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.
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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.
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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
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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
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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
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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
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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
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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.
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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
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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
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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
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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.
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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
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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
-------
3.0 CURRENT TRENDS AND POTENTIAL FOR CHANGE
3.1 Chemical Industry Output and Production Mix
Industry is churning out enormous quantities of chemicals to
satisfy a growing demand for an array of products—from auto parts to
stockings, and from pipe fittings to synthetic coats. Production of
synthetic organic chemicals in 1977 amounted to more than 87 million
tons, up nearly 10 percent from the 79.6 million tons produced in
1976 (U.S. International Trade Commission 1978). Production of the
top 50 organic chemicals totaled 86 million tons in 1978 compared
with 80.3 million in 1977 (American Chemical Society 1979). Outputs
of the 12 organic chemicals produced in the greatest quantities in
1978 are listed in Table 2.
The chemical industry relies heavily on petroleum and associated
products for feedstocks, yet it consumes a small share of available
refined crude oil. Petrochemical feedstocks produced from petroleum,
including liquid refinery gas, totaled about 145 million barrels in
1976 (Bureau of Mines 1976)—a figure that amounted to only about 3
percent of refined petroleum products used in the U.S. (American
Petroleum Institute 1976). Natural gas consumption in 1976 for
petrochemical feedstocks came to more than 630 billion standard cubic
feet—again representing about 3 percent of all U.S. usage. Sales of
liquefied petroleum gases and ethane in this country for feed-
stocks amounted to more than 140 million barrels (Bureau of Mines
1976).
19
-------
TABLE 2
TOP 12 ORGANIC CHEMICALS
Chemicals
Ethylene
Propylene
Benzene
Ethylene Dichloride
Toluene (All Grades)
Ethylbenzene
Vinyl Chloride
Styrene
Formaldehyde (37% by Weight)
Methanol
Xylene
Terephthalic Acid
Production
(106 Tons)
1978
14.1
7.7
5.7
5.2
4.6
4.2
3.5
3.4
3.2
3.2
3.1
3.0
1977
12.7
6.7
5.6
5.5
3.9
4.2
3.0
3.4
3.0
3.2
3.0
2.7
Average Annual
Growth
1968-78 (Percentage)
7.9
7.4
4.1
8.1
6.2
7.6
8.9
6.4
4.1
5.2
4.1
14.4
Source: American Chemical Society 1979.
20
-------
Feedstocks from sources other than petroleum and natural gas
have declined in importance, despite today's renewed interest in
them. In 1975 only about 2 million barrels of petrochemical feed-
stocks were derived from light oils, coke and coal tar processing
(Bureau of Mines 1976). The contribution of this source has declined
markedly since the end of World War II—a fact illustrated by the
trend in production of benzene, a major building block for synthetic
organic chemicals (Liepins et al. 1977). In 1950 only about 5 per-
cent of benzene production came from petroleum but by the early 1960s
the fraction had climbed to more than 75 percent as shown in Figure 1
(Grayson 1963). By 1977, it exceeded 80 percent (Anderson and
Tillman 1979).
Sources such as plant derivatives are currently insignificant.
Before 1945, however, ethanol was commonly derived from grain, molas-
ses, and other plant sources as an important first step in world pro-
duction of ethylene (Kochar and Marcell 1980). Now in the U.S., the
procedure has been reversed. More than 90 percent of ethanol used to
produce organic chemicals is derived from ethylene.
As illustrated in Figure 2, the mix of feedstocks used in the
production of chemicals is roughly as follows: petroleum and lique-
fied refinery gas, 38 percent; natural gas and natural gas liquids
produced at gas processing facilities, 61.5 percent; and other
sources—chiefly coal oils—less than 1 percent (Bureau of Mines
1976). Tiny amounts of plant derivatives are used to produce
21
-------
— ^ —— Projected Range
1950 1955 1960 1965 1970 1975 1980 1985 1990 2000
Year
Source: Adapted from Ayers, G.W. 1964, Debreczeni, £ J. 1977, Purcell, W.P. 1978, and Sherwin and Frank, 1975.
FIGURE 1
U.S. PRODUCTION OF BENZENE
1950-2000
22
-------
BIOMASS
(Trace)
FIGURE2
SOURCES OF PETROCHEMICAL FEEDSTOCKS
1975
23
-------
industrial chemicals. However, somewhat larger quantities are used
by the distillery industry and in food processing. Not all of the
petrochemical feedstocks reflected in these percentages are used in
producing organic chemicals. Nearly 75 percent of the natural gas
devoted to feedstock use in 1976 went to produce ammonia (Bureau of
Mines 1976). Nevertheless, the breakdown is indicative of the
current production mix.
The organic chemicals industry has grown at a rate of nearly 6
percent annually as indicated by a growth rate of 5.7 percent per
year for the top 50 organic chemicals from 1968 to 1978 (American
Chemical Society 1979). Growth through the remainder of the century
is projected at more than 6 percent annually until about 1985 (U.S.
Environmental Protection Agency 1980b). Thereafter, output of
organic chemicals is expected to increase by about 3.5 percent per
year, reaching more than three times the 1978 production volume by
2000 (U.S. Environmental Protection Agency 1980b, Bureau of the
Census 1978).
Hazardous waste generation by the industry could be expected to
keep pace with increased chemical production. Details on hazardous
waste quantities, characteristics, regulations and disposal methods
are provided in Appendix A. Supplies of petroleum-based feedstocks
might not keep up with industry's needs, which would force changes in
chemical manufacturing.
24
-------
3.2 Potential Changes
3.2.1 Same Feedstocks from Different Sources
One set of possible changes in organic chemical production would
involve deriving the same feedstocks from different sources. For
example, hydrocarbon liquids produced in the conversion of coal to
Solvent Refined Coal (SRC II) could compete with the liquid products
of petroleum refining. Synthesis- gas derived from coal gasification
could be used in place of that now derived almost exclusively from
natural or refinery gas. The implications for waste generation in
this situation would not lie directly within the organic chemicals
industry but rather in the production of its feedstocks. Once the
feedstocks were provided, whatever their source, their conversion
into chemicals would be essentially the same. Logically the wastes
generated from that point on could be the same as those now asso-
ciated with the production process, although that point is arguable.
3.2.2 Input Substitution
Input substitutions in organic chemical production processes are
possible. Ethanol derived from plant sources can be used to produce
ethylene, rather than the reverse. This approach is proving attrac-
tive in third world countries lacking petroleum stocks (Kochar and
Marcell 1980). There is also interest in using grain to produce
ethanol for gasohol. Acetylene can be widely used as an alternative
input source for the derivation of several intermediate organic chem-
icals although it now contributes only a small fraction.
25
-------
The effect of such substitutions would be less far-reaching than
those involving the alternative derivation of basic feedstocks, since
each substitution would be chemical-specific. However, when any
chemical is produced in enormous volume, the effect of an input
change could be great. This could be the case for ethylene, regarded
as the most important petrochemical building block in terms of the
quantity produced and its dollar value (Lowenheim and Moran 1975).
Input substitution depends principally on relative costs of
alternatives. A cheaper input material may be associated with a more
expensive production route. Moreover, industrial flexibility is
limited to some degree. Plants producing a given chemical are likely
to be designed for a specific process, or set of related processes,
which may require the same input. The cost of redesign to accommo-
date different starting materials may be prohibitive, making change
desirable only in new plants.
3.2.3 Use of Alternative Processes
Starting from the same input, alternative processes can be used
to produce a given chemical. Acetylene can be derived directly from
coal rather than by today's indirect route and phenol can be produced
from benzene by a sulfonation or a caustic (chlorobenzene) process.
Some of these alternative processes have important implications
for resulting waste loads. Direct production of acetylene from coal
by plasma pyrolysis would yield less waste than when calcium carbide
26
-------
is used (although quantitative data are lacking).* Plant flexi-
bility and comparative energy requirements are likely to affect
industry's willingness to adopt such alternative processes.
3.2.4 Recycling Intermediate Outputs
Input requirements and waste generation can both be reduced by
recycling by-products now regarded as waste, such as acetonitrile.
Such approaches would be attractive to industry if it were cost
effective to recycle waste rather than to dispose of it.
3.3 Regulatory Factors
Constraints imposed on the organic chemical industry under leg-
islative mandates will undoubtedly alter production processes. The
manufacture of some toxic substances might be banned entirely under
the Toxic Substances Control Act (TSCA). Regulations affecting waste
management and disposal can affect the routes chosen to derive chemi-
cal products. As costs of complying with environmental regulations
mount, the economic trade-offs are likely to shift. Processes that
were initially cheaper could become less cost effective when the
price of pollution containment is considered. Recycling intermediate
waste products could become more attractive economically than manag-
ing and ultimately disposing of them as residues, particularly if the
problem of decontaminating hazardous constituents is significant.
