied from liquefaction of coal (as represented by the SRC-II process) equal to about 12 percent of the petroleum-derived quantity hypothesized for the base case. (The SRC output includes 16 percent synthetic natural gas.) d. A quantity of feedstocks derived from synthetic natural gas (SNG) as represented by the Winkler and WESCO pro- cesses equal to 15 percent of the volume of natural gas hypothesized for the base case. e. A quantity of feedstock synthesis gas by the Winkler process equal to 10 percent of the volume of natural gas hypo- thesized for the base case. f. A fourfold increase in the amount of feedstock input derived from coal by carbonization hypothesized for the base case. g. A quantity of feedstocks supplied from oil shale equal to 10 percent of the petroleum-derived quantity hypothesized for the base case. Petroleum imports are expected to fall 25 percent by the year 2000 (McCurdy 1980c), so it is assumed that petroleum use for feed- stocks will drop by more than 25 percent. Assumptions about substi- tute gas and liquids appear reasonable in light of a predicted capacity for 3 million bbl per day or more by 2000 (McCurdy 1980c). Arguments could be raised against the hypothesized reliance on coal and oil shale (roughly 10 percent). Questions might also arise because of the assumed increase in coal feedstocks derived from conventional processes; however, the additional quantity involved is only 3 percent of that postulated to come from petroleum. In short, it can be said that the alternative scenario repre- sents about as strong a contrast with the base case as is reasonable to consider. 33 ------- 4.2.2 Waste Load Projections Table 5 shows one set of waste generation factors associated with production of feedstocks from major alternative sources. Using these waste factors, waste loads for this alternative scenario have been calculated and are shown in Table 6. 4.3 Comparison of Waste Loads As can be seen from Tables 5 and 6, waste loads attributable to production of petrochemical feedstocks are far higher under the alternative scenario than in the base case. In the alternative scenario, oil shale contributes more solid waste than all other feedstock sources combined—despite the relatively small percentage of total feedstocks hypothesized as coming from this source. Even conventional processing of coal by carbonization, which is postulated in the alternate scenario to produce only a small fraction of feed- stocks, would generate more solid waste than the total from all sources projected for the base case. Thus, whether the alternative scenario is realistic or probable is a matter of less consequence than the point it illustrates: use of substitute sources to replace any significant amount of the feed- stocks now derived from petroleum and natural gas will inevitably result in increases in solid, semi-solid and liquid wastes. It has been estimated that of every ton of coal mined for conversion to fuels or feedstocks by the Fischer-Tropsch process, two-thirds repre- sents waste that must be disposed of. The quantities of shale that 34 ------- TABLE 5 WASTE FACTORS ASSOCIATED WITH ALTERNATIVE FEEDSTOCK SOURCES YEAR 2000 Feedstock Source Unit Quantity Waste Factors3 (Tons/Unit Quantity of Feedstock) Liquids Solids Synthetic Natural Gasd Synthetic Natural Gas Synthesis Gas (Ap pr oxima t ely 1:1, H2:CO)e Petroleum Liquid Hydrocarbons (Naphtha, Liquid Petroleum Gas, Solvent Refined Coal) Mixed Hydrocarbons (16% Synthetic Natural Gas)f WESCO gasification of coal SRC-II (solvent refined coal) Winkler gasification of coal Refining SRC II 106 ft3 106 ft3 106 103 bbl 1 ton SRC II 1 ton 5.7b 1.8 14.8C 1.0 1.7 1.5 30.9 2.6 4.0 1.8 2.5 2.1 Tar Oils, Coal Other OilsS Refined Shale Oil shale Oil 103 bbl 103 bbl Unknown 17.8 None 632.3 discharged aCoal waste factors are based only on conversion, excluding earlier mining, drilling and other preparation. Discharge estimated to be 65 tons with 106ft3 treated for reuse. cReportedly not discharged directly. Includes unknown quantity of sludge. Sources: ^Bureau of Reclamation 1976. eJahnig 1975. fShields et al. 1979. SMITRE Corporation 1979. 35 ------- TABLE 6 WASTE RESULTING FROM FEEDSTOCK SOURCES ALTERNATIVE SCENARIO YEAR 2000 Feedstock Source Petroleum, Refining Liquid Petro- leum Gas and Liquid Refinery Gas Tar Oils, Coal carboni- Other Oils zation Estimated r eeds to CK Production 640 x 10& bbl 28 x 10& bbl Waste Loads Year 2000 (106 Tons) Liquids Solids 1,152 640 Unknown 498 Potentially Hazardous Constituents Oils, metals (Cr, Ni, Va, Zn, Pb, Hg, etc.); phenols; cyanide, arsenic Trace metals (Zn, Pb, etc.); arsenic; Natural Gas Processing plants Synthetic WESCO coal Natural Gas gasification 1,720 x 109 ft3 Negligible 325 x 109 ft3 1,852 Synthesis Gas Winkler coal 210 x 109 ft3 3,108* 842 gasification Mixed Hydro- carbons Refined Shale Oil SRC-II Oil shale 17 x 106 tons 26 100 x 106 bbl None dis- charged caustic soda; HCs 10,042 Phenols, other organics in sludge; trace metals from ash, slag Acids, caustic organics in waste- water sludge, trace metals in ash and particulate control refuse 36 Trace metals from ash and spent catalysts; phenols, other organics in sludge 62,000 Arsenic, Cr, Pb, other trace metals Not directly discharged. ------- must be retorted to produce hydrocarbon liquids at a typical rate of 30 gallons per ton are certain to pose a disposition problem. More- over, oil shale tends to increase in volume during retorting.* *It should be noted that factors used in this section are based on processing oil shale and coal to yield hydrocarbon products and do not include the waste generated in extraction and handling before conversion. 37 ------- 5.0 SELECTED PETROCHEMICAL BASICS AND INTERMEDIATES: BASE CASE PRODUCTION AND POTENTIAL FOR CHANGE To provide a frame of reference for a chemical-specific analysis of the waste generated by alternative production routes, current output and basic production routes are shown in Table 7 for selected petrochemical basics and in Table 8 for selected intermediate organic chemicals. The 13 chemicals studied are based largely on petroleum and associated gaseous sources. As seen in Table 7, for four of the five basics, more than 95 percent of production is from petroleum or related sources, including natural gas. Similar reliance on refinery and gas processing is shown by production figures for the selected intermediate organic chemicals (Table 8). An extreme example is acrylonitrile, all of which is currently produced by ammonoxidation of propylene, a petroleum deriv- ative. Methanol shows a 99 percent reliance on natural and liquefied refinery gases, while vinyl chloride depends almost as heavily on petroleum-associated sources. Only 1 percent of phenol is currently produced directly from coal tar processing. The total contribution of coal is somewhat greater because of the intermediate use of benzene and toluene, small amounts of which are derived from that source. At the opposite extreme, about half of acetylene is now derived from coal via calcium carbide. No coal sources are currently used in deriving ethanol (ethyl alcohol), which is predominantly produced from ethylene, with the remainder fermented from plant sources. 39 ------- TABLE 7 PRODUCTION OF SELECTED PETROCHEMICAL BASICS 1977 Petrochemical Basic Derivation Production Volume Percentage of Total Benzene* Solvent extraction 1,050 x 10& gals of reformate and pyrolysis gasoline Dealkylation of toluene (from petroleum or coal) 440 x 106 gals 67.31 28.20 Ethylene Propylene Toluene Xylenes Coal carbonization Total Petroleum gas Petroleum liquids Total Petroleum refinery gas and liquids Ethylene co-products Total Petroleum sources Coke ovens Total Petroleum sources Total 70 1,560 8.4 3.1 11.5 2.6 3.5 6.1 1,008 10 1,018 809 2 811 x 106 x 106 x 106 x 106 x 106 x 106 x 106 x 10& x 106 x 10& x 106 x 106 x 106 x 106 gals gals tons tons tons tons tons tons gals gals gals gals gals gals 4.49 100.00 73.04 26.96 100.00 42.62 57.38 100.00 99.0 1.0 100.00 99.75 0.25 100.00 *Figures do not directly express the fraction of benzene that is derived from petroleum because about 28 percent of benzene is produced by dealkylating toluene. 40 ------- TABLE 8 PRODUCTION OF SELECTED INTERMEDIATE ORGANIC CHEMICALS Total Recent Intermediate Production Organic Chemical (106 Tons) Year Derivation Route Approximate Percentage of Current Production by Derivation Route Source(s) for Production Mix Data Acetic acid Acetylene Acrylonitrile 1.39a 0.27C 0.8753 1978 Oxidation of acetalde- hyde from ethylene (Wacker Process) Liquid phase oxidation of N-butane Carbonylation of methanol Pyroligneous liquor from wood and others 1974 Partial oxidation of methane Ethylene by-product Calcium carbide 1978 Ammonoxidation of propylene 31 51 14 36 3 61 100 ------- TABLE 8 (Continued) .o N) Intermediate Organic Chemical Ethanol (Ethyl Alcohol) Total Recent Production (106 Tons) 0.81C Year Derivation Route 1974 Hydration of ethylene Fermentation (plant Approximate Percentage of Current Production by Derivation Route 93 7 Source(s) for Production Mix Data e e Methanol Phenol 3.18* 1.36a sources) 1978 Natural gas, liquid refinery gas Other (including small fractional amounts from destructive distillation of hardwood 1978 Cumene peroxidation (from petroleum) Chlorobenzene reaction with NaOH Benzene (Hooker Raschig process) Benzene (sulfonation) 99 89 b,d ------- TABLE 8 (Concluded) Intermediate Organic Chemical Total Recent Production (106 Tons) Year Derivation Route Approximate Percentage of Current Production by Derivation Route Source(s) for Production Mix Data Vinyl Chloride 3.5a Vinyl Acetate 0.84a Benzoic acid from toluene Coal tar 1978 Ethylene (chiefly ethylene dichloride by balanced process) Acetylene 1978 Oxyacetylation of ethylene (via acetalydehyde) From acetylene 1 0 94 6 66 34 Sources: aAmerican Chemical Society 1979. bu.S. Environmental Protection Agency 1974. cChemical Information Services 1977. dLiepins et al. 1977. eKeller 1979. ^Lowenheim and Moran 1975. ------- 5.1 Derivation of Projections for Year 2000 Tables 9 and 10 provide year 2000 production estimates for the 13 selected petrochemicals. The production of each petrochemical basic and intermediate organic chemical is derived from growth rates for the specific chemical obtained from the most current data avail- able. For example, the average annual growth rate of acetic acid between 1968 and 1978 was 4 percent (American Chemical Society 1979) and this growth rate was projected for 22 years, resulting in an estimate that the output in 2000 will be approximately 2.37 times that of 1978, or a total of 3.29 million tons. Then the process distribution observed in 1978 was applied to this figure to project the quantity derived by each route in 2000. Sample calculations are shown in Appendix B. The assumptions underlying these base cases or point of refer- ence projections omit any changes in methodology within industries producing organic chemicals and their major feedstocks. 