EPA-600/2-77-023e
January 1977
Environmental Protection Technology Series
INDUSTRIAL PROCESS PROFILES FOh
ENVIRONMENTAL USE: Chapters.
Basic Petrochemicals Industry
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-77-023e
January 1977
INDUSTRIAL PROCESS PROFILES
FOR ENVIRONMENTAL USE:
CHAPTER 5. BASIC PETROCHEMICALS INDUSTRY
by
T.B. Parsons, C.M. Thompson, and G.E. Wilkins
Radian Corporation
P.O. Box 9948
Austin, Texas 78766
Contract No. 68-02-1319, Task 34
ROAPNo. 21AFH-025
Program Element No. 1AB015
EPA Project Officer: I. A. Jefcoat
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
TABLE OF CONTENTS
Page
INDUSTRY DESCRIPTION 1
Raw Materials 9
Products 9
Companies 14
Envi ronmental Impact 15
Bibliography 20
INDUSTRY ANALYSIS 22
Olefins Production Processes 23
Thermal Cracking 28
Oi 1 Quenchi ng 32
Water Quenching 34
Compression 36
Aci d Gas Removal 38
Water Removal 40
Demethanation 41
C2 Separation 43
C3 Separation 46
Cit Separation 48
Heavy Fractionation 49
Butadiene Production Processes 50
Process No. 12. Separation and Purification 53
Process No. 13. Butane Dehydrogenation 57
Process No. 14. Butenes Dehydrogenation 60
BTX Production Processes 63
Process No. 1.
Process No. 2.
Process No. 3.
Process No. 4.
Process No. 5.
Process No. 6.
Process No. 7.
Process No. 8.
Process No. 9.
Process No.10.
Process No.11.
Process No.15.
Process No.16.
Process No.17.
Process No.18.
Process No.19.
Process No.20.
Hydro treati ng 65
Aromatics Extraction 70
C6-C9+ Aromatics Separation 74
Cs Aromatics Fractionation 76
Para-xylene Crystallization 73
Para-xylene Adsorption 81
m
-------
TABLE OF CONTENTS (continued)
Page
Process No.21. C8 Aromatics Isomerization 83
Process No.22. Toluene Disproportionatlon/Transalkylation 86
Process No.23. Hydrodealkylation 89
Naphthalene Production Processes 93
Process No.24. Extraction of Dicyclic Aromatics 95
Process No.25. Hydrodealkylation to Produce Napthalene 98
Cresols and Cresylic Acids Production Processes 102
Process No.26. Acidification 104
Process No. 27. Product Recovery 107
Normal Paraffin Production Processes 109
Process No.28. Separation of Normal Paraffins Ill
APPENDIX A - Raw Materials 115
APPENDIX B - Products , 117
APPENDIX C - Producers of Basic Petrochemicals and
Production Locations 119
IV
-------
LIST OF FIGURES
Figure Page
1 PETROCHEMICAL USE OF ETHYLENE IN 1973 10
2 PETROCHEMICAL USE OF BENZENE IN 1973 11
3 PETROCHEMICAL USE OF BUTADIENE IN 1973 12
4 PETROCHEMICAL USE OF PROPYLENE IN 1973 13
5 OLEFINS PRODUCTION PROCESSES 24
6 BUTADIENE PRODUCTION PROCESSES 51
7 BTX PRODUCTION PROCESSES 64
8 NAPHTHALENE PRODUCTION PROCESSES 94
9 CRESOLS AND CRESYLIC ACIDS PRODUCTION PROCESSES 103
10 SEPARATION OF NORMAL PARAFFINS 110
-------
LIST OF TABLES
Table Page
1 OPERATIONS IN THE BASIC PETROCHEMICAL INDUSTRY 2
2 1974 PRODUCTION OF BASIC PETROCHEMICALS 3
3 GEOGRAPHIC LOCATION OF BASIC PETROCHEMICAL
MANUFACTURING FACILITIES 5
4 PRODUCTS FROM CRUDE OIL CRACKING TO PRODUCE 500 Gg
(ONE BILLION POUNDS) ETHYLENE PER.YEAR 6
5 EXAMPLE PRODUCT SLATE FROM COAL UTILIZATION
FOR PETROCHEMICAL FEEDSTOCKS 6
6 1974 PREDICTIONS FOR FUTURE DEMAND AND GROWTH
RATE OF BASIC PETROCHEMICALS 7
7 1973 FEEDSTOCK REQUIREMENTS OF THE BASIC PETROCHEMICALS
INDUSTRY 8
8 BASIC PETROCHEMICAL PRODUCTION BY PETROLEUM
REFINERS IN 1974 14
9 LARGE VOLUME PETROCHEMICAL PRODUCERS 16
10 UTILITY REQUIREMENTS FOR AN ETHYLENE PLANT 23
11 ESTIMATED HYDROCARBON LOSSES FROM AN ETHYLENE PLANT
PRODUCING 227 Gg {500 MILLION LB)/YR 25
12 WASTEWATER COMPOSITION FROM OLEFIN PLANTS 26
13 TYPICAL EQUIPMENT REQUIREMENTS FOR A 500 Gg/YR
NAPHTHA CRACKER 27
14 STEAM-TO-HYDROCARBON RATIOS 28
15 FEEDSTOCK AND PRODUCTION DATA 29
16 HEAT RECOVERY IN TRANSFER LINE HEAT EXCHANGERS 29
17 COMPOSITION OF A REFINERY GAS 36
18 WASTE CAUSTIC STREAM COMPOSITION 39
19 TYPICAL DEMETHANIZER FEEDS 41