''This alternative, while technically feasible, has not been demon-
strated on a commercial scale.
27
-------
The effect of regulatory factors would be chemical-specific, requir-
ing consideration of different variables with each individual
product.
28
-------
4.0 FEEDSTOCKS FOR CHEMICAL PRODUCTION
This section demonstrates that higher waste loads could accom-
pany a shift to alternative feedstock sources. Such a shift could be
expected to result primarily from forces outside the industry itself
which would alter the relative availability and cost of feedstocks
from different sources—particularly coal, petroleum, and natural
gas.
Feedstock requirements will reflect production rates of all
basic petrochemicals and major intermediate organic chemicals so
changes in the waste loads will involve a complicated interrelation-
ship between the chemical industry and all other sectors of the econ-
omy competing for fuel and energy sources. Waste loads will also be
affected by the types of materials used, particularly the kinds of
coal, and the conversion processes used to achieve gasification and
liquefaction.
4.1 Base Case Projections
4.1.1 Production
Table 3 provides 1975 feedstock production data along with a
base case estimate of feedstock production in 2000. Designed to
serve as a point of reference, these estimates reflect an assumption
that feedstocks for petrochemical use from coal, petroleum and
natural gas will continue to grow at the average annual rate observed
between 1970 and 1978, with no shift in the relative mix among feed-
stocks. At that rate, by 2000, production would be 3.4 times the
1975 output.
29
-------
OJ
o
TABLE 3
FEEDSTOCK PRODUCTION
BASE CASE
1975 and 2000
Feedstock
1975
Feedstock
Source Production
Estimated Feedstock
Production in 2000
Petroleum (Including
Liquid Petroleum
Gas and Liquid
Refinery Gas)
Tar Oils, Other Oils
Natural Gas
Plant Derivatives3
Refining
Coal
Processing plants
Distilleries
288.0 x 106 bbl
2.0 x 106 bbl
632.4 x 109 ft3
<1.0 x 106 bbl
980 x 106 bbl
7 x 106 bbl
2,150 x 109 SCF
2-3 x 106 bbl
Quantitative data on chemical feedstocks from plant sources and other biological materials
not available.
Assumptions: 1. No change in percentage distribution of feedstock sources between 1975
and 2000.
2. Chemical industry grows at a rate such that its output in 2000 is 3.4
times output in 1975 (U.S. Environmental Protection Agency 1980b).
3. Feedstock consumption grows correspondingly.
Source: Bureau of Mines 1975 and 1976.
-------
4.1.2 Waste Generation
Table 4 provides a reference point with regard to wastes asso-
ciated with the base case feedstock production. Potentially
hazardous waste components are identified, but it would be
inappropriate to label particular quantities of waste as hazardous.
The definition of that term will depend upon authoritative ruling by
EPA under the regulations provided. Specification of hazardous
wastes under RCRA and other legislative authority is proceeding.
4.2 Derivation of Alternative Scenario
In order to provide a strong contrast with the base case assump-
tions about feedstock production, an "alternative scenario" is hy-
pothesized in which significant quantities of feedstocks are derived
from coal and oil shale. This scenario is separate and distinct from
others described later. The underlying assumptions are arbitrary,
because no attempt has been made to relate the shifts in feedstock
sources to process changes in the production of particular chemicals.
The assumptions listed are not necessarily regarded as those most
likely to occur by 2000. The purpose is merely to illustrate waste
generation resulting from reasonable changes in feedstock sources.
Assumed characteristics for the alternative scenario are these:
a. A decrease of nearly 35 percent in the quantity of feed-
stocks derived in the base case from petroleum and asso-
ciated sources.
b. A 20 percent decrease in the amount derived from natural
gas.
31
-------
TABLE 4
WASTE* GENERATED FROM FEEDSTOCK PRODUCTION
BASE CASE
1975 AND 2000
U)
Unit
Feedstock Source Quantity
Petroleum Refining 10 bbl
(Including Liquid
Petroleum Gas,
Liquid Refinery Gas)
Tar Oils, Other Oils Coal 103 bbl
(140 tons)
9
Natural Gas Processing 10 SCF
Plants
Plant Material0
Waste Generated
Far Unit Of
Feedstocks Waste Loads
(Tons/Unit) ,,..,„..-,, (103 Tons)
reeastocK
Liquids Solids Production Liquids Solids
1.8 1.0a 288 x 106 518 288
bbl
Unknown 17. 8b 2 x 106 Unknown 35
bbl
Negligible, closed 632 x 109 Negligible
cycle operations,
with liquid dis-
charge limited
to small quan-
tities from leaks
and blowdown
2000
Waste Loads
„ , .. , (103 Tons)
reeostocbc ^ ^ ~^~^~^~^^^~^~
Production Liquids Solids
980 x 106 1,765 980
bbl
7 x 106 Unknown 125
bbl
2,150 x 109
SCF (ft3)
* Potentially hazardous components to be considered with petroleum feedstocks are: oil; metals (Cr, Zn, Ni, Cu, Va, Pb, Hg, etc.); phenols;
cyanide; and arsenic. With tar oils and other oils they are: trace metals (Zn, Pb, etc.); arsenic; caustic soda; and hydrocarbons.
Sources: Rosenberg, et al. 1976.
Anderson and Tillman 1979.
E
comprehensive data available.
stimated from application of waste factors to output.
-------
c. A quantity of feedstocks supplied from liquefaction of
coal (as represented by the SRC-II process) equal to about
12 percent of the petroleum-derived quantity hypothesized
for the base case. (The SRC output includes 16 percent
synthetic natural gas.)
d. A quantity of feedstocks derived from synthetic natural
gas (SNG) as represented by the Winkler and WESCO pro-
cesses equal to 15 percent of the volume of natural gas
hypothesized for the base case.
e. A quantity of feedstock synthesis gas by the Winkler process
equal to 10 percent of the volume of natural gas hypo-
thesized for the base case.
f. A fourfold increase in the amount of feedstock input
derived from coal by carbonization hypothesized for
the base case.
g. A quantity of feedstocks supplied from oil shale equal to
10 percent of the petroleum-derived quantity hypothesized
for the base case.
Petroleum imports are expected to fall 25 percent by the year
2000 (McCurdy 1980c), so it is assumed that petroleum use for feed-
stocks will drop by more than 25 percent. Assumptions about substi-
tute gas and liquids appear reasonable in light of a predicted
capacity for 3 million bbl per day or more by 2000 (McCurdy 1980c).
Arguments could be raised against the hypothesized reliance on coal
and oil shale (roughly 10 percent). Questions might also arise
because of the assumed increase in coal feedstocks derived from
conventional processes; however, the additional quantity involved is
only 3 percent of that postulated to come from petroleum.
In short, it can be said that the alternative scenario repre-
sents about as strong a contrast with the base case as is reasonable
to consider.
33
-------
4.2.2 Waste Load Projections
Table 5 shows one set of waste generation factors associated
with production of feedstocks from major alternative sources. Using
these waste factors, waste loads for this alternative scenario have
been calculated and are shown in Table 6.
4.3 Comparison of Waste Loads
As can be seen from Tables 5 and 6, waste loads attributable to
production of petrochemical feedstocks are far higher under the
alternative scenario than in the base case. In the alternative
scenario, oil shale contributes more solid waste than all other
feedstock sources combined—despite the relatively small percentage
of total feedstocks hypothesized as coming from this source. Even
conventional processing of coal by carbonization, which is postulated
in the alternate scenario to produce only a small fraction of feed-
stocks, would generate more solid waste than the total from all
sources projected for the base case.
Thus, whether the alternative scenario is realistic or probable
is a matter of less consequence than the point it illustrates: use
of substitute sources to replace any significant amount of the feed-
stocks now derived from petroleum and natural gas will inevitably
result in increases in solid, semi-solid and liquid wastes. It has
been estimated that of every ton of coal mined for conversion to
fuels or feedstocks by the Fischer-Tropsch process, two-thirds repre-
sents waste that must be disposed of. The quantities of shale that
34
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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
-------
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
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TABLE 9
PRODUCTION OF SELECTED
PETROCHEMICAL BASICS
BASE CASE AND YEAR 2000
Petrochemical
Basic
Ethylene
Benzene
Propylene
Source
Gas
Petroleum
liquids
Solvent extrac-
tion of refor-
mate and
pyrolysis
gasoline
Coal carboni-
zation
Toluene
dealkylation
Refinery
Ethylene
co-product
Recent* Annual
Production Growth
From Source Rate
16.8 x 109 Ibs .072
6.2 x 109 Ibs
1,050 x 106 gals .061
70 x 106 gals
440 x 10& gals
5.4 x 109 Ibs .07
7.0 x 109 Ibs
Growth Year 2000
to 2000 Production
(Multiplier) From Source
4.22 71 x
26 x
3.39 3,550
gals
250 x
gals
1,490
gals
4.06 21.9
28.4
109 Ibs
109 Ibs
x 106
10&
x 106
x 109 Ibs
x 109 Ibs
Year 1976 for ethylene, 1977 for benzene and propylene.