5.2 Alternative Scenarios Affecting Selected Organic Chemicals The variety of external circumstances that could change produc- tion methods in the organic chemical industry have been discussed. The objective here is to detail the ways in which production of the 13 selected chemicals and waste generation might be affected by the factors noted. The general effects are summarized in Table 11 for the selected intermediate organic chemicals. They may also be seen graphically in the "chemical trees" in Appendix C, which show 44 ------- TABLE 9 PRODUCTION OF SELECTED PETROCHEMICAL BASICS BASE CASE AND YEAR 2000 Petrochemical Basic Ethylene Benzene Propylene Source Gas Petroleum liquids Solvent extrac- tion of refor- mate and pyrolysis gasoline Coal carboni- zation Toluene dealkylation Refinery Ethylene co-product Recent* Annual Production Growth From Source Rate 16.8 x 109 Ibs .072 6.2 x 109 Ibs 1,050 x 106 gals .061 70 x 106 gals 440 x 10& gals 5.4 x 109 Ibs .07 7.0 x 109 Ibs Growth Year 2000 to 2000 Production (Multiplier) From Source 4.22 71 x 26 x 3.39 3,550 gals 250 x gals 1,490 gals 4.06 21.9 28.4 109 Ibs 109 Ibs x 106 10& x 106 x 109 Ibs x 109 Ibs Year 1976 for ethylene, 1977 for benzene and propylene. 45 ------- TABLE 10 PRODUCTION OF SELECTED INTERMEDIATE ORGANIC CHEMICALS BASE CASE AND YEAR 2000 Chemical Acetic acid Acetylene Acryloni- trile Ethanol (Ethyl Alcohol) Source and Derivation Acetaldehyde from ethylene (Wacker process) N-butane (oxidation) Methanol (carbonylation) Wood-pyrol igneous liquor and other Methane (partial oxidation) Ethylene by-product Calcium carbide (coal) Propylene ( ammo noxidat ion) Ethylene (hydration) Plant sources Estimated Recent Outputd (106 Tons) 0.43 0.76 0.19 0.06 0.01 0.01 0.16 0.87 0.75 0.06 Year 1978 1978 1978 1978 1974 1974 1974 1978 1974 1974 Annual Growth Rate .04a .04a .04a .04a .007^ .007b ,007t> .05a .015C .015C Growth to 2000 (Multiplier) 2.37 2.37 2.37 2.37 1.2 1.2 1.2 2.9 1.47 1.47 Output Quantities 2000 (106 Tons) 1.02 1.68 0.45 0.14 0.12 0.01 0.20 2.54 1.10 0.09' (fermentation) ------- TABLE 10 (Concluded) Estimated Chemical Methanol Phenol Vinyl Chloride Vinyl Acetate Source and Derivation Synthesis gas from methane (natural gas, liquid natural gas) Other Cumene from petroleum (peroxidation) Chlorobenzene (reaction with NAOH) Benzene (Hooker Raschig) Benzene (sulfonation) Benzoic acid from toluene Coal tar (pyrolysis) (middle oils) Ethylene Acetylene Ethylene (oxyacetylation) Acetylene Recent 6 Outputd (10 Tons) Year 3.15 0.03 1.22 0.40 0.05 0.04 0.01 0.01 3.30 0.20 0.55 0.29 1978 1978 1978 1978 1978 1978 1978 1978 1978 1978 1978 1978 Annual Growth Rate .05a .05a .06a .06a .06a .06a .06a .06a .08a .08a 1.08a 1.08a Growth to 2000 (Multiplier) 2.9 2.9 3.6 3.6 3.6 3.6 3.6 3.6 5.4 5.4 5.4 5.4 Output Quantities 2000 6 (10 Tons) 9.14 0.09 4.39 0.14 0.18 0.14 0.04 0.04 17.82 1.08 2.97 1.57 Sources: aAmerican Chemical Society 1979. t>Maisel 1980. cBaba and Kennedy 1976. dDerived from production totals and percentages as given in Table 3. Production figures for specific years by derivation routes not available. ------- TABLE 11 EFFECTS OF CHANGES IN FEEDSTOCK SOURCES ON PRODUCTION OF SELECTED INTERMEDIATE ORGANIC CHEMICALS Chemical Acetic Acid Acetylene Aery lonitr ile Ethanol Methanol Phenol Vinyl Acetate Vinyl Chloride Assumed Changes Decreased Petroleum Less from acetaldehyde, N-butane oxidation Less as ethylene by- product Exclusive use of propylene may end Less synthesized from ethylene; more total use of ethanol as route to C- and C, chemicals Greater use of methanol as alter- native source Less from cumene (propylene and benzene) ; produc- tion from other benzene routes and from toluene may increase. Less from ethylene Less from ethylene Increased Coal Car boniz at ion , ?yr oly s is More from calcium carbide, plasma pyrolysis Resort to acetylene as basis Increased use of coal tar oils; benzene and toluene derived from coal More from acetylene More from acetylene Increased Coal Gasification More from methanol (methane) More from methane Would promote tech- niques to derive from synthesis gas Greater use of methanol from synthesis gas Decreased Natural Gas Less from methanol (methane) and N^ butane oxidation Less from methane, ethylene May affect avail- ability of propy- lene, reducing use of this source May affect ethylene supply, decreasing use of this source Reduced source of methanol Reduced ethane may reduce production from ethylene Reduced ethane may reduce production from ethylene Increased Plant Usage More from pyro- ligneous liquor More from fer- mentat ion . May become predomi- nant route, yielding ethy- lene from ethanol More from f ermentat ion route Increased Recycling , Reduced Waste Generation Less from acetaldehyde (hazardous wastes) Favors plasma pyrolysis Favors process based on propylene which recycles acetonitrile Favors plant usage since wastes can be used as feed for livestock. Favors production from refuse Reduced use of cumene (hazardous wastes) , of coal tar oils (high waste generation factor) Less from ethylene dichloride (hazardous wastes) 00 ------- alternative paths to production from different feedstocks and petrochemical basics. 5.2.1 Reduced Petroleum Feedstocks There is a distinction between a shortage of crude oil compensated by equivalent liquid feedstocks from other sources and one in which replacements do not exist. In the first situation, liquid hydrocarbons yielding the same petrochemical basics would be available from shale oil and liquefaction of coal. An absence of adequate liquid hydrocarbons without replacements would require adjustment of the proportions of feedstocks produced from other processes. A result of such a situation could be a reduction in the quan- tity of ethylene, propylene, benzene, toluene and xylene that could be produced from refinery products. In turn, the amounts of the intermediate organic chemicals derived from these products would be reduced as the industry turned to processes using other sources. Processes using ethylene to derive acetic acid (via acetaldehyde), ethyl alcohol, vinyl acetate and vinyl chloride would represent a smaller share of total production than in the base case. Similarly, benzene-based processes might lose favor for producing phenol. An effect which would be expected from at least a partial short- age of petroleum would be a greater use of the heavy hydrocarbon liq- uids as a source of petrochemical feedstocks. This trend has already been observed (Cronan 1978) as partial oxidation of heavy liquids has 49 ------- recently been pushed to offset the scarcity and cost of light petro- leum feedstocks. 5.2.2 Decreased Natural Gas Supply A severe shortage of natural gas could come about through forces affecting foreign supplies. The effect would be most direct in de- creased availability of methane and the heavier paraffins from liq- uefied natural gas (LNG). It could be at least partially offset by a reliance on synthesis gas from coal and, as long as there was not simultaneously a petroleum shortage, partial oxidation of the heavier liquids from crude oil (Cronan 1978). The principal result (in the present context) would be a different feedstock source for methane and methanol, with no change in processes producing chemicals from these. Alternatively, the result could be a reduction in the propor- tion of acetic acid, acetylene and methanol derived from methane. In any event, some reduction in propylene and ethylene available from liquid petroleum gases derived from natural gas liquids would be expected. The possibility of an increase in natural gas supplies is not explored here, although new sources have resulted in a "natural gas bubble"—or an apparently temporary excess of supply over demand. U.S. natural gas production increased slightly from 19.95 trillion standard cubic feet (SCF) in 1976 to 20.03 trillion SCF in 1977 after steady declines in the three previous years (Figure 3) (American Petroleum Institute 1976-1980). Nevertheless, the long term outlook 50 ------- 24 - Actual Marketed Production 1965 1970 1975 1980 1985 Year 1990 1995 2000 Source: Adapted from American Petroleum Institute 1976-1980. FIGURES ACTUAL AND PROJECTED U.S. USE OF NATURAL GAS 51 ------- is for somewhat less natural gas from U.S. production with a figure of some 19 trillion SCF postulated for the year 2000. The decline in U.S. production could be more than offset for the chemical industry by a decline in fuel use for natural gas or by an increase in imports. One foreign source recently predicted a glut in natural gas liquids (NGL) produced in the Middle East in the 1990s (McCurdy 1980b). Thus, a situation in which there is more natural gas—not less—available for petrochemical feedstocks is not unreasonable to postulate for the year 2000. However, this hypothesis hardly constitutes a separate scenario, distinct from the base case. What is of interest is to investigate the situation which might result from a deficiency of natural gas. 5.2.3 Increased Use of Coal Coal can be expected, out of necessity, to assume an even larger role, both as feedstock and fuel. Consequently, the following basic routes for deriving chemicals from coal are considered: liquefac- tion, gasification, and more direct production by carbonization (pyrolysis),* or by plasma pyrolysis, which is not yet available on *Hach's Chemical Dictionary (Grant 1969) defines carbonization in the present context as the distillation of coal at a high tempera- ture. Coal is heated in the absence of air at 1,000 to 1,300°C with the formation of gas, tar oil, ammonia, and coke. The same source defines pyrolysis as "decomposition of organic substances by heat." Since pyrolysis (a more general term) occurs in the process of car- bonizing coal, the two terms are frequently used synonymously in reference to obtaining coal derivatives. Carbonization is also known as "coking." In plasma pyrolysis, coal is placed on an elec- trode in an electric reduction process. A plasma is created that "reaches higher temperatures than conventional coal processing reac- tions," producing acetylene and other small molecules. (Anderson and Tillman 1979.) 