20 TYPICAL ETHYLENE PRODUCT SPECIFICATIONS 43
21 COMPOSITION OF WASTE FROM A BUTADIENE PLANT 52
22 BUTADIENE YIELDS FROM THERMAL CRACKING 54
23 ACETYLENICS CONTENT OF VARIOUS d, STREAMS 54
24 WASTEWATER FROM BUTADIENE PLANTS 55
25 OPERATING PARAMETERS FOR DEHYDROGENATION
OF BUTENES 61
-------
LIST OF TABLES (continued)
Table Page
26 HYDROCARBONS IN TYPICAL PYROLYSIS GASOLINE
CONTAINING 70% AROMATICS 66
27 DESIGN CASE COMPOSITION OF FEED AND PRODUCT FROM TWO-STAGE
HYDROGENATION OF PYROLYSIS GASOLINE 66
28 UTILITY REQUIREMENTS FOR 182,000 METRIC TON/YR TWO-STAGE
PYROLYSIS GASOLINE HYDROTREATER 67
29 CHARACTERISTICS OF WASTEWATER FROM TWO-STAGE
HYDROTREATING OF PYROLYSIS GASOLINE 68
30 TYPICAL AROMATICS CONTENT IN REFORMATS 71
31 OPERATING PARAMETERS FOR UDEX AND SULFOLANE
AROMATICS EXTRACTION PROCESSES 71
32 UTILITY REQUIREMENTS FOR UDEX AND SULFOLANE
AROMATICS EXTRACTION PROCESSES 72
33 TYPICAL COMPOSITION OF C8 AROMATICS MIXTURES FROM
VARIOUS SOURCES 76
34 UTILITY REQUIREMENTS FOR PARA-XYLENE CRYSTALLIZATION 79
35 UTILITY REQUIREMENTS FOR COMBINED ADSORPTION (AROMAX PROCESS)
AND ISOMERIZATION PROCESS PRODUCING 100 Gg/YEAR
PARA-XYLENE 81
36 OPERATING CONDITIONS FOR COMMERCIAL C8 AROMATICS
ISOMERIZATION PROCESSES 84
37 UTILITY REQUIREMENTS FOR COMBINED XYLENE
CRYSTALLIZATION-ISOMERIZATION PROCESS 84
38 VARIATIONS OF DISPROPORTIONATION/TRANSALKYLATION
PRODUCT RATIOS WITH C9 CONTENT OF FEED 87
39 UTILITY REQUIREMENTS FOR VAPOR PHASE CATALYTIC TOLUENE
DISPROPORTIONATE WITH C9 RECYCLE 87
40 TYPICAL COMPOSITION OF FEEDSTOCKS FOR HOUDRY
HYDRODEALKYLATION PROCESS 90
41 UTILITY CONSUMPTION RATES FOR BENZENE PRODUCTION FROM
TOLUENE BY THE HYDEAL PROCESS 91
42 UTILITY REQUIREMENTS FOR THE HOUDRY CATALYTIC
HYDRODEALKYLATION PROCESS 91
43 STREAM COMPOSITIONS FOR EXTRACTION PROCESS 95
44 UTILITY REQUIREMENTS FOR EXTRACTION OF ALKYL
NAPHTHALENES FROM DIFFERENT FEEDSTOCKS 96
45 TYPICAL COMPOSITION OF NAPHTHALENE CHARGE STOCKS 98
VI1
-------
LIST OF TABLES (continued)
Table Page
46 PRODUCT YIELDS FROM THE HYDEAL PROCESS 99
47 UTILITY REQUIREMENTS FOR THE HYDEAL PROCESS 99
48 TYPICAL COMPOSITION OF CAUSTIC STREAM 105
49 PHENOL CONTENT OF AQUEOUS WASTES FROM SPRINGING 106
50 UTILITY REQUIREMENTS FOR ISO SIV PROCESS 112
A-l HYDROCARBON RAW MATERIALS FOR THE BASIC PETROCHEMICALS
INDUSTRY 116
B-l PRODUCTS AND BY-PRODUCTS OF THE BASIC PETROCHEMICALS
INDUSTRY 118
C-l BENZENE PRODUCERS 120
C-2 BUTADIENE PRODUCERS 124
C-3 CRESOLS AND CRESYLIC ACIDS PRODUCERS 126
C-4 ETHYLENE PRODUCERS 127
C-5 NAPHTHALENE PRODUCERS 130
C-6 MIXED XYLENES PRODUCERS 131
C-7 NORMAL PARAFFINS PRODUCERS 133
C-8 PROPYLENE PRODUCERS 134
C-9 TOLUENE PRODUCERS 138
C-10 BASIC PETROCHEMICAL PRODUCTION SITES DIRECTLY ASSOCIATED
WITH PETROLEUM REFINERIES 141
C-ll BASIC PETROCHEMICAL PRODUCTION SITES NOT DIRECTLY ASSOCIATED
WITH A PETROLEUM REFINERY 144
vm
-------
BASIC PETROCHEMICALS INDUSTRY
INDUSTRY DESCRIPTION
The basic petrochemicals industry described in this chapter includes
companies which treat hydrocarbon streams from the petroleum refining
industry (Chapter 3) and natural gas liquids from the oil and gas pro-
duction industry (Chapter 2). These raw materials are used to produce
feedstocks for the organic chemical industry including benzene, the
butylenes, cresols and cresylic acids, ethylene, naphthalene, paraffins,
propylene, toluene, and xylenes. The products are pure or mixed chemicals
for use as solvents or chemical intermediates. Other product streams are
captively consumed or used as feedstocks for certain processes within the
refining industry. The industry is very difficult to define because its
operations are "intertwined functionally or physically with the inorganic
sector of the chemical industry, with downstream (manufacturing,) fabri-
cation or compounding activities, or with the petroleum refining industry.