45
-------
TABLE 10
PRODUCTION OF SELECTED
INTERMEDIATE ORGANIC CHEMICALS
BASE CASE AND YEAR 2000
Chemical
Acetic acid
Acetylene
Acryloni-
trile
Ethanol
(Ethyl
Alcohol)
Source
and
Derivation
Acetaldehyde from
ethylene (Wacker
process)
N-butane (oxidation)
Methanol
(carbonylation)
Wood-pyrol igneous
liquor and other
Methane (partial
oxidation)
Ethylene by-product
Calcium carbide (coal)
Propylene
( ammo noxidat ion)
Ethylene (hydration)
Plant sources
Estimated
Recent Outputd
(106 Tons)
0.43
0.76
0.19
0.06
0.01
0.01
0.16
0.87
0.75
0.06
Year
1978
1978
1978
1978
1974
1974
1974
1978
1974
1974
Annual
Growth
Rate
.04a
.04a
.04a
.04a
.007^
.007b
,007t>
.05a
.015C
.015C
Growth
to 2000
(Multiplier)
2.37
2.37
2.37
2.37
1.2
1.2
1.2
2.9
1.47
1.47
Output
Quantities
2000
(106 Tons)
1.02
1.68
0.45
0.14
0.12
0.01
0.20
2.54
1.10
0.09'
(fermentation)
-------
TABLE 10 (Concluded)
Estimated
Chemical
Methanol
Phenol
Vinyl
Chloride
Vinyl
Acetate
Source
and
Derivation
Synthesis gas from
methane (natural
gas, liquid natural
gas)
Other
Cumene from petroleum
(peroxidation)
Chlorobenzene
(reaction with NAOH)
Benzene (Hooker Raschig)
Benzene (sulfonation)
Benzoic acid from
toluene
Coal tar (pyrolysis)
(middle oils)
Ethylene
Acetylene
Ethylene
(oxyacetylation)
Acetylene
Recent
6
Outputd
(10 Tons) Year
3.15
0.03
1.22
0.40
0.05
0.04
0.01
0.01
3.30
0.20
0.55
0.29
1978
1978
1978
1978
1978
1978
1978
1978
1978
1978
1978
1978
Annual
Growth
Rate
.05a
.05a
.06a
.06a
.06a
.06a
.06a
.06a
.08a
.08a
1.08a
1.08a
Growth
to 2000
(Multiplier)
2.9
2.9
3.6
3.6
3.6
3.6
3.6
3.6
5.4
5.4
5.4
5.4
Output
Quantities
2000
6
(10 Tons)
9.14
0.09
4.39
0.14
0.18
0.14
0.04
0.04
17.82
1.08
2.97
1.57
Sources: aAmerican Chemical Society 1979.
t>Maisel 1980.
cBaba and Kennedy 1976.
dDerived from production totals and percentages as given in Table 3. Production figures
for specific years by derivation routes not available.
-------
TABLE 11
EFFECTS OF CHANGES IN FEEDSTOCK SOURCES
ON PRODUCTION OF SELECTED
INTERMEDIATE ORGANIC CHEMICALS
Chemical
Acetic Acid
Acetylene
Aery lonitr ile
Ethanol
Methanol
Phenol
Vinyl
Acetate
Vinyl
Chloride
Assumed Changes
Decreased Petroleum
Less from acetaldehyde,
N-butane oxidation
Less as ethylene by-
product
Exclusive use of
propylene may end
Less synthesized
from ethylene;
more total use of
ethanol as route to
C- and C, chemicals
Greater use of
methanol as alter-
native source
Less from cumene
(propylene and
benzene) ; produc-
tion from other
benzene routes and
from toluene may
increase.
Less from ethylene
Less from
ethylene
Increased Coal
Car boniz at ion , ?yr oly s is
More from calcium
carbide, plasma
pyrolysis
Resort to acetylene
as basis
Increased use of coal
tar oils; benzene and
toluene derived from
coal
More from acetylene
More from acetylene
Increased Coal
Gasification
More from methanol
(methane)
More from methane
Would promote tech-
niques to derive
from synthesis gas
Greater use of
methanol from
synthesis gas
Decreased
Natural Gas
Less from methanol
(methane) and
N^ butane oxidation
Less from methane,
ethylene
May affect avail-
ability of propy-
lene, reducing use
of this source
May affect ethylene
supply, decreasing
use of this source
Reduced source of
methanol
Reduced ethane may
reduce production
from ethylene
Reduced ethane may
reduce production
from ethylene
Increased
Plant Usage
More from pyro-
ligneous liquor
More from fer-
mentat ion . May
become predomi-
nant route,
yielding ethy-
lene from
ethanol
More from
f ermentat ion
route
Increased Recycling ,
Reduced Waste Generation
Less from acetaldehyde
(hazardous wastes)
Favors plasma pyrolysis
Favors process based
on propylene which recycles
acetonitrile
Favors plant usage since
wastes can be used as feed
for livestock.
Favors production from
refuse
Reduced use of cumene
(hazardous wastes) , of
coal tar oils (high waste
generation factor)
Less from ethylene
dichloride (hazardous
wastes)
00
-------
alternative paths to production from different feedstocks and
petrochemical basics.
5.2.1 Reduced Petroleum Feedstocks
There is a distinction between a shortage of crude oil
compensated by equivalent liquid feedstocks from other sources and
one in which replacements do not exist. In the first situation,
liquid hydrocarbons yielding the same petrochemical basics would be
available from shale oil and liquefaction of coal. An absence of
adequate liquid hydrocarbons without replacements would require
adjustment of the proportions of feedstocks produced from other
processes.
A result of such a situation could be a reduction in the quan-
tity of ethylene, propylene, benzene, toluene and xylene that could
be produced from refinery products. In turn, the amounts of the
intermediate organic chemicals derived from these products would be
reduced as the industry turned to processes using other sources.
Processes using ethylene to derive acetic acid (via acetaldehyde),
ethyl alcohol, vinyl acetate and vinyl chloride would represent a
smaller share of total production than in the base case. Similarly,
benzene-based processes might lose favor for producing phenol.
An effect which would be expected from at least a partial short-
age of petroleum would be a greater use of the heavy hydrocarbon liq-
uids as a source of petrochemical feedstocks. This trend has already
been observed (Cronan 1978) as partial oxidation of heavy liquids has
49
-------
recently been pushed to offset the scarcity and cost of light petro-
leum feedstocks.
5.2.2 Decreased Natural Gas Supply
A severe shortage of natural gas could come about through forces
affecting foreign supplies. The effect would be most direct in de-
creased availability of methane and the heavier paraffins from liq-
uefied natural gas (LNG). It could be at least partially offset by
a reliance on synthesis gas from coal and, as long as there was not
simultaneously a petroleum shortage, partial oxidation of the heavier
liquids from crude oil (Cronan 1978). The principal result (in the
present context) would be a different feedstock source for methane
and methanol, with no change in processes producing chemicals from
these. Alternatively, the result could be a reduction in the propor-
tion of acetic acid, acetylene and methanol derived from methane. In
any event, some reduction in propylene and ethylene available from
liquid petroleum gases derived from natural gas liquids would be
expected.
The possibility of an increase in natural gas supplies is not
explored here, although new sources have resulted in a "natural gas
bubble"—or an apparently temporary excess of supply over demand.
U.S. natural gas production increased slightly from 19.95 trillion
standard cubic feet (SCF) in 1976 to 20.03 trillion SCF in 1977 after
steady declines in the three previous years (Figure 3) (American
Petroleum Institute 1976-1980). Nevertheless, the long term outlook
50
-------
24 -
Actual Marketed
Production
1965 1970 1975
1980 1985
Year
1990 1995 2000
Source: Adapted from American Petroleum Institute 1976-1980.
FIGURES
ACTUAL AND PROJECTED
U.S. USE OF NATURAL GAS
51
-------
is for somewhat less natural gas from U.S. production with a figure
of some 19 trillion SCF postulated for the year 2000.