52 ------- a commercial scale. Liquefaction and gasification are now promoted primarily for fuel needs; however, there is some chemical company interest in gasification. Liquefaction of coal produces hydrocarbon oils which can compete with or be supplemental to crude oil or natural gas liquids. Gasifi- cation, by producing synthesis gas (CO + H2), can compete with meth- ane in natural gas. Coal carbonization and pyrolysis, a derivation method using coal tar oils, once represented the predominant route for the BTX aromatics. Calcium carbide from coke was formerly the major source of acetylene. Details of these three processes are included in Appendix C and Table 11 summarizes the chemical processes potentially affected by these coal derivations. Selection of these coal routes would be influenced by the costs of other sources of feedstocks relative to coal, plant flexibility, and waste management. Faced with a long-term petroleum shortage, the chemical industry can be expected to take steps which would ensure an adequate production capacity from coal. 5.2.4 Increased Use of Biological Material A number of chemicals currently derived from fossil fuels can also be made by bioconversion of carbohydrate raw materials (usually plant materials and sometimes other substances such as whey). The process for deriving ethanol by fermentation is among the most widely known and approximately 6 percent of industrial ethyl alcohol is produced by this route. Methanol can also be produced through the 53 ------- destructive distillation of hardwood, while acetic acid can be made with pyroligneous liquor, obtained from the same source. A number of C3 and 04 chemicals (the "C" denoting carbon) not examined here can also be obtained by fermentation (long 1978, Lowenheim and Moran 1975). A disadvantage of the fermentation route for ethanol lies in weight conversion. Yields exceed 80 percent for synthetic ethanol compared to theoretical weight yields of less than 70 percent for fermentation. Nevertheless, feedstock costs could make derivation from plant sources more attractive. "Cornstarch and sugar from cane can become competitive as chemical feedstocks when crude oil prices approach $18 to $20 a barrel" (long 1978). However, significant increases in the quantity of ethanol pro- duced by fermentation are viewed as dependent on improved fermenta- tion technology and the design of integrated production facilities. Moreover, the availability of agricultural raw materials for chemical production over the long term is in question. According to one opin- ion, current requirements for ethanol as well as CL and C, chemicals 3 4 could be met by less than a 10 percent increase in yearly cereal grain and sugar crop production. Molasses and unutilized whey would also augment the source of fermentable carbohydrates (long 1978). With expected population growth in third world countries, the diversion of grains on a major scale could become a political issue tied to concern for world hunger. This problem might be avoided by 54 ------- use of nonedible biomass. The Tennessee Valley Authority (TVA) recently announced a policy promoting the development of wood-based alcohol production. According to the manager of TVA's project on liquid fuels from biomass, "The question is not whether there will be an alcohol fuels industry. The question relates to the nature of that industry" (McCurdy 1980a). Although the program is aimed at developing one billion gallons of fuel per year in the 1990s, if it is successful, it may also be a potential source of chemical feed- stocks . The most significant impact of increased use of plant sources would be a shift in production of ethanol and ethylene. As shown in Table 11, ethyl alcohol could become a feedstock for derivation of ethylene rather than the reverse procedure used today. Some increase in methanol and acetic acid derived from hardwood could also be expected. 5.2.5 Recycling and Reduction of Waste Generated Regulations imposed under RCRA and other legislation could affect the processes used to produce chemicals, shifting the produc- tion mix. Regulations could result in increased costs for waste man- agement and control, for example, thus encouraging the use of pro- cedures which generate less waste or recycle intermediate output that would otherwise be treated as waste. Such a trend could be aided by rising property, values. In some cases, land for waste disposal might be difficult to obtain at any price by the year 2000. Higher feed- stock costs could also push industry toward increased recycling. For 55 ------- example, as noted above, by recycling acetonitrile, currently a waste in the production of acrylonitrile from propylene, output could be increased approximately 12 percent with no increase in the quantity of feedstocks purchased or solid waste generated. The same factors could lead to greater production of methane and its derivatives from waste products. Through pyrolysis, thermal gas- ification and liquefaction processes, organic solid wastes and resi- dues can be converted to synthesis gas and methane as well as to low-molecular weight organic liquids including organic acids and aromatics. This process could be used to recycle municipal refuse, tires, sludge, waste plastics, packaging materials and agricultural and forestry residues. This route is discussed in a recent analysis (Jones 1978) as a way to produce fuel gases that can be discharged directly into a combustion chamber for firing steam boilers. How- ever, the production of chemical feedstocks is also possible with advanced technology. The result would be not only an increase in methane and the production of chemicals by processes using it (methanol, acetylene, acetic acid, acrylonitrile, vinyl acetate and vinyl chloride) but also a net reduction in the volume of waste. Other shifts in the relative contributions of alternative pro- duction processes would be observed in a trend toward routes which generate less net waste—particularly less hazardous waste (such as vinyl chloride from ethylene dichloride, detailed below). 56 ------- 6.0 PROJECTIONS FOR SELECTED PETROCHEMICAL BASICS The variety of changes in waste loads that could accompany shifts to alternative production routes is illustrated in this sec- tion. Year 2000 projections, offered in chemical-specific scenarios, show a range of possibilities for the future. Few generalities can be made about these projections, but it appears that alternative production processes will often yield larger quantities of potentially hazardous waste—if not larger quantities of waste over all. For example, in ethylene production, shortages of natural gas and petroleum would naturally cause a drop in wastewater resulting from processing natural gas. However, there would be substantial increases in potentially hazardous spent caustic from processing shale oil liquid (from 0 in the base case to 5.2 billion pounds). 6.1 General Characteristics of the Scenarios Each scenario is distinct; however, there are common points which can be used to relate them. Some reflect forces causing increased use of feedstocks derived from coal at the expense of petroleum sources. Others are linked by the greater reliance on plant sources which they assume and some reflect regulatory constraints presumed to induce greater recycling and reduction of wastes, particularly of hazardous components. The tables of waste considerations document the source or pro- cess, and the type and quantity of waste generated. The projected waste loads were derived by applying waste generation factors for 57 ------- TABLE 12 WASTE GENERATION FACTORS FOR SELECTED PETROCHEMICAL BASICS Chemical Source and Derivation Nature of Waste Waste Generation Factor Ethylene Gas Wastewater Spent caustic Dessicant 0.75 Ib/lb 0.11 Ib/lb 1.3 x 10-4 Petroleum Liquids Benzene Solvent extrac- tion of refor- mate and pyr- lysis gasoline Coal carboniza- tion Propylene Refinery Ethylene co-product Spent caustic Dessicant Spent clay Spent acid and oil Spent caustic Spent clay Spent caustic Subsumed under ethylene 0.19 Ib/lb 1.3 x 10~4 Ib/lb 0.73 Ib/gal 1.39 Ib/gal 0.16 Ib/gal 0.15 Ib/gal 0.11 Ib/lb See above As function of product output. 58 ------- each of the chemical production processes considered (Table 12) to the projected production quantities for the base case and following scenarios. The waste load figures, however, are not necessarily the quantities which would be discharged into the environment. This applies particularly to wastewater flows where the ultimate residual depends heavily on the method of treatment used. When information on the solid content of the flows was available it has been included in the tables. It is also recognized that recycling practices may vary from one plant to another, particularly with liquid effluents. Although an effort was made to exclude volumes of material regularly recycled, the available information is inadequate to ensure that this was done comprehensively. 6.2 The Petrochemical Basics 6.2.1 Ethylene The basic building block for numerous chemical products and intermediates, ethylene is generally regarded as the most important olefinic petrochemical. The projected demand for ethylene in the year 2000, based on the demand for products currently derived from ethylene, is 97.5 billion pounds per year (Sherwin et al. 1975). Currently in the U.S. about 65 percent of ethylene is made by cracking liquefied petroleum gas (a mixture of ethane, propane, and butane). Approximately 33 percent is made by cracking heavier petroleum fractions, e.g., naphtha, and the remainder is recovered from refinery off-gases (Debreczeni 1977). 