(This results in) mixing of vertical operating steps in official statistics."*
The processes conducted in the basic petrochemicals industry are
mainly separation and purification processes. Some chemical conversion
processes such as cracking, hydrogenation, isomerization, and dispropor-
tionation are carried out. As defined in Chapter 1, a process converts a
raw material into products, by-products, intermediate products, or waste
streams. Six groups of related processes, termed operations, are employed
by the industry. Table 1 lists the six operations along with their raw
materials and products. Each of the operations listed in Table 1 is
described in detail on a separate flow sheet containing a collection of
processes which are indicated by numbered boxes. A process description
was prepared for each process in the numbered boxes.
The 1975 Directory of Chemiqal Producers indicates that there are
some 107 faci1i ties at which basic petrochemicals are produced from refinery
streams or natural gas liquids. Sixty-five percent of these facilities
are closely associated with refineries, while the other thirty-five percent
of the locations are not directly associated with a refinery. "Information
is not available on the relative size of basic petrochemical operations
by company because these operations are completely integrated with other
manufacturing functions."*
The literature consulted for this study did not provide employment data
for the separate group of companies or subsidiaries defined as producers of
basic petrochemicals from petroleum refining streams. Employment data were
found for the larger group of companies defined in SIC Code 2911. The
larger group includes the refinery-associated companies but probably does
not include the companies not associated with a refinery. In 1974, 94,000
production workers were involved in petroleum refining operations. These
operations included production of BTX, solvents, and probably some olefins;
but this production was a small percent of the total production of the refining
industry. Table 2 shows the total volume of production for the basic petro-
chemical industry in 1974 by product.
Federal Energy Administration (Office of Economic Impact). Report to Congress
on Petrochemicals. Public Law 93-275, Section 23 (no date: circa 1974).
1
-------
Table 1. OPERATIONS IN THE BASIC PETROCHEMICALS INDUSTRY
Raw Material
Operation
Product or Intermediate
Product
Natural gas liquids
Refinery gases
Naphtha and heavier
feedstocks
Mixed Cit stream from
olefins production
Refinery gases
Pyrolysis gasoline from
olefins production
C6-C9 fraction of
catalytic reformate
Olefins Production
(Processes 1-13)
Butadiene Production
(Processes 14 - 22)
BTX Production
(Processes 15 - 23)
Ethylene
Propylene
Mixed Cit Stream
Pyrolysis Gasoline
Butadiene
Butenes
Isobutylene or
Polymerized Product
Benzene
Toluene
Mixed C8 Aromatics
Separated C8 Isomers
Heavy reformate
Heavy fraction of
pyrolysis gasoline
from olefins
production
Catalytic cycle oil
Caustic extract from
treatment of petroleum
distillate
Naphtha
Gas-oil
Kerosene
Naphthalene Production
(Processes 24 and 25)
Naphthalene
Production of Cresols
and Cresylic Acids
(Processes 26 and 27)
Separation of Normal
Paraffins
(Process 28)
Mixed Cresols
Separated Cresol
Isomers
Cresylic Acid
Xylenols
Phenol
C5-C7 Normal Paraffins
CIO-CIB Normal Paraffins
-------
Table 2. 1974 PRODUCTION OF BASIC PETROCHEMICALS
Material
Ethyl ene
Benzene
Propylene
Toluene
Mixed xylenes
Butadiene (1 ,3-)
Para-xylene
Naphthalene
Ortho-xylene
Normal paraffins3
Mixed cresols, cresylic
Production
(billion Ibs)
23.52
11.07
9.82
7.49
5.79
3.66
2.68
1.0 - 1.3
1.05
0.67
acids 0.197
(Tg, billion kg)
10.67
5.02
4.45
3.40
2.63
1.66
1.22
0.45 - 0.59
0.476
0.30
0.089
a 1971 Consumption
Source: Anonymous. "Recession Clamped a Lid on Growth in Chemical Output
Last Year, with Production Down for Many Major Producers." Chemical
& Engineering News, 53(22) (2 June 1975), 31-34.