The decline in U.S. production could be more than offset for the
chemical industry by a decline in fuel use for natural gas or by an
increase in imports. One foreign source recently predicted a glut in
natural gas liquids (NGL) produced in the Middle East in the 1990s
(McCurdy 1980b). Thus, a situation in which there is more natural
gas—not less—available for petrochemical feedstocks is not
unreasonable to postulate for the year 2000. However, this
hypothesis hardly constitutes a separate scenario, distinct from the
base case. What is of interest is to investigate the situation which
might result from a deficiency of natural gas.
5.2.3 Increased Use of Coal
Coal can be expected, out of necessity, to assume an even larger
role, both as feedstock and fuel. Consequently, the following basic
routes for deriving chemicals from coal are considered: liquefac-
tion, gasification, and more direct production by carbonization
(pyrolysis),* or by plasma pyrolysis, which is not yet available on
*Hach's Chemical Dictionary (Grant 1969) defines carbonization in
the present context as the distillation of coal at a high tempera-
ture. Coal is heated in the absence of air at 1,000 to 1,300°C with
the formation of gas, tar oil, ammonia, and coke. The same source
defines pyrolysis as "decomposition of organic substances by heat."
Since pyrolysis (a more general term) occurs in the process of car-
bonizing coal, the two terms are frequently used synonymously in
reference to obtaining coal derivatives. Carbonization is also
known as "coking." In plasma pyrolysis, coal is placed on an elec-
trode in an electric reduction process. A plasma is created that
"reaches higher temperatures than conventional coal processing reac-
tions," producing acetylene and other small molecules. (Anderson
and Tillman 1979.)
52
-------
a commercial scale. Liquefaction and gasification are now promoted
primarily for fuel needs; however, there is some chemical company
interest in gasification.
Liquefaction of coal produces hydrocarbon oils which can compete
with or be supplemental to crude oil or natural gas liquids. Gasifi-
cation, by producing synthesis gas (CO + H2), can compete with meth-
ane in natural gas. Coal carbonization and pyrolysis, a derivation
method using coal tar oils, once represented the predominant route
for the BTX aromatics. Calcium carbide from coke was formerly the
major source of acetylene. Details of these three processes are
included in Appendix C and Table 11 summarizes the chemical processes
potentially affected by these coal derivations.
Selection of these coal routes would be influenced by the costs
of other sources of feedstocks relative to coal, plant flexibility,
and waste management. Faced with a long-term petroleum shortage, the
chemical industry can be expected to take steps which would ensure an
adequate production capacity from coal.
5.2.4 Increased Use of Biological Material
A number of chemicals currently derived from fossil fuels can
also be made by bioconversion of carbohydrate raw materials (usually
plant materials and sometimes other substances such as whey). The
process for deriving ethanol by fermentation is among the most widely
known and approximately 6 percent of industrial ethyl alcohol is
produced by this route. Methanol can also be produced through the
53
-------
destructive distillation of hardwood, while acetic acid can be made
with pyroligneous liquor, obtained from the same source. A number of
C3 and 04 chemicals (the "C" denoting carbon) not examined here
can also be obtained by fermentation (long 1978, Lowenheim and Moran
1975).
A disadvantage of the fermentation route for ethanol lies in
weight conversion. Yields exceed 80 percent for synthetic ethanol
compared to theoretical weight yields of less than 70 percent for
fermentation. Nevertheless, feedstock costs could make derivation
from plant sources more attractive. "Cornstarch and sugar from cane
can become competitive as chemical feedstocks when crude oil prices
approach $18 to $20 a barrel" (long 1978).
However, significant increases in the quantity of ethanol pro-
duced by fermentation are viewed as dependent on improved fermenta-
tion technology and the design of integrated production facilities.
Moreover, the availability of agricultural raw materials for chemical
production over the long term is in question. According to one opin-
ion, current requirements for ethanol as well as CL and C, chemicals
3 4
could be met by less than a 10 percent increase in yearly cereal
grain and sugar crop production. Molasses and unutilized whey would
also augment the source of fermentable carbohydrates (long 1978).
With expected population growth in third world countries, the
diversion of grains on a major scale could become a political issue
tied to concern for world hunger. This problem might be avoided by
54
-------
use of nonedible biomass. The Tennessee Valley Authority (TVA)
recently announced a policy promoting the development of wood-based
alcohol production. According to the manager of TVA's project on
liquid fuels from biomass, "The question is not whether there will
be an alcohol fuels industry. The question relates to the nature of
that industry" (McCurdy 1980a). Although the program is aimed at
developing one billion gallons of fuel per year in the 1990s, if it
is successful, it may also be a potential source of chemical feed-
stocks .
The most significant impact of increased use of plant sources
would be a shift in production of ethanol and ethylene. As shown in
Table 11, ethyl alcohol could become a feedstock for derivation of
ethylene rather than the reverse procedure used today. Some increase
in methanol and acetic acid derived from hardwood could also be
expected.
5.2.5 Recycling and Reduction of Waste Generated
Regulations imposed under RCRA and other legislation could
affect the processes used to produce chemicals, shifting the produc-
tion mix. Regulations could result in increased costs for waste man-
agement and control, for example, thus encouraging the use of pro-
cedures which generate less waste or recycle intermediate output that
would otherwise be treated as waste. Such a trend could be aided by
rising property, values. In some cases, land for waste disposal might
be difficult to obtain at any price by the year 2000. Higher feed-
stock costs could also push industry toward increased recycling. For
55
-------
example, as noted above, by recycling acetonitrile, currently a waste
in the production of acrylonitrile from propylene, output could be
increased approximately 12 percent with no increase in the quantity
of feedstocks purchased or solid waste generated.
The same factors could lead to greater production of methane and
its derivatives from waste products. Through pyrolysis, thermal gas-
ification and liquefaction processes, organic solid wastes and resi-
dues can be converted to synthesis gas and methane as well as to
low-molecular weight organic liquids including organic acids and
aromatics. This process could be used to recycle municipal refuse,
tires, sludge, waste plastics, packaging materials and agricultural
and forestry residues. This route is discussed in a recent analysis
(Jones 1978) as a way to produce fuel gases that can be discharged
directly into a combustion chamber for firing steam boilers. How-
ever, the production of chemical feedstocks is also possible with
advanced technology. The result would be not only an increase in
methane and the production of chemicals by processes using it
(methanol, acetylene, acetic acid, acrylonitrile, vinyl acetate and
vinyl chloride) but also a net reduction in the volume of waste.
Other shifts in the relative contributions of alternative pro-
duction processes would be observed in a trend toward routes which
generate less net waste—particularly less hazardous waste (such as
vinyl chloride from ethylene dichloride, detailed below).
56
-------
6.0 PROJECTIONS FOR SELECTED PETROCHEMICAL BASICS
The variety of changes in waste loads that could accompany
shifts to alternative production routes is illustrated in this sec-
tion. Year 2000 projections, offered in chemical-specific scenarios,
show a range of possibilities for the future. Few generalities can
be made about these projections, but it appears that alternative
production processes will often yield larger quantities of
potentially hazardous waste—if not larger quantities of waste over
all. For example, in ethylene production, shortages of natural gas
and petroleum would naturally cause a drop in wastewater resulting
from processing natural gas. However, there would be substantial
increases in potentially hazardous spent caustic from processing
shale oil liquid (from 0 in the base case to 5.2 billion pounds).
6.1 General Characteristics of the Scenarios
Each scenario is distinct; however, there are common points
which can be used to relate them. Some reflect forces causing
increased use of feedstocks derived from coal at the expense of
petroleum sources. Others are linked by the greater reliance on
plant sources which they assume and some reflect regulatory
constraints presumed to induce greater recycling and reduction of
wastes, particularly of hazardous components.
The tables of waste considerations document the source or pro-
cess, and the type and quantity of waste generated. The projected
waste loads were derived by applying waste generation factors for
57
-------
TABLE 12
WASTE GENERATION FACTORS FOR SELECTED
PETROCHEMICAL BASICS
Chemical
Source and
Derivation
Nature of
Waste
Waste Generation
Factor
Ethylene
Gas
Wastewater
Spent caustic
Dessicant
0.75 Ib/lb
0.11 Ib/lb
1.3 x 10-4
Petroleum
Liquids
Benzene Solvent extrac-
tion of refor-
mate and pyr-
lysis gasoline
Coal carboniza-
tion
Propylene Refinery
Ethylene
co-product
Spent caustic
Dessicant
Spent clay
Spent acid and oil
Spent caustic
Spent clay
Spent caustic
Subsumed under
ethylene
0.19 Ib/lb
1.3 x 10~4 Ib/lb
0.73 Ib/gal
1.39 Ib/gal
0.16 Ib/gal
0.15 Ib/gal
0.11 Ib/lb
See above
As function of product output.