59 ------- TABLE 13 ETHYLENE - PRODUCTION ASSUMPTIONS YEAR 2000 Percentage of Total Produced by Process Scenario Base Case Scenario 1— A Output (109 Lbs) 97.5 97.5 Cracking Liquid Natural or Pe- troleum Gas 65 23 Cracking Heavier Petroleum Liquids 33 77 Recovery From Refinery Off-Gas 2 0 Cracking Shale Oil 0 0 External Conditions o Declining availability of natural gas and petroleum gas liquids o Extensive use of heav- ier petroleum or crude o Increased availability of petroleum to chemi- cal industry o Increased supplies of domestic oil Scenario 2-A 97.5 23 51 28 o Reduced availability of petroleum and develop- ment of shale oil with 1 million barrels per day available for ethylene ------- TABLE 13 (Concluded) Percentage of Total Produced by Process Output Scenario (109 Lbs) Cracking Liquid Natural or Pe- troleum Gas Cracking Heavier Petroleum Liquids Recovery From Refinery Off-Gas Cracking Shale Oil External Conditions Scenario 3-A 68.2 23 77" o Acetylene is produced from coal and used to make vinyl chloride and vinyl acetate. Other chemicals, i.e., ethylene oxide and ethylene glycol derived from coal- synthesis gas. Up to 30% of potential demand for ethylene in year 2000 could be met by these alternatives. This figure also represents a combination of shale liquids and petroleum liquids. ------- TABLE 14 ETHYLENE - WASTE PROJECTIONS YEAR 2000 Source Type of Waste Total Amount of Waste - Year 2000 - (10 Lbs) Base Case Scenario 1-A Scenario 2-A Scenario 3-A Gas Petroleum Liquids Shale Oil Liquid Wastewater Spent caustic Dessicant Spent caustic Dessicant Spent caustic Dessicant 53.4 7.8 0.01 5.0 0.0003 0.0 0.0 16.8 2.5 0.003 14.3 0.01 0.0 0.0 16.8 2.5 0.003 9.1 0.006 5.2 0.0004 16.8 2.5 0.003 8.0 0.006 0.0 0.0 62 ------- Changes in the availability of natural gas liquids are forcing a shift toward the use of the heavier petroleum liquids in U.S. plants (Debreczeni 1977). Advances in cracking technology will enable the direct use of crude oil for producing ethylene and associated by- products (Hatch and Matar 1978). A growing share of available petroleum will be needed to meet the increased demand for ethylene, requiring that substitutes be found for competing uses of petroleum supplies. More petroleum would be available for chemical production if utilities used coal or nuclear fuel instead of oil or gas to generate electricity. On the other hand, unconventional hydrocarbon liquids such as shale oil could be used to make up the shortfall in conventional petroleum supplies needed for ethylene production. The demand for ethylene could be lower than projected if alter- native technologies for production of products currently derived from ethylene were to become economical. For example, vinyl chloride and vinyl acetate, which are currently derived from ethylene, can also be derived from acetylene. New technology under development for deriving acetylene directly from coal could make the acetylene route to these chemicals competitive. Coal-derived synthesis gas may also be used to make ethylene and its derivatives, reducing the demand for petroleum-derived ethylene. If coal-derived feedstocks were substituted for petroleum-based ethylene, the coal processing might generate more waste than the production of oil and feedstocks derived from oil. 63 ------- 6.2.2 Propylene The projected demand for propylene in the year 2000, based on demand for products derived from this olefin, is 49.75 billion pounds per year (Sherwin and Frank 1975). Currently, about half the propy- lene is recovered from refining catalytic cracker streams, and the remainder is a by-product of ethylene production (Sanders et al. 1977, Debreczeni 1977). Improvements in catalytic cracking technol- ogy to increase gasoline yields have reduced the production and, thus, availability of propylene from refineries. However, the switch to heavier feedstocks for ethylene production has resulted in an in- crease in the production of co-product propylene. It is anticipated that the increased co-production of propylene with ethylene, combined with increased production of ethylene, will provide adequate feed- stocks to support the growth of propylene derivatives (Debreczeni 1977). When propylene is co-produced with ethylene, there is no additional waste generated over that reported for the production of ethylene. 6.2.3 Benzene, Xylene, and Toluene The projected demands for benzene, xylene, and toluene for chem- icals in the year 2000 are 5.25, 3.88, and 2.08* billion gallons per year, respectively (Sherwin and Frank 1975). In 1977, more than The figures for toluene do not include the amount of toluene con- verted to benzene. The volume of benzene and other aromatic com- pounds recovered for chemical industry use is a minor portion of the total supply. 64 ------- TABLE 15 PROPYLENE - PRODUCTION ASSUMPTIONS YEAR 2000 Percentage of Total Produced by Process Scenario Base Case Scenario 1-B Output (109 Lbs) 49.75 49.75 Recovery From Refining Catalytic Cracker Streams 50 15 By-Product of Ethylene Production External Conditions 50 85 o Normal growth in availability of propylene from refineries o Increase in yield of co-product propylene from ethylene to 43 Ibs per 100 Ibs of ethylene o Debreczeni (1977) projects ratio of 50:100 for the year 1990 Scenario 2-B 46.45 17 83 o Alternative feedstocks used to produce some acrylonitrile, phenol, and propyl alcohols would be available for incremental produc- tion after 1990 Scenario 3-B 46.45 91 o Propylene less available from refineries following increased gasoline yields from catalytic crackers o Reduction in oil supplies reducing refinery yields Scenario 4-B 46.45 27 73 o Reduced ethylene production, and propylene to ethylene production ratio of 1:2, based on Scenario 3 for ethylene o Rise in availability of propylene from refineries ------- TABLE 16 PROPYLENE - WASTE PROJECTIONS YEAR 2000 Total Amount of Waste - Year 2000 - (109 Lbs) Type of Source Waste Base Case Scenario 1-B Scenario 2-B Scenario 3-B Scenario 4-B Refinery Spent Caustic 2.4 0.85 0.85 0.48 1.4 Ethylene By-Product* Subsumed under ethylene ------- 85 percent of all aromatics produced was used in gasoline (Cox 1979c). Currently, almost 96 percent of the U.S. benzene supply is recovered directly or indirectly from crude oil or natural gas liquids while the remainder comes from coal (Debreczeni 1977). As a result of the trend toward increased utilization of coal resources, more aromatics will be derived as a by-product of the production of coke, fuel gases, and synthesis gas from coal (Collin 1978). Tables 17 and 18 illustrate the factors in production and waste generation for each of the processes used to produce benzene, xylene, and toluene. The three aromatics are obtained as a mixture from refinery reformate streams, pyrolysis gasoline (a by-product of ethylene manufacture) and from coal tars. Because no additional waste streams are produced during the separation of the compounds from the mixture, the tables list the production and wastes only for benzene. A slight reduction in benzene demand could occur as a result of the use of butane instead of benzene to make maleic anhydride. If all incremental production of maleic anhydride between 1980 and 2000 were derived from butane, the benzene demand would be reduced by 25 million gallons per year in 2000. If all production of maleic anhydride in the year 2000 were based on butane, benzene demand would be reduced by 100 million pounds (Sherwin and Frank 1975). If incremental phenol production between the year 1990 and 2000 were made by toluene oxidation instead of from cumene, a further 67 ------- TABLE 17 BENZENE - PRODUCTION ASSUMPTIONS YEAR 2000 00 Output Scenario (109 Gallons) Base Case 5.25 Scenario 1-C 5.25 Scenario 2-C 5.25 Scenario 3-C 5.25 Percentage of Total Produced by Process Solvent Extraction of Reformate and Coal Toluene Pyrolysis Gasoline Carbonization Dealkylation 67 5 28 80 5 15 70 9 21 47 16 37 External Conditions o Increased availability of benzene from pyrolysis gasoline as a by-product of ethylene o Increased availability of toluene as by-product of coal derived synfuel o Increase in benzene obtained as a coal by-product (Sherwin and Frank 1975) o More than half of available toluene is coal derivative (Sherwin and Frank 1975) Scenario 4-C 5.25 60 37 o Increased toluene derived from coal for benzene production ------- TABLE 18 BENZENE - WASTE PROJECTIONS YEAR 2000 Total Amount of Waste - Year 2000 - (109 Lbs) Type of Process Waste Base Case Scenario 1-C Scenario 2-C Scenario 3-C Scenario 4-C Solvent Extraction Spent clay 2.58 4.23 2.80 1.8 3.14 of Reformate and Pyrolysis Gasoline Coal Carbonization Spent acid and 0.328 0.328 0.460 1.19 0.229 oil Spent caustic 0.038 0.038 0.053 0.137 0.026 Toluene Dealkylation Spent clay 0.22 0.12 0.16 0.29 0.12 ------- reduction in the demand for benzene of 350 million gallons per year would occur. This would probably result in a reduction in the amount of benzene produced by toluene dealkylation. In summary, as illustrated in Tables 17 and 18, waste generation in the production of benzene is likely to increase—but not because of increased benzene production. Instead, more waste will accompany a shift from petroleum derivation to coal derivation. 70 ------- 7.0 PROJECTIONS FOR INTERMEDIATE ORGANIC CHEMICALS As with the petrochemical basics, a variety of waste load variations can be expected to accompany changes in the methods used to produce intermediate organic chemicals. This point is illustrated by year 2000 projections for four scenarios, numbered I through IV, to distinguish them from the scenarios in Section 7. 7.1 General Characteristics of the Scenarios Scenario I shows a petroleum shortage. It is assumed that the deficiency in feedstock liquids from this source is not compensated by coal conversion or oil shale.