Hedley, W. H., et al. Potential Pollutants From Petrochemical Processes
MRC-DA-406. Dayton, Ohio: Monsanto Research Corp., December 1973.
-------
Tables C-10 and C-ll in the Appendix list locations at which basic
petrochemicals are manufactured. The tables indicate whether or not the
location is directly associated with a refinery and also indicate which
basic petrochemicals are produced at the location. Table 3, which sum-
marizes the information in Tables C-10 and C-ll by state, shows that 47
percent of the facilities are located in Texas and Louisiana. Many of the
Texas and Louisiana locations are centered in the highly populated Gulf
Coast area, but some of the Texas facilities are located in the less highly
populated cities of West Texas.
Some interrelated factors which influence change or growth in the basic
petrochemicals industry are feedstock availability, capacity, and demand
for products from downstream users. World trade and its influence on the
import/export situation are also related to growth or change in the industry.
Growth or increase in production can be predicted to occur when demand exceeds
capacity and domestic production is economically favored over importing.
Significant feedstock changes are anticipated from the industry.
Recent petroleum and natural gas shortages have limited petrochemical
production. As a result, a shift toward petrochemical production from
other fossil fuels and heavier petroleum feedstocks is predicted. The
amount of ethylene production from naphtha, crude distillation residuals,
and crude will increase. Table 4 shows predicted products from cracking
crude oil to produce 500 Gg (one billion pounds) of ethylene per year. Crude
oil requirements for ethylene production from crude oil cracking are one-
fifth of the crude requirements for the naphtha required to produce the same
amount of ethylene. Table 5 shows a predicted product slate for coal based
production of petrochemicals. Predictions are that by 1980 all petrochemical
feedstock demand could be supplied by processing 0.5 Tg (500,000 tons) of
coal per day.
The years 1974 and 1975 were generally a time of shortages in capacity
for the industry. Increases in capacity require massive capital investments
and three- to five-year lead times. Such increases are anticipated to occur
mainly through alterations in industry structure through forward integration
of the oil companies and backward integration of the chemical companies.
Petroleum refiners are expected to invest in chemical production in an at-
tempt to increase profits, since chemical operations provide better profits
than other oil company operations. It is predicted that oil companies will
gain a share of the market in downstream large volume intermediates such as
phenol, ethylene oxide, polyethylene, styrene, and vinyl chloride. Table 6
summarizes published predictions of future demand and projected growth rates
for some of the basic petrochemicals.
-------
Table 3. GEOGRAPHIC LOCATION OF BASIC PETROCHEMICAL
MANUFACTURING FACILITIES
State or Location
Texas
Louisiana
Illinois
California
New Jersey
Puerto Rico
Kentucky
Ohio
Pennsylvania
Del aware
Michigan
Oklahoma
Indiana
Kansas
Arkansas
Six* other locations
Number of Facilities
38
12
9
7
6
5
4
4
3
3
2
2
2
2
2
1 each
Percent of Total
36
11
8
7
6
5
4
4
3
3
2
2
2
2
2
6
* Alabama, Iowa, Mississippi, New York, Virginia, Virgin Islands
-------
Table 4. PRODUCTS FROM CRUDE OIL CRACKING TO PRODUCE 500 Gg
(ONE BILLION POUNDS) ETHYLENE PER YEAR
Product
Ethyl ene
Acetyl ene
Propylene
Crude butadiene
Crude BTX
By-product fuel
Gq/yr
500
90
60
40
200
Quantity
106 Ib/yr
1,000
200
135
90
435
Sufficient quantity
to supply the
ethylene plant
Source: Ponder, T. C. "Petrochemicals--More for 1974."
Hydrocarbon Processing, 53 (May 1974), 81-83.
Table 5. EXAMPLE PRODUCT SLATE FROM COAL UTILIZATION
FOR PETROCHEMICAL FEEDSTOCKS
Approximate Percent
Product By Weight
Ci-Cit hydrocarbons 30
Fuel oil 16
Naphtha 3
BTX 33
Char, H2S, NH3> H20 18
Source: Ponder, T. C. "Petrochemicals--More for 1974."
Hydrocarbon Processing, 53 (May 1974), 81-83.
-------
Table 6. 1974 PREDICTIONS FOR FUTURE DEMAND AND GROWTH RATE
OF BASIC PETROCHEMICALS
Basic
Petrochemical
Predicted
Demand
Year
Predicted
Annual Growth
Rate
Ethylene 16.8 Tg (18.5xl06 tons) 1980
capacity
15.4 Tg (17x10* tons)
consumption
7.5% (ethylene production)
8.5% (ethylene feedstocks)
Naphthalene 7.57 dm3 (2xl06 gallons) 1980
Butadiene
Benzene
Toluene
Xylenes
7.199 hm3 (1902xl06
gallons)
1.21 hm3 (319xl06
gallons)
3.34 hm3 (882x1O6
gallons)
1980
1980
1980
Expect demand to decrease
due to replacement by
ortho-xylene in phthalic
anhydride production
4.2 percent
Worldwide demand will
increase 10% per year
Source: Ponder, T. C. "Petrochemicals--More for 1974." Hydrocarbon Processing,
53 (May 1974), 81-83.