58
-------
each of the chemical production processes considered (Table 12) to
the projected production quantities for the base case and following
scenarios. The waste load figures, however, are not necessarily the
quantities which would be discharged into the environment. This
applies particularly to wastewater flows where the ultimate residual
depends heavily on the method of treatment used. When information on
the solid content of the flows was available it has been included in
the tables. It is also recognized that recycling practices may vary
from one plant to another, particularly with liquid effluents.
Although an effort was made to exclude volumes of material regularly
recycled, the available information is inadequate to ensure that this
was done comprehensively.
6.2 The Petrochemical Basics
6.2.1 Ethylene
The basic building block for numerous chemical products and
intermediates, ethylene is generally regarded as the most important
olefinic petrochemical. The projected demand for ethylene in the
year 2000, based on the demand for products currently derived from
ethylene, is 97.5 billion pounds per year (Sherwin et al. 1975).
Currently in the U.S. about 65 percent of ethylene is made by
cracking liquefied petroleum gas (a mixture of ethane, propane, and
butane). Approximately 33 percent is made by cracking heavier
petroleum fractions, e.g., naphtha, and the remainder is recovered
from refinery off-gases (Debreczeni 1977).
59
-------
TABLE 13
ETHYLENE - PRODUCTION ASSUMPTIONS
YEAR 2000
Percentage of Total Produced by Process
Scenario
Base Case
Scenario 1— A
Output
(109 Lbs)
97.5
97.5
Cracking Liquid
Natural or Pe-
troleum Gas
65
23
Cracking Heavier
Petroleum
Liquids
33
77
Recovery From
Refinery
Off-Gas
2
0
Cracking
Shale Oil
0
0
External
Conditions
o Declining availability
of natural gas and
petroleum gas liquids
o Extensive use of heav-
ier petroleum or crude
o Increased availability
of petroleum to chemi-
cal industry
o Increased supplies of
domestic oil
Scenario 2-A 97.5
23
51
28
o Reduced availability of
petroleum and develop-
ment of shale oil
with 1 million barrels
per day available for
ethylene
-------
TABLE 13 (Concluded)
Percentage of Total Produced by Process
Output
Scenario (109 Lbs)
Cracking Liquid
Natural or Pe-
troleum Gas
Cracking Heavier
Petroleum
Liquids
Recovery From
Refinery
Off-Gas
Cracking
Shale Oil
External
Conditions
Scenario 3-A 68.2
23
77"
o Acetylene is produced
from coal and used to
make vinyl chloride and
vinyl acetate. Other
chemicals, i.e.,
ethylene oxide and
ethylene glycol
derived from coal-
synthesis gas. Up to
30% of potential demand
for ethylene in year
2000 could be met by
these alternatives.
This figure also represents a combination of shale liquids and petroleum liquids.
-------
TABLE 14
ETHYLENE - WASTE PROJECTIONS
YEAR 2000
Source
Type of
Waste
Total Amount of Waste - Year 2000 - (10 Lbs)
Base Case
Scenario
1-A
Scenario
2-A
Scenario
3-A
Gas
Petroleum Liquids
Shale Oil Liquid
Wastewater
Spent caustic
Dessicant
Spent caustic
Dessicant
Spent caustic
Dessicant
53.4
7.8
0.01
5.0
0.0003
0.0
0.0
16.8
2.5
0.003
14.3
0.01
0.0
0.0
16.8
2.5
0.003
9.1
0.006
5.2
0.0004
16.8
2.5
0.003
8.0
0.006
0.0
0.0
62
-------
Changes in the availability of natural gas liquids are forcing a
shift toward the use of the heavier petroleum liquids in U.S. plants
(Debreczeni 1977). Advances in cracking technology will enable the
direct use of crude oil for producing ethylene and associated by-
products (Hatch and Matar 1978).
A growing share of available petroleum will be needed to meet
the increased demand for ethylene, requiring that substitutes be
found for competing uses of petroleum supplies. More petroleum would
be available for chemical production if utilities used coal or
nuclear fuel instead of oil or gas to generate electricity. On the
other hand, unconventional hydrocarbon liquids such as shale oil
could be used to make up the shortfall in conventional petroleum
supplies needed for ethylene production.
The demand for ethylene could be lower than projected if alter-
native technologies for production of products currently derived from
ethylene were to become economical. For example, vinyl chloride and
vinyl acetate, which are currently derived from ethylene, can also be
derived from acetylene. New technology under development for
deriving acetylene directly from coal could make the acetylene route
to these chemicals competitive. Coal-derived synthesis gas may also
be used to make ethylene and its derivatives, reducing the demand for
petroleum-derived ethylene.
If coal-derived feedstocks were substituted for petroleum-based
ethylene, the coal processing might generate more waste than the
production of oil and feedstocks derived from oil.
63
-------
6.2.2 Propylene
The projected demand for propylene in the year 2000, based on
demand for products derived from this olefin, is 49.75 billion pounds
per year (Sherwin and Frank 1975). Currently, about half the propy-
lene is recovered from refining catalytic cracker streams, and the
remainder is a by-product of ethylene production (Sanders et al.
1977, Debreczeni 1977). Improvements in catalytic cracking technol-
ogy to increase gasoline yields have reduced the production and,
thus, availability of propylene from refineries. However, the switch
to heavier feedstocks for ethylene production has resulted in an in-
crease in the production of co-product propylene. It is anticipated
that the increased co-production of propylene with ethylene, combined
with increased production of ethylene, will provide adequate feed-
stocks to support the growth of propylene derivatives (Debreczeni
1977). When propylene is co-produced with ethylene, there is no
additional waste generated over that reported for the production of
ethylene.
6.2.3 Benzene, Xylene, and Toluene
The projected demands for benzene, xylene, and toluene for chem-
icals in the year 2000 are 5.25, 3.88, and 2.08* billion gallons
per year, respectively (Sherwin and Frank 1975). In 1977, more than
The figures for toluene do not include the amount of toluene con-
verted to benzene. The volume of benzene and other aromatic com-
pounds recovered for chemical industry use is a minor portion of
the total supply.
64
-------
TABLE 15
PROPYLENE - PRODUCTION ASSUMPTIONS
YEAR 2000
Percentage of Total Produced by Process
Scenario
Base Case
Scenario 1-B
Output
(109 Lbs)
49.75
49.75
Recovery From
Refining Catalytic
Cracker Streams
50
15
By-Product
of Ethylene
Production External Conditions
50
85 o Normal growth in availability of propylene
from refineries
o Increase in yield of co-product propylene
from ethylene to 43 Ibs per 100 Ibs of
ethylene
o Debreczeni (1977) projects ratio of
50:100 for the year 1990
Scenario 2-B 46.45
17
83
o Alternative feedstocks used to produce some
acrylonitrile, phenol, and propyl alcohols
would be available for incremental produc-
tion after 1990
Scenario 3-B 46.45
91
o Propylene less available from refineries
following increased gasoline yields from
catalytic crackers
o Reduction in oil supplies reducing refinery
yields
Scenario 4-B
46.45
27
73
o Reduced ethylene production, and propylene to
ethylene production ratio of 1:2, based on
Scenario 3 for ethylene
o Rise in availability of propylene from
refineries
-------
TABLE 16
PROPYLENE - WASTE PROJECTIONS
YEAR 2000
Total Amount of Waste - Year 2000 - (109 Lbs)
Type of
Source Waste Base Case Scenario 1-B Scenario 2-B Scenario 3-B Scenario 4-B
Refinery Spent Caustic 2.4 0.85 0.85 0.48 1.4
Ethylene By-Product*
Subsumed under ethylene
-------
85 percent of all aromatics produced was used in gasoline (Cox
1979c). Currently, almost 96 percent of the U.S. benzene supply is
recovered directly or indirectly from crude oil or natural gas
liquids while the remainder comes from coal (Debreczeni 1977).
As a result of the trend toward increased utilization of coal
resources, more aromatics will be derived as a by-product of the
production of coke, fuel gases, and synthesis gas from coal (Collin
1978). Tables 17 and 18 illustrate the factors in production and
waste generation for each of the processes used to produce benzene,
xylene, and toluene. The three aromatics are obtained as a mixture
from refinery reformate streams, pyrolysis gasoline (a by-product of
ethylene manufacture) and from coal tars. Because no additional
waste streams are produced during the separation of the compounds
from the mixture, the tables list the production and wastes only for
benzene.
A slight reduction in benzene demand could occur as a result
of the use of butane instead of benzene to make maleic anhydride. If
all incremental production of maleic anhydride between 1980 and 2000
were derived from butane, the benzene demand would be reduced by 25
million gallons per year in 2000. If all production of maleic
anhydride in the year 2000 were based on butane, benzene demand would
be reduced by 100 million pounds (Sherwin and Frank 1975).