* Hence, there will be a decrease in intermediate organic chemicals made from basics now derived prin- cipally from petroleum, such as ethylene and propylene. To compen- sate, alternative routes using basics from other sources are assumed to increase as necessary. In particular, basics that can be derived from conventional coal processes such as acetylene (and to some extent benzene) will be used in greater proportion. However the scenario does not assume a breakthrough in commercialization of new or pilot processes for using coal such as plasma pyrolysis. More reliance is placed on methanol in Scenario I, since no natural gas shortage is hypothesized. Some increases in the small fraction of chemicals produced from biomass will occur to support production levels, but no breakthrough in commercialization of fermentation *It may be noted that a petroleum deficiency fully compensated by hydrocarbon liquids from alternative sources would constitute "business as usual" and would fall under the base case. 71 ------- technology is postulated. Therefore, increases in the use of plant materials are slight. Scenario II illustrates the effects of reduced waste generation, particularly wastes requiring ultimate disposal under RCRA. Pro- cesses which recycle intermediate products (as is possible for acrylonitrile) or which start with refuse (such as the processes for developing methane from a variety of solid wastes) provide a larger contribution to the production mix. Conversely, those derivation routes which generate the greatest amounts of solid, semi-solid and liquid wastes are used less. In particular, procedures associated with hazardous wastes provide a reduced contribution to the produc- tion mix. Some decline in feedstocks from petroleum is also assumed for this scenario, so that derivation routes using other starting points provide a greater percentage of output than in the base case. The technological advances necessary to accomplish the process sub- stitutions (such as commercialization of the recycling technology for acrylonitrile and of plasma pyrolysis of coal) are assumed for Sce- nario II. However, a breakthrough which would lead to widespread industrial use of fermentation from biomass is reserved for the next scenario. In Scenario III, commercialized use of plant sources is the dominant characteristic. Derivation routes based on fermentation increase markedly over other processes. The effect is most immediate for those selected chemicals which can be made directly from biomass 72 ------- such as acetic acid, ethanol, and methanol. A secondary effect is a greater reliance on methanol and ethanol for further production. Since from the latter, ethylene can be derived, the postulated effect is to offset a potential shortage of this petrochemical basic which was hypothesized for Scenario I. Otherwise, petroleum-derived basics are assumed to be less plentiful than in the base case. In Scenario IV, the principal feature is an assumed deficiency in natural gas as a feedstock source.* Production of methanol is particularly affected, along with derivation routes which employ it. Sources based on petroleum are also assumed to be less plentiful than in the base case, although the deficiency is not hypothesized to be as extreme as in Scenario I. Derivation routes using petrochemical basics from other sources are—where available—favored as replace- ments for methane and methanol. It should be noted that quantitative data from which to calculate waste factors were not available for a few derivation routes so the impacts of these cannot be measured. 7.2 The Intermediate Organic Chemicals 7.2.1 Acetic Acid Projected waste loads were examined for three methods of making acetic acid. Data were not available to derive waste factors for manufacture by oxidation of N-butane and other petroleum gases, so *Without compensation from coal gasification which would amount simply to a special situation under the base case. 73 ------- this route is considered only with regard to production. In all scenarios shown in Tables 19 and 20, the proportion manufactured by this process is assumed to decrease from the base case. Scenario II is particularly interesting. Here, the sharp drop shown in Table 19 for use of the Wacker process reflects a decreased use of that process because of the hazardous waste associated with its intermediate product, acetaldehyde. Distillation bottoms and sidecuts from the production of acetaldehyde from ethylene are assigned EPA hazardous waste numbers K09 and KlO, under recently released RCRA regulations (U.S. Environmental Protection Agency 1980a). The availability of alternative production routes offers a way to reduce hazardous waste. The high factor for solid waste in pyrolysis of liquor from wood reflects the low yield of acetic acid from hardwood. In some instances, other outputs might be obtained from the same feedstock (see flow diagram in Appendix C), thus reducing the quantity of waste attributable to production of acetic acid. If the chemical industry turns heavily to plant sources (as hypothesized in Scenario III) integrated facilities producing acetic acid, along with other outputs such as methane and methanol, could reduce total waste loads. Evidence was not found in the literature to suggest whether this would be hazardous waste, nor is it known how the refuse may be disposed of. 7.2.2 Acetylene For the acetylene production routes considered here, only par- tial quantitative data on waste were available. As shown in Table 22 74 ------- TABLE 19 ACETIC ACID - WASTE PROJECTIONS YEAR 2000 Percentage of Total Produced by Process Scenario Output 106 Tons From Ethylene (Wacker Process) From Methanol (Carbonylation) Wood Pyroligneous Liquor Oxidation of Petroleum Gases External Conditions Base Case 1.86 31 14 51 Scenario I 1.86 27 31 10 32 o Decreased availability of petroleum feedstocks o Cost-effective methanol Scenario II 1.86 12* 64 19 o Use of processes reducing waste generation and pro- moting recycling o Increased reliance on methanol from refuse- derived methyl alcohol Scenario III 1.86 33 38 20 o Decreased use of petro- leum feedstocks o Technological advances in processes using plant sources o Increase in ethylene from fermentation-derived ethanol Scenario IV 1.86 30 11 49 o Deficiency of natural gas with no offset from coal- gasification products *Sharp drop reflects hazardous wastes associated with intermediate product, acetaldehyde. ------- TABLE 20 ACETIC ACID - WASTE PROJECTIONS YEAR 2000 Process Acetaldehyde From Ethylene by Wacker Process Methanol by Carbonylation Wood-Pyroligneous Liquor Oxidation of Petroleum Gases Waste Type Nature Catalyst metals; Wastewater organics; sulfates; oils; corrosiveness; acidity Solid content Propionic acid, Wastewater higher organics Solid content Wood pulp Solids Unknown Waste Factor Per Ton of Product Units Base Case 1,000 Galsa 106 1,020.00 Gals 130 Lbsa 106 0.07 Tons 23 Galsb 106 10.0 Gals 80 Lbsb 106 0.02 Tons 13 Lbsc 106 1.80 Tons Amount of Waste Scenario I Scenario II Scenario III Scenario IV 890.00 410.00 1,100.00 100.00 0.06 0.03 0.07 0.07 23.00 49.00 29.00 7.00 0.04 0.08 0.05 0.01- 4.30 2.10 8.50 4.60 (No quantitative data available) Sources: aLiepins et al. 1977. bHedley 1975. cDerived from materials balance in Lowenheim and Moran 1975. ------- TABLE 21 ACETYLENE - PRODUCTION ASSUMPTIONS YEAR 2000 Percentage of Total Produced by Process Output Methane Calcium Carbide Coal-Plasma Scenario (106 Tons) Partial Oxidation From Coal Pyrolysis Base case .27 38 62 0 Scenario I Same as base case Scenario II .27 47 25 28 Scenario III Same as base case External Conditions o No commercial use of plasma pyrolysis of coal o Natural gas deficiency, without coal gasification as substitute Scenario IV .27 19 81 o Waste generation constraints; plasma pyrolysis significantly reduces waste in coke production and derivation of calcium carbide ------- the use of plasma pyrolysis in Scenario II would reduce the amount of waste generated compared to alternative derivation from coke and subsequently calcium carbide, but the amount is unknown. The calcium hydroxide which constitutes most of the solid waste may be disposed of as a by-product of this process. 7.2.3 Acrylonitrile All acrylonitrile is now manufactured by ammonoxidation of propylene, but it can also be produced from acetylene using hydrogen cyanide (HCN). Both a liquid phase and a vapor phase process exist although the latter has never been commercialized (Furgate 1963). As noted above there is also a process available to convert acetonitrile (now an intermediate waste) to acrylonitrile by catalytic oxidation with methane (Gelbein 1979). This is an important process hypothe- sized for Scenario II, which emphasizes recycling. Still bottoms and bottom streams from acrylonitrile production have hazardous waste numbers KOI 1 through K014 under RCRA regulations (U.S. Environmental Protection Agency 1980). Some components classified as hazardous under these regulations are also contained in waste generated when acrylonitrile is produced from acetylene, specifically HCN and residual acrylonitrile itself in the stripper-effluent water from the liquid phase process. 7.2.4 Ethanol The two basic routes for deriving ethanol (ethyl alcohol) are from ethylene or from biological material (including whey and plant sources) by fermentation. These are compared in the simplified flow 79 ------- TABLE 23 ACRYLONITRILE - PRODUCTION ASSUMPTIONS YEAR 2000 Percentage of Total Produced by Process Output Ammonoxidation Ammonoxidation of Scenario (10^ Tons) of Propylene Acetylene Propylene With Recycle Base case 2.54 100 0 0 Scenario I 2.64 75 25 0 GO O External Conditions o Reduced use of propylene reflects 25 percent decrease in available petroleum feedstock o Technological advances with acety- lene route commercially attractive Scenario II 2.54 25 75 o Use of process reducing waste gen- eration and promoting recycling Scenario III Same as base case Scenario IV Same as base case ------- TABLE 24 ACRYLONITRILE - WASTE PROJECTIONS YEAR 2000 00 Process Type Propylene Ammonoxidation Sulfate; acetonltrile organic polymers Propylene Ammonoxidation With Recycle Acetylene Unknown Waste Waste Factor Per Ton of Nature Product Wastewater 929 Gals3 Solids 269 Lbsa Wastewater 532 Galsb Solids 28 Lbsb Amount of Waste Units Base Case Scenario I Scenario II 106 Gals 2,360.0 1,765.0 106 Gals 0.34 0.26 106 Gals 1,010.0 10& Gals 0.03 (No quantitative data available) Sources: aLowenbach and Schlesinger 1978. bDerived from Gelbein 1979. ------- diagrams in Appendix C. As already noted, about 94 percent of etha- nol is now produced from ethylene and this percentage is assumed in the base case. In the alternative scenarios for ethanol shown in Tables 25 and 26, greater use is made of fermentation to derive ethyl alcohol for chemical use. Since further products can be made from it, ethanol production in Scenario III is assumed to increase by 55 percent over the base case. The wastes generated in the fermentation route to ethanol are far greater than those resulting from use of ethylene. However, much of the material suitable for fermentation produces waste which can be used as livestock feed. 7.2.5 Methanol Methanol is now derived almost exclusively for chemical use from methane and synthesis gas, and this situation is assumed to continue in the base case. However, it can also be derived from plant sources (witness the time-honored name "wood alcohol"). Methane and syn- thesis gas now used for production of methanol generally come from natural gas feedstocks, but could also be derived from processes which gasify coal (such as the WESCO or Winkler processes), and from organic solid wastes including municipal refuse (Jones 1978). If petroleum feedstocks were unduly costly or in short supply, the requirement for methanol could be expected to increase as an alterna- tive raw material for several chemicals, including acetic acid and acetylene, which are examined in this section. 