-------
Table 7. 1973 FEEDSTOCK REQUIREMENTS OF THE BASIC PETROCHEMICALS INDUSTRY
—
Raw Material
and
Description
- -•- • •
Total
Volume
Consumed
or Produced
Volume
Utilized
For Basic
Petrochemical
Production
—
Remarks
Natural Gas (Methane)
623 km3 (22 x 1012 ft3
(not including gas
liquids and other
hydrocarbons)
22.7 km3 (800 x 109
(3.6% of total
consumption)
ft ) Used for ammonia
and methanol manu-
facture. Also used
for steam and power
generation and plant
fuel.
Ethane from natural
gas (less than 10
percent is obtained
from refineri-es)
C3 and Ci, Hydrocarbons
including propane,
n-butane, isobutane,
propylene, and
butylene from natural
gas processing plants
and refineries
Naphtha (gasoline
boiling range
hydrocarbons)
including field
condensate and
raffinates
Reformate
Heavy fractions
Kerosene
Gas-Oil
Most recovered ethane is used for
petrochemical feedstock. Total ethane
consumption contained energy equivalent
to 1.5 percent of the energy of natural
gas consumed in U.S.
Half of ethylene
production was based
on ethane
53.9 hm3 (339 x 106
barrels) of propane
(63%), n-butane (27%).
and isobutane
(10%) recovered in 1973.
55-60 hm3 (350-400 x 10s
barrels) Cj and Ci,
hydrocarbons produced
in refineries by crack-
ing and reforming.
416 hm3 (2,620 x 106
barrels) were consumed
60.4 hm3 (380 x 106
barrels) of kerosene
used for jet and other
fuel
20.7 hm3 (130 x 10G
barrels) or 20 per-
cent of production
10 hm3 (70 x 106
barrels) or 2.7 per-
cent of consumption .
8.27 x hm3 (52 x 106
barrels) of reformate
were used for aromatics.
0.3 hm3 (2 x 10s
barrels) of normal
paraffins extracted
from kerosene in
1973.
4.3 hm3 (27 x 106
barrels) were used
for olefin production
or about one percent
of the distillate oils
produced from crude.
Governed by
allocations
SOURCE: Federal Energy Administration (Office of Economic Impact). Report to Congress on Petrochemicals
Public Law 93-275. Section 23, (no date: circa 1974).
-------
Raw Materials
"The petrochemical industry is dependent upon the natural gas and
petroleum refining industries for its feedstock. In 1973, estimated
petrochemical feedstock usage of natural gas was about 800 billion cubic
feet, or 3.6 percent of total consumption. Natural gas liquids and re-
finery fraction consumption was about 330 million barrels, or 5.1 percent
of 1973 demand. The energy content of petroleum and natural gas hydrocarbons
consumed as petrochemical feedstocks was about 4 percent of the total energy
from these sources."* Table 7 summarizes volumes of each raw material
consumed by the basic petrochemical industry in 1973. The U.S. government
exercises price and allocation controls on the feedstocks employed by this
industry.
In general, basic petrochemical plants can be characterized on the basis
of their location with respect to a refinery and their feedstocks. Some plants
are refinery connected. These are located at or near refineries; they isolate
ethylene from refinery off-gases and they use other refinery products (ethane
reformate, or naphtha) for at least part of their feedstock. Others use feed-
stocks obtained from natural gas processing or oil field condensate plants.
Products
The basic petrochemicals industry produces solvents and chemicals of
various grades or specifications which are used to produce industrial
organic chemicals. For some of the basic petrochemicals only a portion
of the production is diverted to petrochemical use. A large portion of the
production of aromatics and other petrochemicals is returned to the refinery
for use in gasoline and aviation fuels.
Approximately 2500 organic chemical products are produced directly or
indirectly from basic petrochemicals. The industrial organic chemicals
produced from basic petrochemicals are employed in downstream industries
including plastics and resins, synthetic fibers, elastomers (synthetic
rubber), plasticizers, explosives, surface active agents, dyes, surface
coatings, Pharmaceuticals, and pesticides. Figures 1 through 4 show the
major industrial organic chemicals produced from ethylene, propylene, benzene
and butadiene. Toluene is used as a high octane gasoline component, to
produce benzene, and in the production of plastics, dyes, solvents, explosives
and specialty chemicals. Only a small portion of the C8 aromatics (mixed
xylene) production is used for chemical production. Ortho- and para-xylene
are the isomers used most widely for chemical intermediates. Ortho-xylene
is used to produce phthalic anhydride, and para-xylene is used to produce
* Federal Energy Administration (Office of Economic Impact). Report to
Congress on Petrochemicals. Public Law 93-275, Section 23, (no date:
circa 1974).
-------
SOURCE
Refinery Gases
Cracking Licht
Hydrocarbons
Cracking Liquid
Feedstocks
Ethylene
(22.4)
PRINCIPAL INTERMEDIATES
Polyethylene
40% (9.0)
Ethylene Oxide
20% (4.5)
Ethylene Dichloride
14% (3.1)
Ethyl Benzene
8% (1.8)
Ethanol
6% (1.4)
Misc.