If incremental phenol production between the year 1990 and 2000
were made by toluene oxidation instead of from cumene, a further
67
-------
TABLE 17
BENZENE - PRODUCTION ASSUMPTIONS
YEAR 2000
00
Output
Scenario (109 Gallons)
Base Case 5.25
Scenario 1-C 5.25
Scenario 2-C 5.25
Scenario 3-C 5.25
Percentage of Total Produced by Process
Solvent Extraction of
Reformate and Coal Toluene
Pyrolysis Gasoline Carbonization Dealkylation
67 5 28
80 5 15
70 9 21
47 16 37
External Conditions
o Increased availability of benzene from
pyrolysis gasoline as a by-product of
ethylene
o Increased availability of toluene as
by-product of coal derived synfuel
o Increase in benzene obtained as a coal
by-product (Sherwin and Frank 1975)
o More than half of available toluene
is coal derivative (Sherwin and Frank
1975)
Scenario 4-C
5.25
60
37
o Increased toluene derived from coal
for benzene production
-------
TABLE 18
BENZENE - WASTE PROJECTIONS
YEAR 2000
Total Amount of Waste - Year 2000 - (109 Lbs)
Type of
Process Waste Base Case Scenario 1-C Scenario 2-C Scenario 3-C Scenario 4-C
Solvent Extraction Spent clay 2.58 4.23 2.80 1.8 3.14
of Reformate and
Pyrolysis Gasoline
Coal Carbonization Spent acid and 0.328 0.328 0.460 1.19 0.229
oil
Spent caustic 0.038 0.038 0.053 0.137 0.026
Toluene Dealkylation Spent clay 0.22 0.12 0.16 0.29 0.12
-------
reduction in the demand for benzene of 350 million gallons per year
would occur. This would probably result in a reduction in the amount
of benzene produced by toluene dealkylation.
In summary, as illustrated in Tables 17 and 18, waste generation
in the production of benzene is likely to increase—but not because
of increased benzene production. Instead, more waste will accompany
a shift from petroleum derivation to coal derivation.
70
-------
7.0 PROJECTIONS FOR INTERMEDIATE ORGANIC CHEMICALS
As with the petrochemical basics, a variety of waste load
variations can be expected to accompany changes in the methods used
to produce intermediate organic chemicals. This point is illustrated
by year 2000 projections for four scenarios, numbered I through IV,
to distinguish them from the scenarios in Section 7.
7.1 General Characteristics of the Scenarios
Scenario I shows a petroleum shortage. It is assumed that the
deficiency in feedstock liquids from this source is not compensated
by coal conversion or oil shale.* Hence, there will be a decrease
in intermediate organic chemicals made from basics now derived prin-
cipally from petroleum, such as ethylene and propylene. To compen-
sate, alternative routes using basics from other sources are assumed
to increase as necessary. In particular, basics that can be derived
from conventional coal processes such as acetylene (and to some
extent benzene) will be used in greater proportion. However the
scenario does not assume a breakthrough in commercialization of new
or pilot processes for using coal such as plasma pyrolysis. More
reliance is placed on methanol in Scenario I, since no natural gas
shortage is hypothesized. Some increases in the small fraction of
chemicals produced from biomass will occur to support production
levels, but no breakthrough in commercialization of fermentation
*It may be noted that a petroleum deficiency fully compensated by
hydrocarbon liquids from alternative sources would constitute
"business as usual" and would fall under the base case.
71
-------
technology is postulated. Therefore, increases in the use of plant
materials are slight.
Scenario II illustrates the effects of reduced waste generation,
particularly wastes requiring ultimate disposal under RCRA. Pro-
cesses which recycle intermediate products (as is possible for
acrylonitrile) or which start with refuse (such as the processes for
developing methane from a variety of solid wastes) provide a larger
contribution to the production mix. Conversely, those derivation
routes which generate the greatest amounts of solid, semi-solid and
liquid wastes are used less. In particular, procedures associated
with hazardous wastes provide a reduced contribution to the produc-
tion mix. Some decline in feedstocks from petroleum is also assumed
for this scenario, so that derivation routes using other starting
points provide a greater percentage of output than in the base case.
The technological advances necessary to accomplish the process sub-
stitutions (such as commercialization of the recycling technology for
acrylonitrile and of plasma pyrolysis of coal) are assumed for Sce-
nario II. However, a breakthrough which would lead to widespread
industrial use of fermentation from biomass is reserved for the next
scenario.
In Scenario III, commercialized use of plant sources is the
dominant characteristic. Derivation routes based on fermentation
increase markedly over other processes. The effect is most immediate
for those selected chemicals which can be made directly from biomass
72
-------
such as acetic acid, ethanol, and methanol. A secondary effect is a
greater reliance on methanol and ethanol for further production.
Since from the latter, ethylene can be derived, the postulated effect
is to offset a potential shortage of this petrochemical basic which
was hypothesized for Scenario I. Otherwise, petroleum-derived basics
are assumed to be less plentiful than in the base case.
In Scenario IV, the principal feature is an assumed deficiency
in natural gas as a feedstock source.* Production of methanol is
particularly affected, along with derivation routes which employ it.
Sources based on petroleum are also assumed to be less plentiful than
in the base case, although the deficiency is not hypothesized to be
as extreme as in Scenario I. Derivation routes using petrochemical
basics from other sources are—where available—favored as replace-
ments for methane and methanol.
It should be noted that quantitative data from which to
calculate waste factors were not available for a few derivation
routes so the impacts of these cannot be measured.
7.2 The Intermediate Organic Chemicals
7.2.1 Acetic Acid
Projected waste loads were examined for three methods of making
acetic acid. Data were not available to derive waste factors for
manufacture by oxidation of N-butane and other petroleum gases, so
*Without compensation from coal gasification which would amount
simply to a special situation under the base case.
73
-------
this route is considered only with regard to production. In all
scenarios shown in Tables 19 and 20, the proportion manufactured by
this process is assumed to decrease from the base case.
Scenario II is particularly interesting. Here, the sharp drop
shown in Table 19 for use of the Wacker process reflects a decreased
use of that process because of the hazardous waste associated with
its intermediate product, acetaldehyde. Distillation bottoms and
sidecuts from the production of acetaldehyde from ethylene are
assigned EPA hazardous waste numbers K09 and KlO, under recently
released RCRA regulations (U.S. Environmental Protection Agency
1980a). The availability of alternative production routes offers a
way to reduce hazardous waste. The high factor for solid waste in
pyrolysis of liquor from wood reflects the low yield of acetic acid
from hardwood. In some instances, other outputs might be obtained
from the same feedstock (see flow diagram in Appendix C), thus
reducing the quantity of waste attributable to production of acetic
acid. If the chemical industry turns heavily to plant sources (as
hypothesized in Scenario III) integrated facilities producing acetic
acid, along with other outputs such as methane and methanol, could
reduce total waste loads. Evidence was not found in the literature
to suggest whether this would be hazardous waste, nor is it known how
the refuse may be disposed of.
7.2.2 Acetylene
For the acetylene production routes considered here, only par-
tial quantitative data on waste were available. As shown in Table 22
74
-------
TABLE 19
ACETIC ACID - WASTE PROJECTIONS
YEAR 2000
Percentage of Total Produced by Process
Scenario
Output
106 Tons
From Ethylene
(Wacker Process)
From Methanol
(Carbonylation)
Wood Pyroligneous
Liquor
Oxidation of
Petroleum Gases
External Conditions
Base Case
1.86
31
14
51
Scenario I
1.86
27
31
10
32 o Decreased availability of
petroleum feedstocks
o Cost-effective methanol
Scenario II
1.86
12*
64
19
o Use of processes reducing
waste generation and pro-
moting recycling
o Increased reliance on
methanol from refuse-
derived methyl alcohol
Scenario III 1.86
33
38
20
o Decreased use of petro-
leum feedstocks
o Technological advances in
processes using plant
sources
o Increase in ethylene
from fermentation-derived
ethanol
Scenario IV
1.86
30
11
49 o Deficiency of natural gas
with no offset from coal-
gasification products
*Sharp drop reflects hazardous wastes associated with intermediate product, acetaldehyde.
