Waste Generation in the
Organic Chemicals Industry:
A Future Perspective
The MITRE Corporation

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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

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                              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

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                     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

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                          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

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                    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

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                          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

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                           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

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                     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

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                          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;
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      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
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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

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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.

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 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

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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

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                                    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

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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.

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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.

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     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

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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.

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      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

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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.


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     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

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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,






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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

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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







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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

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     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

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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

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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

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                               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

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     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

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                — ^ ——  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

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                         BIOMASS
                          (Trace)
                FIGURE2
SOURCES OF PETROCHEMICAL FEEDSTOCKS
                  1975
                   23

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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

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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

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     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

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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

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The effect of regulatory factors would be chemical-specific, requir-




ing consideration of different variables with each individual




product.
                                28

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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

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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

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                                                                     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

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      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

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                                       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

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                                    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

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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

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                            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

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                                                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

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     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

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                                                      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

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                                                     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

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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

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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

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                                                 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

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                                                  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

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                                                       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

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                                                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

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                                                                    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

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                                                   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.

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     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

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                                                  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

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                                                       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

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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

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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

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                            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

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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

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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).

Still bottoms - The high boiling temperature fraction of a mixture
     that remains in the bottom of a distillation column.

Wacker process - The direct oxidation of ethylene to acetaldehyde by
     means of liquid phase homogeneous catalysis.
                                 118

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                             REFERENCES
Abelson, H.  1980.  Synthetic Chemicals from Coal.  Science,
     February, 207 (4430):479.

American Chemical Society.  1979.  Facts and Figures for the  Chemical
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                                 123

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                                 124

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  Department Approval:,
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MITRE Project Approval:

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