82 ------- TABLE 25 ETHANOL (ETHYL ALCOHOL) - PRODUCTION ASSUMPTIONS YEAR 2000 Scenario Output (106 Tons) Percentage of Total Produced by Process Ethylene Plant Sources Hydration Fermentation External Conditions Base Case .89 93 Scenario I CD OJ .89 67 33 o Decrease in petroleum feedstocks o Technological advances allow plant source feedstocks to be competitive for ethyl alcohol synthesis from ethylene Scenario II Same as Scenario III o Technological cost-effective advances in use of fermentation from plant sources Scenario III 1.38 59 41 o Wider use of ethanol as route to Cj and C^ chemicals, offsetting high cost or low availability of petroleum Scenario IV Same as Scenario I ------- TABLE 26 ETHANOL (ETHYL ALCOHOL) - WASTE PROJECTIONS YEAR 2000 CO Process Ethylene (Hydration) Fermentation Plant Sources , Other Biologic Material Type NaOH Silage; can be used for annual feed Waste Waste Factor Per Ton of Nature Product Wastewater 5.4 Galsa Solids 5.0 Lbsb Solids 2000.0 Lbs Amount of Waste Units Base Case Scenario I 106 Gals 5.90 4.30 106 Tons 0.003 0.002 106 Tons 0.09 0.390 Scenario III 5.9 0.003 0.75 Sources: aLiepins et al. 1977. bTong 1978. ------- The scenarios for methanol production, which are contrasted with the base case, reflect an overall increase in output, a shift in the relative contributions of input sources, or both. Three of the scenarios assume that total production will increase over the base case in the year 2000, with hardwood, refuse, and synthesis gas from fossil-fuel sources contributing varying amounts. Scenario III hypothesizes that the output will drop slightly from the base case (from 9.23 to 9 million tons), as a result of deficiences in natural gas for feedstocks. Scenario II again may be of greatest interest. It represents regulatory pressures which result in recycling refuse to reduce the amount of solid waste requiring ultimate disposal. However, the quantities that would be consumed in producing methane and synthesis gas (out of which methanol can be derived) are not known so the net reduction cannot be estimated. There are also no data on the poten- tially hazardous components which may remain in the residuals after various discarded industrial products, sludge, and other refuse are consumed. These points could be of considerable future interest. 7.2.6 Phenol Most phenol (more than 80 percent) is now made by peroxidation of cumene derived from alkylation of benzene by propylene. Small quantities are also made from tar and other oils produced by carbon- ization of coal, from benzoic acid from toluene, from chlorobenzene, and from sulfonation of benzene. These processes are considered in 85 ------- TABLE 27 METHANOL - PRODUCTION ASSUMPTIONS YEAR 2000 Output Methane Scenario (10^ Tons) Synthesis Gas Percentage of Total Produced by Process Hardwood Refuse External Conditions Base Case 9.2 99 1 0 Scenario I 11.1 99 o Decreased availability of petroleum o Increase in methanol production to compensate o No shortage of natural gas o No increase commercialization of derivation technologies from plant Scenario II 11.1 49 50 o Regulatory pressures for greater use of waste material lead to increased use of methanol and greater produc- tion from refuse Scenario III 10.0 90 10 o Increased commercialization of deriva- tion technologies from plant source Scenario IV 9.0 39 11 50 o Decreased availability of natural gas o Partly compensated by increased reliance on plant sources o Slight overall decreases in methanol production ------- TABLE 28 METHANOL - WASTE PROJECTIONS YEAR 2000 Waste Waste Factor Amount of Waste Process Type Nature Product Units Methane, Synthesis Wastewater 300 Gals 10 Gals CO »J Gas Solids 6.6 lbsa 106 Tons Hardwood Oil; higher boiling Solids 2.4 Tonsb 106 Tons point organics Refuse Unknown Base Case Scenario I Scenario II Scenario III Scenario IV 2,740.00 3,300.00 1,620.00 2,700.00 2,400.00 0.30 0.36 0.18 0.30 0.26 0.22 0.24 0.24 2.40 2.40 (No quantitative data available) Sources: Liepins et al. 1977. Derived from materials balance, Lowenheim and Moran 1975. ------- the scenarios defined in Tables 29 and 30. Derivation from benzene by the Hooker-Raschig process, which in 1978 accounted for about 4 percent of phenol production and for which waste factors could not be derived, is conveniently assumed to be phased out in the scenarios. There appears to be a trade-off between volumes of waste and hazardous components. Total waste volumes are lowest in the base case. Scenario II shows reductions in hazardous components of waste—but not in the volume of waste generated. 7.2.7 Vinyl Acetate and Vinyl Chloride Vinyl acetate and vinyl chloride are produced either from ethy- lene or acetylene. The use of ethylene predominates overwhelmingly: about two-to-one in the production of vinyl acetate, and on a ratio of more than fifteen-to-one for vinyl chloride. These proportions are assumed in the base case, while the alternative scenarios consider changes in the production mix between these two routes. With vinyl chloride, hazardous waste generation could be reduced by using the acetylene process rather than the one employing ethylene. The ethylene route generates a greater quantity of waste and the heavy ends from the distillation of ethylene dichloride and of vinyl chloride have been assigned hazardous waste numbers K019 and K020 under the latest RCRA regulations (U.S. Environmental Protection Agency 1980a). *As represented by the balanced process in which ethylene dichloride is first formed and then pyrolyzed to yield vinyl chloride monomer (VCM). 88 ------- TABLE 29 PHENOL - PRODUCTION ASSUMPTIONS YEAR 2000 Percentage of Total Produced by Process Output Cumene Benzene Coal Tar Benzole Acid Benzene Scenario (106 Tons) Peroxldation Chlorobenzene Sulfonatlon Middle Oils From Toluene Hooker-Raschig External Conditions Base Case 4.93 89 oo Scenario I 4.93 61 19 o Reduction of petroleum- associated sources leads to increased reliance on coal replacing propylene as feedstock Scenario II 4.93 50 36 o Regulatory pressures to reduce waste disposal under RCRA, etc. Scenario III Same as Scenario I Scenario IV Same as Scenario I ------- TABLE 30 PHENOL - WASTE PROJECTIONS YEAR 2000 Waste Waste Factor Per Ton of Process Type Nature Product Cumene (Perox- Phenol; aceto- Wastewater 445 Galsa idation) phene Solids 40 'Lbsa Chlorobenzene Diphenyl ether Solids 81 Lbsa Benzene (Sulfon- Solids 432 Lbsb ation) Coal Tar Middle Tar; phenate; Solids 1,313 Lbsc Oils cresylate in bottom stills Benzoic Acid, Tar; acetate; Solids 276 Lbs From Toluene benzoates Benzene (Hooker- Unknown Raschig Process) Amount of Waste Units Base Case Scenario I 106 Gals 1,953.00 1,335.00 106 Tons 0.09 0.06 106 Tons 0.006 0.01 106 Tons 0.03 0.06 106 Tons 0.03 0.62 106 Tons 0.05 0.06 No quantitative data available Scenario II 1,100.00 0.05 0.07 0.05 0.07 0.06 Sources: aLiepins et al. 1977. bHedley 1975. °Derived from materials balance, Lowenheim and Moran 1975. ------- The issue is not clear cut. In deriving vinyl chloride from acetylene, mercuric sulfide may be produced in the waste from the catalyst used. However, it appears that this metallic component can be reclaimed through recycling, which could be easier than disposing of the heavy ends that result from producing VCM by the ethylene dichloride route. Thus, on both quantitative and qualitative grounds, the acety- lene route is preferred in Scenario I, a scenario emphasizing waste reduction—particularly of hazardous constituents. This is achieved by increasing the quantity of vinyl chloride produced from acetylene at the expense of the alternate route from ethylene which plays a larger role in Scenarios II and III. For vinyl acetate the derivation route from acetylene generates 15 times as much waste as the ethylene route. Hence in Scenario II greater use of ethylene is hypothesized than in Scenario I (which emphasizes a deficiency of petroleum-derived feedstocks). More ethy- lene is also assumed to be used in Scenario III in which widespread commercialization of fermentation processes is hypothesized, leading to derivation of ethylene from ethyl alcohol. Vinyl acetate waste loads are lowest for the base case (which assumes maximum use of ethylene) and highest for Scenario II (which assumes minimum use of that petrochemical basic). Neither vinyl chloride nor vinyl acetate production is significantly affected by an assumed deficiency in natural gas 91 ------- TABLE 31 VINYL ACETATE - PRODUCTION ASSUMPTIONS YEAR 2000 VD Percentage of Total Scenario Base Case Output (106 Tons) 4.54 Ethylene by Oxyacetylin 66 Produced by Process From Acetylene 34 External Conditions Scenario I 4.54 33 67 o Decreased availability of petroleum feedstocks o Switch to coal-derived feedstocks Scenario II 4.54 55 45 o Use of processes generating less waste (acetylene route has higher waste factors) Scenario III Same as Scenario II Scenario IV Same as Scenario I ------- TABLE 32 VINYL ACETATE - WASTE PROJECTIONS YEAR 2000 Process Ethylene, Oxyacetylation Acetylene Type Acetates; benzene; acetic acid Catalyst metals; tars; organics Waste Nature Wastewater Solids Solids Amount of Waste Waste Factor Per Ton of Product 56 Galsa 5 Lbsb 144 Lbsb Units 106 106 106 Gals Tons Tons Base Case 166.000 0.008 0.113 Scenario I 84. 0. 0. 