-------
TABLE 20
ACETIC ACID - WASTE PROJECTIONS
YEAR 2000
Process
Acetaldehyde From
Ethylene by Wacker
Process
Methanol by
Carbonylation
Wood-Pyroligneous
Liquor
Oxidation of
Petroleum Gases
Waste
Type Nature
Catalyst metals; Wastewater
organics; sulfates;
oils; corrosiveness;
acidity Solid
content
Propionic acid, Wastewater
higher organics
Solid
content
Wood pulp Solids
Unknown
Waste Factor
Per Ton of
Product Units Base Case
1,000 Galsa 106 1,020.00
Gals
130 Lbsa 106 0.07
Tons
23 Galsb 106 10.0
Gals
80 Lbsb 106 0.02
Tons
13 Lbsc 106 1.80
Tons
Amount of Waste
Scenario I Scenario II Scenario III Scenario IV
890.00 410.00 1,100.00 100.00
0.06 0.03 0.07 0.07
23.00 49.00 29.00 7.00
0.04 0.08 0.05 0.01-
4.30 2.10 8.50 4.60
(No quantitative data available)
Sources: aLiepins et al. 1977.
bHedley 1975.
cDerived from materials balance in Lowenheim and Moran 1975.
-------
TABLE 21
ACETYLENE - PRODUCTION ASSUMPTIONS
YEAR 2000
Percentage of Total Produced by Process
Output Methane Calcium Carbide Coal-Plasma
Scenario (106 Tons) Partial Oxidation From Coal Pyrolysis
Base case .27 38 62 0
Scenario I Same as base case
Scenario II .27 47 25 28
Scenario III Same as base case
External Conditions
o No commercial use of plasma pyrolysis
of coal
o Natural gas deficiency, without coal
gasification as substitute
Scenario IV
.27
19
81
o Waste generation constraints; plasma
pyrolysis significantly reduces waste
in coke production and derivation of
calcium carbide
-------
the use of plasma pyrolysis in Scenario II would reduce the amount of
waste generated compared to alternative derivation from coke and
subsequently calcium carbide, but the amount is unknown. The calcium
hydroxide which constitutes most of the solid waste may be disposed
of as a by-product of this process.
7.2.3 Acrylonitrile
All acrylonitrile is now manufactured by ammonoxidation of
propylene, but it can also be produced from acetylene using hydrogen
cyanide (HCN). Both a liquid phase and a vapor phase process exist
although the latter has never been commercialized (Furgate 1963). As
noted above there is also a process available to convert acetonitrile
(now an intermediate waste) to acrylonitrile by catalytic oxidation
with methane (Gelbein 1979). This is an important process hypothe-
sized for Scenario II, which emphasizes recycling. Still bottoms and
bottom streams from acrylonitrile production have hazardous waste
numbers KOI 1 through K014 under RCRA regulations (U.S. Environmental
Protection Agency 1980). Some components classified as hazardous
under these regulations are also contained in waste generated when
acrylonitrile is produced from acetylene, specifically HCN and
residual acrylonitrile itself in the stripper-effluent water from the
liquid phase process.
7.2.4 Ethanol
The two basic routes for deriving ethanol (ethyl alcohol) are
from ethylene or from biological material (including whey and plant
sources) by fermentation. These are compared in the simplified flow
79
-------
TABLE 23
ACRYLONITRILE - PRODUCTION ASSUMPTIONS
YEAR 2000
Percentage of Total Produced by Process
Output Ammonoxidation Ammonoxidation of
Scenario (10^ Tons) of Propylene Acetylene Propylene With Recycle
Base case 2.54 100 0 0
Scenario I 2.64 75 25 0
GO
O
External Conditions
o Reduced use of propylene reflects
25 percent decrease in available
petroleum feedstock
o Technological advances with acety-
lene route commercially attractive
Scenario II 2.54
25
75
o Use of process reducing waste gen-
eration and promoting recycling
Scenario III Same as base case
Scenario IV
Same as base case
-------
TABLE 24
ACRYLONITRILE - WASTE PROJECTIONS
YEAR 2000
00
Process Type
Propylene Ammonoxidation Sulfate; acetonltrile
organic polymers
Propylene Ammonoxidation
With Recycle
Acetylene Unknown
Waste
Waste Factor
Per Ton of
Nature Product
Wastewater 929 Gals3
Solids 269 Lbsa
Wastewater 532 Galsb
Solids 28 Lbsb
Amount of Waste
Units Base Case Scenario I Scenario II
106 Gals 2,360.0 1,765.0
106 Gals 0.34 0.26
106 Gals 1,010.0
10& Gals 0.03
(No quantitative data available)
Sources: aLowenbach and Schlesinger 1978.
bDerived from Gelbein 1979.
-------
diagrams in Appendix C. As already noted, about 94 percent of etha-
nol is now produced from ethylene and this percentage is assumed in
the base case. In the alternative scenarios for ethanol shown in
Tables 25 and 26, greater use is made of fermentation to derive ethyl
alcohol for chemical use. Since further products can be made from
it, ethanol production in Scenario III is assumed to increase by 55
percent over the base case.
The wastes generated in the fermentation route to ethanol are
far greater than those resulting from use of ethylene. However, much
of the material suitable for fermentation produces waste which can be
used as livestock feed.
7.2.5 Methanol
Methanol is now derived almost exclusively for chemical use from
methane and synthesis gas, and this situation is assumed to continue
in the base case. However, it can also be derived from plant sources
(witness the time-honored name "wood alcohol"). Methane and syn-
thesis gas now used for production of methanol generally come from
natural gas feedstocks, but could also be derived from processes
which gasify coal (such as the WESCO or Winkler processes), and from
organic solid wastes including municipal refuse (Jones 1978). If
petroleum feedstocks were unduly costly or in short supply, the
requirement for methanol could be expected to increase as an alterna-
tive raw material for several chemicals, including acetic acid and
acetylene, which are examined in this section.
82
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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
-------
TABLE 27
METHANOL - PRODUCTION ASSUMPTIONS
YEAR 2000
Output Methane
Scenario (10^ Tons) Synthesis Gas
Percentage of Total Produced by Process
Hardwood Refuse
External Conditions
Base Case
9.2
99
1
0
Scenario I 11.1
99
o Decreased availability of petroleum
o Increase in methanol production to
compensate
o No shortage of natural gas
o No increase commercialization of
derivation technologies from plant
Scenario II 11.1
49
50 o Regulatory pressures for greater use
of waste material lead to increased
use of methanol and greater produc-
tion from refuse
Scenario III 10.0
90
10
o Increased commercialization of deriva-
tion technologies from plant source
Scenario IV 9.0
39
11
50 o Decreased availability of natural gas
o Partly compensated by increased
reliance on plant sources
o Slight overall decreases in methanol
production
-------
TABLE 28
METHANOL - WASTE PROJECTIONS
YEAR 2000
Waste
Waste Factor
Amount of Waste
Process Type Nature Product Units
Methane, Synthesis Wastewater 300 Gals 10 Gals
CO
»J Gas
Solids 6.6 lbsa 106 Tons
Hardwood Oil; higher boiling Solids 2.4 Tonsb 106 Tons
point organics
Refuse Unknown
Base Case Scenario I Scenario II Scenario III Scenario IV
2,740.00 3,300.00 1,620.00 2,700.00 2,400.00
0.30 0.36 0.18 0.30 0.26
0.22 0.24 0.24 2.40 2.40
(No quantitative data available)
Sources: Liepins et al. 1977.
Derived from materials balance, Lowenheim and Moran 1975.
-------
the scenarios defined in Tables 29 and 30. Derivation from benzene
by the Hooker-Raschig process, which in 1978 accounted for about 4
percent of phenol production and for which waste factors could not be
derived, is conveniently assumed to be phased out in the scenarios.
There appears to be a trade-off between volumes of waste and
hazardous components. Total waste volumes are lowest in the base
case. Scenario II shows reductions in hazardous components of
waste—but not in the volume of waste generated.
7.2.7 Vinyl Acetate and Vinyl Chloride
Vinyl acetate and vinyl chloride are produced either from ethy-
lene or acetylene. The use of ethylene predominates overwhelmingly:
about two-to-one in the production of vinyl acetate, and on a ratio
of more than fifteen-to-one for vinyl chloride. These proportions
are assumed in the base case, while the alternative scenarios
consider changes in the production mix between these two routes.
With vinyl chloride, hazardous waste generation could be reduced
by using the acetylene process rather than the one employing
ethylene. The ethylene route generates a greater quantity of
waste and the heavy ends from the distillation of ethylene dichloride
and of vinyl chloride have been assigned hazardous waste numbers K019
and K020 under the latest RCRA regulations (U.S. Environmental
Protection Agency 1980a).
*As represented by the balanced process in which ethylene
dichloride is first formed and then pyrolyzed to yield vinyl
chloride monomer (VCM).