12% (2.6)
END USES
Molded Plastics
Film and Sheet
Mono Filament
Glycols
Surfactants
Resins
Solvents
Plastics
Solvents
Misc. Chemicals
Plastics
Resins
Misc. Chemicals
Solvents
Misc. Chemicals
Source: Federal Energy Administration (Office of Economic Impact). Report to Congress on
Petrochemicals. Public Law 93-275, Section 23, (no date: circa 1974).
Figure 1. PETROCHEMICAL USE OF ETHYLENE IN 1973 (BILLION POUNDS)
-------
CATALYTIC
REFORMING
TOLUENE
HYDRO-
DEALKYLATION
OLEFINS
PLANT
BYPRODUCT
COAL TAR
BENZENE
PRINCIPAL INTERMEDIATES
ETHYLBiNZENE/
I"E (699)
(297)
LEIC ANHYDRIDE
DETERGENT
ALKYLATE
2,5% (36)
MISCELLANEOUS
4,9% (72)
PLASTICS
RUBBER
PLASTICS
SURFACTANTS
NYLON
NYLON
DYES
RUBBER CHEMICAL
PLASTICS
PLASTICS
FOOD ADDITIVE
SURFACTANTS
DRUGS
FUNGICIDES
DYES
Source-Federal Energy Administration (Office of Economic Impact). Report to Congress on
Petrochemicals. Public Law 93-275, Section 23, (no date: circa 1974).
Figure 2. PETROCHEMICAL USE OF BENZENE IN 1973 (MILLION GALLONS)
-------
r\s
Domestic Production
- Dehydration of
n Butane/Butylene
91.4% (3663)
70%
- By-product of Ethylene
Cracking 30%
Net Imports
Imports (365)
Exports (64)
Net (301)
Other (Inventory)
7.5% (301)
1.1% (46)
Butadiene
Calc. Consumption (4010)
Elastomers
78.5% (3151)
Nylon Intermediates
9.0% (360)
Plastic and Resins
9.7% (388)
Miscellaneous
2.8% (111)
SBR
Poly Butadiene
Nitrite
Neoprene
Nylon
ABS
Other
Source: Federal Energy Administration (Office of Economic Impact). Report to Congress on
Petrochemicals. Public Law 93-275, Section 23, (no date: circa 1974).
Figure 3. PETROCHEMICAL USE OF BUTADIENE IN 1973 (MILLION POUNDS)
-------
Petroleum
Refining
(85%)
Cracking
Heavier Stocks
to Make (15%)
Olefins
Propylene
(Calculated Consumption-10.06)
Polypropylene
25% (2.48)
Acrylonitrile
18% (1.83)
Isopropanol
15% (1.49)
Propylene Oxide
16% (1.65) '
Molded Plastics
Fibers
Film
Sheet
Fibers
Rubber
Resins
Misc.
Plastics
Resins
Misc.
Surface Active Agents
Foams
Resins
Other
26% (2.61)
Source.—Federal Energy Administration (Office of Economic Impact). Report to Congress on
Petrochemicals. Public Law 93-275, Section 23, (no date: circa 1974).
Figure 4. PETROCHEMICAL USE OF PROPYLENE IN 1973 (BILLION POUNDS)
-------
terephthalic acid and dimethyl terephthalate. These chemicals are used in
the plasticizers and synthetic fibers industries. Seventy-five percent
of the naphthalene produced is used in phthalic anhydride manufacture.
Normal paraffins in the C5-C7 range are used as specialty solvents,
while those in the Ci0-Ci5 range are used in the production of linear
alkylbenzene sulfonates for biodegradable detergents. The largest use for
cresols and cresylic acids is for phosphate esters.
Table B-l in the Appendix lists products and by-products of the basic
petrochemicals industry- The limited resources available for this study
did not permit the inclusion of information describing the grades and
specifications available for each chemical or mixture. Since the basic
petrochemicals serve either as raw materials for downstream organic
products or as precursors to intermediates for downstream organic products,
their purity is critical and is usually determined by the most demanding end
use. They are produced in purities ranging from 90+% to 99.99+%. The
maximum impurities allowed are from 0.5 to 5000 ppm depending on the impurity
and ultimate end use.
Companies
The majority of the output from the basic petrochemicals industry, is
produced by petrochemical divisions or subsidiaries of major oil companies
as indicated in Table 8. While these are legal subdivisions of oil companies
and probably separate entities for accounting purposes, they are actually a
part of the oil companies. Since the petrochemical plants are dependent on
refineries, gas processing plants, or field condensate plants for their raw
materials, they are located near the petroleum processing sites to facilitate
stream transfers. In some cases they are actually located within the same
fence.
Table 8. BASIC PETROCHEMICAL PRODUCTION BY
PETROLEUM REFINERS IN 1974
Percent of 1974 Capacity
Petroleum Chemica"
Basic Petrochemical Refiners Companies Other
Benzene
Ethyl ene
Chemical Grade Propylene
70
40
>60
r
17
45
13
15
>v.i»tvMiw I I^IA 111 1_ U I C VI 1C \J I | lllQUS L I V
Chemical & Engineering News, 53(50) (15 December 1975), 12-14
Large, multiline chemical companies also produce a portion of the
basic petrochemicals. As is the case for major oil companies, there is a
significant incidence of vertical integration in the chemical'companies
which produce basic petrochemicals.