000 004 219 Scenario II 140.000 0.007 0.147 Sources: aU.S. Environmental Protection Agency 1974. bHedley 1975. ------- feedstocks so the projections in Scenario IV and Scenario I are the same. 94 ------- TABLE 33 VINYL CHLORIDE - PRODUCTION ASSUMPTIONS YEAR 2000 Scenario Output (106 Tons) Percentage of Total Produced by Process Ethylene Dichloride Balanced Process Acetylene External Conditions Base Case 18.9 94 vo Ln Scenario I 18.9 33 67 o Switch to coal-derived feedstocks o Efforts to reduce genera- tion of hazardous waste Scenario II 18.9 79 21 o Increased reliance on plant Sources o Ethylene derived from ethanol partly compensates for reduced availability from petroleum feedstocks Scenario III Same as Scenario II o Widespread commercializa- tion of fermentation processes Scenario IV Same as Scenario I ------- TABLE 34 VINYL CHLORIDE - WASTE PROJECTIONS YEAR 2000 Process Waste Type Nature Waste Factor Per Ton of Product Units Amount of Waste Base Case Scenario I Scenario II Ethylene Bichloride Trichloroethane, Wastewater 3.0 Galsa 10^ Gals (Balanced Process) tetrachloroethane, vinyl chloride and ethylene dichloride 5,970.00 2,110.00 5,025.00 VD a-- Acetylene Mercury (HgS) -01/Ton Product Solids Wastewater Solids 96.0 Lbsa 480.0 Galsa 4.8 lbsb 106 Tons 106 Gals 106 Tons 1.01 518.00 0.01 0.36 6,048.00 0.03 0.85 1,872.00 0.01 Sources: aLiepin; et al. 1977. t>Lowenheim and Moran 1975 (derived from catalyst loss). ------- APPENDIX A HAZARDOUS WASTE A.1 Quantities of Hazardous Waste Manufacturers of chemicals and allied products have been esti- mated in one study to represent 7,100 generators of hazardous waste, producing about 1.65 million tons of such waste each month. The petroleum refining industry (a major source of petrochemical basics) has been estimated to generate another 0.08 million tons monthly (Fred C. Hart Associates, Inc. 1977). EPA has estimated that, in 1977, the organic chemical industry alone produced some 12.9 million tons of hazardous waste or about 34 percent of the national total (U.S. Environmental Protection Agency 1980b). Hazardous waste totals are projected to grow at an annual rate of about 3 percent and to exceed 75 million tons by the year 2000 (U.S. Environmental Protec- tion Agency 198Ob). Inevitably, significant increases in the future output of chemi- cals will be accompanied by greater quantities of waste materials. That future output is likely to be influenced by economic factors—an effect observed in the short term during recent temporary slumps in the economy. For example, the output of most organic chemicals pro- duced in large volume declined in 1975 as compared with 1974 (Chemi- cal Information Services 1977). On the basis of present trends, hazardous wastes from the chemi- cal industry would be projected to increase between now and the year 97 ------- 2000 at an annual rate of 3 to 4 percent. Applying the growth rate of the organic chemicals industry to the rate of hazardous waste gen- eration and assuming no change in processing methods and feedstock sources, this industry alone could generate as much as 32 million tons of hazardous waste in the year 2000. Of course changes within the industry can be expected to affect both production mix and waste generation, but this figure provides a reference point for compara- tive purposes. A. 2 Characteristics and Implications Toxicity is a characteristic of a chemical substance defining the degree of adversity for an organism exposed at a given dose level. Hazard refers to the likelihood that a chemical will be pres- ent at a harmful exposure level. A chemical can have relatively high inherent toxicity but can be considered non-hazardous if exposure results in insufficient dosages to produce a toxic effect (U.S. Environmental Protection Agency 1980b). Estimates of likely exposures can be obtained from such sources as: o Current or proposed production rates; o Data on probable environmental releases from production, use and disposal through mass-balance engineering assessments; and o Study of basic chemical/physical properties. The traditional technique for studying the acute effects of toxic agents is lethality dose determination, a short-term animal test to determine what dose of a chemical agent would result in the death of 50 percent of the test animal population (LD5Q). While 98 ------- exposures capable of producing such acute effects are the result of rare events such as spills, prolonged or repeated exposures to chem- ical agents in the environment can result in chronic toxicity. Cause-effect relationships are often not as apparent in chronic exposures as they are in studies of acute toxic exposure. The toxic response may result from storage of the chemical; the action of its metabolic products in the body; repeated and additive insults on target organs, enzymes, hormones, or other body systems; or a long- delayed response to a single or time-limited exposure. Chronic exposures to toxicants may induce behavior modification, mutagenic alterations, loss of reproductive capabilities, cancer or cellular damage (U.S. Environmental Protection Agency 1980b). Known toxicants in industry have affected employees and spread to the general population. Vinyl chloride has been implicated as a cause of liver cancer in industrial workers and other toxicants, identified in laboratory studies, have been found at some workplaces in the air and drinking water where they pose a hazard. Polychlori- nated biphenyls (PCBs), suspected as carcinogens, are found at levels exceeding one part per million in the tissues of nearly 40 percent of the U.S. population (U.S. Environmental Protection Agency 1980b). Perhaps the most dramatic U.S. example of the impacts that can result from hazardous wastes is afforded by Love Canal, which came to national attention in 1978. More than 25 years ago 20,000 tons of chemical waste had been placed in a dumpsite along the canal near 99 ------- Niagara Falls, N.Y., and numerous chemicals have leached from the site. Of the 100 chemicals identified, 11 were suspected carcinogens and one—benzene—is classified as a known carcinogen. Estimates are that as much as 10 percent of the chemicals in the dumpsite may be mutagens, carcinogens, or teratogens. Area health statistics show increased miscarriage and birth defect rates among residents (three and three and-a-half times the normal rate, respectively). Signs of liver damage among adults have also been noted (U.S. Environmental Protection Agency 1980b). Hazardous waste can cause economic disrupution—as was the case when Virginia fisheries were closed after officials discovered that the insecticide kepone had been discharged into the James River near Hopewell, Va., from the mid-1960s until 1975. A. 3 Current Laws and Regulations A number of Federal laws give EPA statutory authority to regu- late solid waste and control toxic and hazardous materials. Among the key enactments are the following (in chronological order of Congressional passage): o 1963, Clean Air Act (PL 88-206); o 1976, Resource Recovery and Conservation Act (PL 94-580); o 1976, Toxic Substances Control Act (PL 94-466); o 1977, Major amendments to the Clean Air Act under PL 95-95; and o 1977, Water Pollution Control Act, or Clean Water Act (PL 95-217). 100 ------- EPA has developed a three-pronged approach to address the solid waste problem: o The quantity of solid waste generated annually should be reduced; o Whenever possible, solid waste should be recovered as a source of material and energy; and o Whatever solid waste cannot be recycled must be disposed of in a way that is safe for human health and the environment. This approach reflects the Resource Conservation and Recovery Act (RCRA), which amended Title II of the Solid Waste Disposal Act, providing EPA with its broadest authority relating to solid wastes. It defines solid waste as, Any garbage, refuse, sludge from a waste treatment plant, water supply treatment plant, or air pollution con- trol facility and other discarded material, including solid, liquid, semi-solid or contained gaseous material resulting from industrial, commercial, mining, and agricultural opera- tions and from community activities (U.S. Congress 1978). Most of the regulatory provisions of RCRA are contained in three sections. Under Subtitle A, EPA must publish guidelines for solid waste management. Subtitle C requires that EPA promulgate hazardous waste regulations in order to monitor and control such wastes from generation to final disposal. This section also defines hazardous waste. Subtitle D is intended to "assist in developing and encourag- ing methods for the disposal of solid wastes which are environmental- ly sound and which maximize the resource conservation." Under the Toxic Substances and Control Act (TSCA), EPA is empowered to obtain industry data on production and tests involving 101 ------- chemicals which are regulated to avoid "...an unreasonable risk of injury to health or the environment." As necessary, EPA may require that manufacturers or processors perform tests at their own expense to provide data on the chemicals. The manufacturer must also notify EPA 90 days before commercial production of a new chemical. A range of regulatory actions is authorized under the act, from requiring labeling to limiting or prohibiting the manufacture, processing, distribution, use or disposal of a toxic substance. TSCA is unique among environmental laws because it is designed to be a gap-filling law (U.S. Environmental Protection Agency 1980b). EPA is to defer to other agencies for action if they have statutory authority under another law. Also, if EPA itself has sufficient authority to deal with a problem under another law, the agency must use that other authority (U.S. Environmental Protection Agency 1980b). Since TSCA is a gap-filling law, other statutes are of consider- able importance. For example, Section 112 of the Clean Air Act has provided regulatory authority for hazardous air pollutants. It pre- scribes procedures for the EPA Administrator to list hazardous air pollutants, establish a standard for each pollutant, and issue infor- mation on techniques for their control. The initial list of hazard- ous pollutants was limited to asbestos, beryllium and mercury, for which standards were issued in April 1973 (38 FR 8820). Standards for vinyl chloride and benzene were added in 1976 and 1977 and arsenic and cadmium are being considered. Other substances may be added later. 102 ------- Section 307 (Toxic and Pretreatment Effluent Standards) of the Clean Water Act of 1977 (PL 95-217) provides authority to regulate toxic effluents. This section identified an initial list of 65 toxic pollutants or combinations of pollutants which has been expanded into a new list of 129 ''priority pollutants" (114 organic compounds, 13 metals, asbestos and cyanide). Further details on legislation applicable to hazardous materials may be found in Environmental Outlook, 1980 (U.S. Environmental Protection Agency 1980b). A.4 Management and Disposal Techniques What happens to the tons of hazardous waste produced each year as a by-product of industry? A recent study estimated that 80 per- cent of the hazardous waste generated by the chemical industry is managed* on site (Fred C. Hart Associates, Inc. 1977). Wastes are temporarily stored in surface impoundments, basins and lagoons before they are disposed of—largely in landfills, through biological treat- ment or in deep wells (Maugh 1979). Data submitted in industry comments on proposed Section 3004 regulations under RCRA indicate that chemical companies operate approximately 2,500 surface impoundments which actually or probably contain hazardous wastes (Manufacturing Chemists Association 1979). It can also be estimated—by extrapolating data from one major oil *The term "waste management" has not been technically defined, but it is used here to indicate the techniques for storing, treating and disposing of waste. 