88
-------
TABLE 29
PHENOL - PRODUCTION ASSUMPTIONS
YEAR 2000
Percentage of Total Produced by Process
Output Cumene Benzene Coal Tar Benzole Acid Benzene
Scenario (106 Tons) Peroxldation Chlorobenzene Sulfonatlon Middle Oils From Toluene Hooker-Raschig External Conditions
Base Case
4.93
89
oo
Scenario I
4.93
61
19
o Reduction of petroleum-
associated sources leads
to increased reliance on
coal replacing propylene
as feedstock
Scenario II 4.93
50
36
o Regulatory pressures to
reduce waste disposal
under RCRA, etc.
Scenario III Same as Scenario I
Scenario IV Same as Scenario I
-------
TABLE 30
PHENOL - WASTE PROJECTIONS
YEAR 2000
Waste
Waste Factor
Per Ton of
Process Type Nature Product
Cumene (Perox- Phenol; aceto- Wastewater 445 Galsa
idation) phene
Solids 40 'Lbsa
Chlorobenzene Diphenyl ether Solids 81 Lbsa
Benzene (Sulfon- Solids 432 Lbsb
ation)
Coal Tar Middle Tar; phenate; Solids 1,313 Lbsc
Oils cresylate in
bottom stills
Benzoic Acid, Tar; acetate; Solids 276 Lbs
From Toluene benzoates
Benzene (Hooker- Unknown
Raschig Process)
Amount of Waste
Units Base Case Scenario I
106 Gals 1,953.00 1,335.00
106 Tons 0.09 0.06
106 Tons 0.006 0.01
106 Tons 0.03 0.06
106 Tons 0.03 0.62
106 Tons 0.05 0.06
No quantitative data available
Scenario II
1,100.00
0.05
0.07
0.05
0.07
0.06
Sources: aLiepins et al. 1977.
bHedley 1975.
°Derived from materials balance, Lowenheim and Moran 1975.
-------
The issue is not clear cut. In deriving vinyl chloride from
acetylene, mercuric sulfide may be produced in the waste from the
catalyst used. However, it appears that this metallic component can
be reclaimed through recycling, which could be easier than disposing
of the heavy ends that result from producing VCM by the ethylene
dichloride route.
Thus, on both quantitative and qualitative grounds, the acety-
lene route is preferred in Scenario I, a scenario emphasizing waste
reduction—particularly of hazardous constituents. This is achieved
by increasing the quantity of vinyl chloride produced from acetylene
at the expense of the alternate route from ethylene which plays a
larger role in Scenarios II and III.
For vinyl acetate the derivation route from acetylene generates
15 times as much waste as the ethylene route. Hence in Scenario II
greater use of ethylene is hypothesized than in Scenario I (which
emphasizes a deficiency of petroleum-derived feedstocks). More ethy-
lene is also assumed to be used in Scenario III in which widespread
commercialization of fermentation processes is hypothesized, leading
to derivation of ethylene from ethyl alcohol. Vinyl acetate waste
loads are lowest for the base case (which assumes maximum use of
ethylene) and highest for Scenario II (which assumes minimum use of
that petrochemical basic).
Neither vinyl chloride nor vinyl acetate production is
significantly affected by an assumed deficiency in natural gas
91
-------
TABLE 31
VINYL ACETATE - PRODUCTION ASSUMPTIONS
YEAR 2000
VD
Percentage of Total
Scenario
Base Case
Output
(106 Tons)
4.54
Ethylene by
Oxyacetylin
66
Produced by Process
From
Acetylene
34
External Conditions
Scenario I
4.54
33
67
o Decreased availability of
petroleum feedstocks
o Switch to coal-derived
feedstocks
Scenario II 4.54
55
45
o Use of processes generating
less waste (acetylene route
has higher waste factors)
Scenario III Same as Scenario II
Scenario IV Same as Scenario I
-------
TABLE 32
VINYL ACETATE - WASTE PROJECTIONS
YEAR 2000
Process
Ethylene,
Oxyacetylation
Acetylene
Type
Acetates; benzene;
acetic acid
Catalyst metals;
tars; organics
Waste
Nature
Wastewater
Solids
Solids
Amount of Waste
Waste Factor
Per Ton of
Product
56 Galsa
5 Lbsb
144 Lbsb
Units
106
106
106
Gals
Tons
Tons
Base Case
166.000
0.008
0.113
Scenario I
84.
0.
0.
000
004
219
Scenario II
140.000
0.007
0.147
Sources: aU.S. Environmental Protection Agency 1974.
bHedley 1975.
-------
feedstocks so the projections in Scenario IV and Scenario I are the
same.
94
-------
TABLE 33
VINYL CHLORIDE - PRODUCTION ASSUMPTIONS
YEAR 2000
Scenario
Output
(106 Tons)
Percentage of Total Produced by Process
Ethylene Dichloride
Balanced Process
Acetylene
External Conditions
Base Case
18.9
94
vo
Ln
Scenario I 18.9
33
67
o Switch to coal-derived
feedstocks
o Efforts to reduce genera-
tion of hazardous waste
Scenario II 18.9
79
21
o Increased reliance on plant
Sources
o Ethylene derived from
ethanol partly compensates
for reduced availability
from petroleum feedstocks
Scenario III Same as Scenario II
o Widespread commercializa-
tion of fermentation
processes
Scenario IV Same as Scenario I
-------
TABLE 34
VINYL CHLORIDE - WASTE PROJECTIONS
YEAR 2000
Process
Waste
Type
Nature
Waste Factor
Per Ton of
Product
Units
Amount of Waste
Base Case Scenario I Scenario II
Ethylene Bichloride Trichloroethane, Wastewater 3.0 Galsa 10^ Gals
(Balanced Process) tetrachloroethane,
vinyl chloride and
ethylene dichloride
5,970.00 2,110.00 5,025.00
VD
a--
Acetylene
Mercury (HgS)
-01/Ton Product
Solids
Wastewater
Solids
96.0 Lbsa
480.0 Galsa
4.8 lbsb
106 Tons
106 Gals
106 Tons
1.01
518.00
0.01
0.36
6,048.00
0.03
0.85
1,872.00
0.01
Sources: aLiepin; et al. 1977.
t>Lowenheim and Moran 1975 (derived from catalyst loss).
-------
APPENDIX A
HAZARDOUS WASTE
A.1 Quantities of Hazardous Waste
Manufacturers of chemicals and allied products have been esti-
mated in one study to represent 7,100 generators of hazardous waste,
producing about 1.65 million tons of such waste each month. The
petroleum refining industry (a major source of petrochemical basics)
has been estimated to generate another 0.08 million tons monthly
(Fred C. Hart Associates, Inc. 1977). EPA has estimated that, in
1977, the organic chemical industry alone produced some 12.9 million
tons of hazardous waste or about 34 percent of the national total
(U.S. Environmental Protection Agency 1980b). Hazardous waste totals
are projected to grow at an annual rate of about 3 percent and to
exceed 75 million tons by the year 2000 (U.S. Environmental Protec-
tion Agency 198Ob).
Inevitably, significant increases in the future output of chemi-
cals will be accompanied by greater quantities of waste materials.
That future output is likely to be influenced by economic factors—an
effect observed in the short term during recent temporary slumps in
the economy. For example, the output of most organic chemicals pro-
duced in large volume declined in 1975 as compared with 1974 (Chemi-
cal Information Services 1977).
On the basis of present trends, hazardous wastes from the chemi-
cal industry would be projected to increase between now and the year
97
-------
2000 at an annual rate of 3 to 4 percent. Applying the growth rate
of the organic chemicals industry to the rate of hazardous waste gen-
eration and assuming no change in processing methods and feedstock
sources, this industry alone could generate as much as 32 million
tons of hazardous waste in the year 2000. Of course changes within
the industry can be expected to affect both production mix and waste
generation, but this figure provides a reference point for compara-
tive purposes.
A. 2 Characteristics and Implications
Toxicity is a characteristic of a chemical substance defining
the degree of adversity for an organism exposed at a given dose
level. Hazard refers to the likelihood that a chemical will be pres-
ent at a harmful exposure level. A chemical can have relatively high
inherent toxicity but can be considered non-hazardous if exposure
results in insufficient dosages to produce a toxic effect (U.S.
Environmental Protection Agency 1980b). Estimates of likely
exposures can be obtained from such sources as:
o Current or proposed production rates;
o Data on probable environmental releases from production, use
and disposal through mass-balance engineering assessments;
and
o Study of basic chemical/physical properties.
The traditional technique for studying the acute effects of
toxic agents is lethality dose determination, a short-term animal
test to determine what dose of a chemical agent would result in the
death of 50 percent of the test animal population (LD5Q). While
98
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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
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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
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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
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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
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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
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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
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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
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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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124
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Department Approval:,
/-•-)
MITRE Project Approval:
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