14
-------
The data utilized for this study did not readily indicate the existence
of a significant population of independent companies that purchase natural
gas processing or refinery products, produce basic petrochemicals, then
sell them to distinctly separate companies that use them to produce indus-
trial organic chemical intermediates. It is possible that some of the
companies in Table C-ll (Appendix C), such as Petro-Tex Chemical Corporation,
are classified in this category.
There are other companies that also produce a small volume of the aromatic
chemicals produced by this industry. These companies use primarily coal-
derived rather than petroleum-derived raw materials, and the operations
(groups of processes) employed are somewhat different than those employed
by the basic petrochemical industry. Some petroleum-based petrochemical
plants have facilities for treating purchased coke oven light oil or coal
tar distillates. In general, however, production of chemicals from coal is
accomplished by a separate population of companies. The published pro-
duction data for some products in Table 1 may include production from coal-
derived raw materials. This portion of the production is generally small.
An attempt was made to exclude companies utilizing coal-derived raw
materials from the company/product lists in Appendix C.
Table 9 lists companies which have the major capacities for each basic
petrochemical. Sources of data and inconsistencies in data are described
in the footnotes to the table.
En v1ronmen ta1 Impact
In general the waste streams from this industry are quite similar to
those of the petroleum refining industry. The industry employs processes
which separate hydrocarbon mixtures into pure components and byproduct
hydrocarbons. To avoid discarding valuable hydrocarbon streams, the by-
products are used for fuel or are converted to other refinery products.
Estimated hydrocarbon emissions are in the range from 0.1 to 0.6 percent
of plant throughput. Hydrocarbons are emitted in low concentrations in
wastewater, as fugitive gaseous emissions, and in solid residues. Some
of the hydrocarbons emitted are photochemically reactive. Other non-hydro-
carbon pollutants emitted are water treatment wastes including fouling and
corrosion inhibitors, products from sulfur and nitrogen removal processes,
spent catalysts and solid adsorbents, combustion and incineration products,
and wastes from catalyst cleaning operations.
Auxiliary processes are employed by the basic petrochemical industry
for process heating (steam or fired heaters) and cooling (cooling water or
refrigeration). Operation of the steam generation and cooling water systems
produces the majdr portion of wastewater from the industry. Emissions from
fired heaters are described in Chapter 3, The Petroleum Refining Industry.
Electric power is usually purchased by this industry rather than produced
oil-site.
15
-------
Table 9. LARGE VOLUME PETROCHEMICAL PRODUCERS3>b*c
Products and Companies (10* Ib/yr) §£
Cresols and Cresylic Acids
(Recovered from Petroleum)
Merichem Co. 100 45
Northwest Petroleum 15 7
Pitt-Consol 50 20
Productol Chem. Co. 30 10
Butadiene
Atlantic Richfield Co. 280 130
El Paso Natural Gas Co. 200 90
Exxon Chemical Co., USA 340 150
Firestone Tire & Rubber Co. 220 100
Neches Butane Products 640 290
Petro-Tex Chemical Corp. 990 450
Phillips Petroleum Co. 290 130
Puerto Rico Olefins Co. 200 90
Shell Chemical Co. 265 120
Mixed Xylenes (from Petroleum)
Atlantic Richfield Co. 430 200
Cities Service Co., Inc. 520 240
Commonwealth Oil Refining Co. 570 260
Phillips Petroleum Co. 720 330
Shell Oil Company 505 230
Standard Oil of California 980 440
Standard Oil Co. (Indiana) 1075 488
Standard Oil Co. (New Jersey) 860 390
Sun Oil Company 465 211
Tenneco, Inc. 360 160
Toluene (from Petroleum)
Amerada Hess Corp. 290 130
Ashland Oil, Inc. 360 ]60
Atlantic Richfield Co. 420 190
Mobil Oil Corp. 500 200
Monsanto Co. 325 143
Phillips Petroleum Co. 650 300
Shell Oil Co. 360 160
Standard Oil Co. (Indiana) 1150 522
Standard Oil Co. (New Jersey) 940 430
Sun Oil Co. 530 240
Propylene
Amoco Chemicals Corp. 1090 490
Atlantic Richfield Co. 505 230
Chevron Chemical Co. 740 340
Oow Chemical USA 910 410
Exxon Chemical Co., USA 1990 903
Gulf Oil Corp. 495 225
Shell Oil Co. 1170 531
Sun Oil Co. 450 200
Union Carbide Co. 1285 583
Percentage
of Total
Assumed 100%
Remarks
Some synthetic
production in-
cluded.
1973 Data
78%
1975 Data
78%
1971 Data
68%
1972 Data
66%
All Grades.
1975 Data
16
-------
Table 9. LARGE VOLUME PETROCHEMICAL PRODUCERS3'15'0 (Cont.)
Products and Companies
Naphthalene (from Petroleum)
Ashland Oil, Inc.
Getty Oil Co.
Kewanee Oil Co.
Monsanto Co.