103 ------- company (Exxon Corporation 1979)—that about 250 to 300 impoundments are associated with petroleum refineries, a primary source of petro- chemical feedstocks. In waste1 disposal, a wide practice is biological treatment of wastewater streams discharged to waterways under National Pollutant Discharge Elimination System (NPDES) permits. A survey of surface impoundments showed that approximately 95 percent had NPDES permits. Of those, 61 percent contained hazardous wastes (Manufacturing Chemists Association 1979). Landfilling is another important method for disposing of hazard- ous wastes from the chemical industry. Extrapolation of data for a number of companies indicates as many as 250 existing hazardous waste landfills (Manufacturing Chemists Association 1979). Solidification techniques have been and are being developed as preparation processes before landfilling the wastes. Still other disposal methods are deep wells, used for many years to dispose of hazardous liquid wastes, and land farming or soil in- corporation, a particularly popular method for nonchlorinated waste. This latter method has been used for years by the petroleum refining industry for disposing of refinery sludge (U.S. Environmental Protec- tion Agency 1980b). EPA has concluded that land disposal is the least desirable method because of the severe problems associated with landfilling, such as lack of available sites, contamination of ground and surface 104 ------- water and health hazards (U.S. Environmental Protection Agency 1980b). Controlled incineration is a preferred method for organic wastes, but is restricted by such drawbacks as cost, lack of effec- tive means to control release of hazardous atmospheric pollutants, and poor combustion properties of many wastes (U.S. Environmental Protection Agency 1980b). EPA favors minimizing wastes requiring disposal by recycling. The agency also prefers altering production processes to eliminate hazardous wastes (U.S. Environmental Protection Agency 1980b) and direct reuse is being investigated. Hazardous materials may be removed from the waste stream and reused in the production process. As a result, the total volume of hazardous wastes may be reduced (U.S. Environmental Protection Agency 1980b). A.5 Distribution of Chemical Waste A survey of industries producing organic chemicals, pesticides and explosives showed Texas, Louisiana and Puerto Rico to be the major centers of production. These industries are also heavily con- centrated in New Jersey, California, Pennsylvania and Ohio (Fred C. Hart, Associates, Inc. 1977). Traditionally, these industries have tended to locate plants along the waterways of the Northeast and Mid- west and along the West and Gulf coasts. (States producing the 13 selected petrochemical basics and intermediate organic chemicals treated in this study are shown in Figure A-l.) The industry is shifting from the Northeast and Midwest to the Southeast and South Central U.S. (U.S. Environmental Protection Agency 1980b). 105 ------- FIGURE A-1 STATES PRODUCING SELECTED PETROCHEMICAL BASICS AND INTERMEDIATES ------- APPENDIX B CALCULATION OF ESTIMATED PRODUCTION IN YEAR 2000 This appendix explains the method used to project total output of individual intermediate organic chemicals estimated to be produced in 2000 under the base case. The assumption, inherent in the defini- tion of the base case, is that present growth rates of chemical pro- duction will continue unchanged. The latest available information on trends in production of selected chemicals was used to define the average annual growth rate of that chemical. Starting from a given year, yo, production in the following year, yo + 1, will be greater by a factor of 1 + r, where r denotes the annual growth rate. In n years (year yo + n), production will accordingly be (1 + r)n times that of the base year, yo. The value (1 4- r)n represents the growth multiple, M. Production in year 2000, P, is given by the expression P = Mp, where p denotes the production in the year 2000 - n. In calculating the growth multiple, natural logarithms (In), or logarithms to the base e, were used and M was obtained from the ex- pression In M = n ln(l + r), so that M = eln M The method is illustrated by actual calculations which project the output in year 2000, P, for acrylonitrile from total production 107 ------- in the year 1978 and average annual growth rate for the period 1968 to 1978 (American Chemical Society 1979). r = 0.04 so that 1 -1- r = 1.04. n = 22 p = 0.875 (in million of tons) In 1 + r = 0.04879 and In M = 22(0.04879) = 1.0734 M = eln M = 2.925 and P = Mp = 2.925 x 0.875 = 2.56. 108 ------- APPENDIX C SIMPLIFIED DIAGRAMS ILLUSTRATING DERIVATION PROCESS FOR SELECTED CHEMICALS This appendix presents several chemical trees and flow diagrams illustrating derivation routes and processes employed to produce selected chemicals. In the highly simplified graphic material, no attempt is made to be comprehensive in treatment or to portray the chemistry of the processes involved. The diagrams are intended merely to depict some major points of commonality and contrast in the derivation paths and to shed some light on the processing sequence, from feedstock source to selected chemical, alluded to throughout this study. 109 ------- NATURAL GAS AND NATURAL GAS LIQUIDS METHANOL - ACETIC ACID REFINERY LIQUIDS ACETIC ACID - ACETYLENE • ETHYLENE • PROPYLENE• BENZENE TOLUENE • XYLENE ' VINYL CHLORIDE • VINYL ACETATE • ETHYLENE DICHLORIDE - VINYL • VINYL ACETATE • ETHANOL • ACETALDEHYDE • CUMENE - PHENOL • ACRYLONITRILE C-1 PRODUCTION SOURCES OF CHEMICALS SELECTED FOR STUDY 110 ------- COAL TOLUENE GASIFICATION SYNTHESIS GAS ARC PLASMA PROCESS ACETYLENE PHENOL PROPYLENE OXIDE PROPYL ALCOHOL ACRYLONITRILE CRUDE OIL PROPYLENE PETROLEUM LIQUIDS PROPYLENE ETHYLENE FIGURE C-2 ALTERNATIVE ROUTES TO PROPYLENE DERIVATIVES • ACRYLONITRILE •CUMENE PHENOL •PROPYLENE OXIDE •PROPYL ALCOHOL ------- CRUDE OIL OR NATURAL GAS ' COAL SEPARATION OF NATURAL ETHYLENE CRACKING OF GAS, GAS LIQUIDS OR PETROLEUM LIQUIDS GASIFICATION ARC PLASMA PROCESS • ETHYLENE • SYNTHESIS GAS• ACETYLENE ETHYLENE — ETHYLENE —— VINYL ACETATE VINYL CHLORIDE • ETHANOL • ACETALDEHYDE — ACETIC ACID ETHYLENE _ VINYL ' BICHLORIDE CHLORIDE • VINYL ACETATE FIGURE C-3 ALTERNATIVE PATHS FOR PRODUCING ETHYLENE AND ETHYLENE DERIVATIVES ------- CRUDE OIL GAS NATURAL GAS COAL — HARDWOOD — — SEPARATION PROCESSES REFORMING GASIFICATION GASIFICATION PYROLYSIS NATURAL GAS LIQUID __„ TTTir- —^-^— SYNTHESIS GAS SYNTHESIS GAS SYNTHESIS GAS FYROLIGSEODS LIQUIOR — OXYGEN 1 Y 2 CO 1 i SEPARATION —^— METHANOL — ^ AND __ ACEIIC ACID PURIFICATION OXIDATION ACETIC ACID FIGURE C-4 ALTERNATIVE ROUTES TO ACETIC ACID ------- YEAST i 1 GROWING CROP -* HARVESTING CROP ^ TRANSPORTATION — * STRORAGE \~* GRINDING — * HYDROLYSIS --* FERMENTATION h ETHANOL T RESIDUE BY PRODUCTS & WASTE WATER RECOVERY OF OIL OR NATURAL GAS TRANSPORTATION TO REFINERY OR NATURAL GAS PLANT SEPARATION OF NATURAL ETHYLENE CRACKING OF GAS, GAS LIQUIDS OR PETROLEUM LIQUIDS • E1EYLESE • •ETHYLENE. WATER 1 HYDRATION RECYCLE ETHYLENE f, BY PRODUCTS ETHANOL Source: Shreve and Brink 1977. PURIFICATION DISTILLATION HASTE C-5 ETHANOL FROM PLANT SOURCES AND ETHANOL FROM ETHYLENE ------- HARVESTED WOOD GASIFICATION AQUEOUS PROCESSING SYNTHESIS GAS METHANE METHANOL METHANOL ACETIC ACID CARBOXYLYSIS METHANE BACTERIAL DIGESTION METHANE HYDROLYSIS AND FERMENTATION ETHANOL Source: Bliss and Blake 1977. FIGURE C-6 PROCESSES AND DERIVATIVES OF HARVESTED WOOD ------- APPENDIX D GLOSSARY Ammonoxidation [Ammoxidation] - a process in which nitrites are formed by the reaction of ammonia, in the presence of air or oxygen, with olefins, organic acid, or the alkyl group of alkylated aromatic compounds. Bottom streams - The process stream from the bottom of a distillation column. Carbonylation - The combination of an organic compound with carbon monoxide. Cracking - A process in which hydrocarbon modules are decomposed to form molecules smaller in size and with a lower level of satura- tion than the original molecules. Cracking occurs by exposing the molecules to high temperature or to moderate temperatures in the presence of a catalyst. Esterification - Formation of an organic salt from an alcohol and an organic acid by eliminating water. Fischer Tropsch process - A process for the conversion of coal to liquid hydrocarbons consisting of gasification of the coal to form carbon monoxide and hydrogen which are subsequently com- bined under the influence of a catalyst to form a series of paraffince compounds. Gasoline pool - Crude oil that is converted to and marketed as gaso- line. Heavy ends - High molecular weight component of a hydrocarbon mix- ture. Hooker Raschig process - Vapor phase process for the manufacture of phenol involving the oxychlorination of benzene to produce chlorobenzene followed by hydrolysis of the chlorobenzene to produce phenol. Liquefied refinery gases - Liquefied gases produced at petroleum re- fineries, so-called to distinguish them from liquefied petroleum gases obtained by processing natural gas (Bureau of Mines 1975). Monsanto process - A low pressure, rhodium catalyzed liquid phase methanol carbonylation process for producing active acid. 117 ------- Peroxidation - An oxidation reaction in which a peroxide is used as the oxidying agent. Plasma Pyrolysis process - A process in which coal can be converted to acetylene directly by passage through a plasma created by electric arc temperatures of between 8,000 and 15,000 K. Reformate streams - Streams from reforming reactor in which hydro- carbons are converted into aromatic compounds (benzene, xylene, toluene). 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