Sun Oil Co.
n-Paraffins
Continental Oil Co.
Exxon Corp.
Shell Chemical Co.
South Hampton Co.
Union Carbide Corp.
Ethylene
Cities Service Co., Inc.
Dow Chemical, USA
Exxon Chemical Co., USA
Gulf Oil Chemicals Co.
Phillips Petroleum Co.
Shell Oil Co.
Union Carbide Corp.
Capacity ,
IIP6 lb/yr)d
100
100
Not Available
100
150
225
220
100
60
240
940
3770
1770
1570
1140
2050
4315
Benzene
Atlantic Richfield Co.
Coastal States Gas Corp.
Commonwealth Oil Refining
Co.
Dow Chemical USA
Exxon Corp.
Gulf Oil Corp.
Monsanto Co.
Phillips Petroleum Co.
Shell Chemical Co.
Standard Oil Co. (Indiana)
Sun Oil Co.
Tenneco, Inc.
625
515
1360
515
985
1045
550
970
1030
625
510
660
45
45
45
68
102
100
45
30
110
430
1710
804
710
518
930
1959
284
234
617
234
447
474
250
440
470
284
230
300
Percentage
of Total
Not Available
Remarks
1974 Data
Assumed 100%
1974 Data.
o-Cis Range
67%
1974 Data
68%
1975 Data
8 Production of subsidiaries may be listed with parent company's capacity.
Butylenes are generally used captively. Their production capacity is hard to
determine.
C Information provided by Monsanto Research Corporation, Directory of Chemical
Producers. 1975. and Chemical Marketing Reporter, 18 Feb., 1974. Details are
summarized in Tables C-l through C-9. Data therein may be inconsistent with
data in Tables C-10 and C-11.
Estimates assumed accurate to the nearest 5xl06 Ibs. Conversions made to the
same number of significant figures or to the nearest Gg.
17
-------
Wastewater, which is the major source of emissions from the basic
petrochemical industry, has been described in five categories:
(1) Wastes containing a principal raw material or product;
(2) By-products produced during reactions;
(3) Spills, leaks, washdowns, vessel cleanouts, or point overflows;
(4) Cooling tower and boiler blowdown, steam condensate, water
treatment wastes, and general washing water; and
(5) Surface runoff.
For purposes of developing wastewater emission control guidelines for
the industry, basic petrochemical production processes have been categorized
according to modes of water use. The categories and some examples are listed
as follows:
Non-aqueous processes: Hydrotreatment of pyrolysis gasoline, solvent
extraction of BTX from reformate, C8 aromatics isomerization and
crystallization.
Processes with water contact as steam diluent or absorbent: Production
of ethylene and propylene by pyrolysis, butadiene production by
dehydrogenation.
Aqueous liquid phase reactions: Isobutylene extraction with sulfuric
acid.
Solids disposal is a significant problem for the industry. The waste
solids occur in diverse forms. Nearly every plant has some form of solid
waste disposal or handling facility on site. The general methods of dis-
posal are: land disposal, incineration, salvage and recycle, and chemical
and biological treatment. In some cases ocean disposal is permitted. The
solids are composed of water treatment sludge; ashes, flyash and incinerator
residue; plastics; ferrous and nonferrous metals including catalysts; organic
chemicals; inorganic chemicals; filter cakes; and viscous solids.
Gaseous emissions are minor in comparison to the solids and wastewater.
The major air pollutants are particulatos and hydrocarbons. Particulates
are vented to the air during steam-air decoking. Hydrocarbons may be emitted
to the atmosphere through fugitive losses or as vent gases from process
operations. Large quantities of hydrocarbon containing gases may be emitted
during upset conditions by passage through safety valves, usually to a flare
for disposal. Some emissions of SO , NOX, and carbon monoxide occur from
pyrolysis facilities, decoking, or fired'heaters. In general there are few
processes that emit large volume waste gas streams to the atmosphere.
18
-------
Data on volumes and compositions of emissions to air, land, and water
from the industry as defined herein were unavailable. Waste streams from
particular processes were identified either from descriptions in the liter-
ature or by predictions based on knowledge of the process. Plant wastes
result from a combination of waste streams from particular processes.
Waste management operations and facilities are probably of the same degree
of sophistication as those of the petroleum refining industry. Ethylene
plant emissions are an exception in that they are well described. Data
are given in the section on Olefins Production.
19
-------
Bibliography
(1) Anonymous. "Recession Clamped a Lid on Growth in Chemical Output Last
Year, with Production Down for Many Major Producers." Chemical &
Engineering News, 53(22) (2 June 1975), 31-34.
(2) Catalytic, Inc. Capabilities and Costs of Technology for the Organic
Chemical Industry to Achieve the Effluent Limitations of P. L. 92-500.
Final Report, PB 244 544. Philadelphia, Pennsylvania, June 1975.
(3) Clancy, G. M. Radian Corporation, personal communication (March 1976).
(4) DeWitt, J. D. "Olefins Outlook." Hydrocarbon Processing, 53 (November
1974), 121-128.
(5) Erskine, Mimi G. "Benzene," 618.5021 A. Chemical Economics Handbook.
Menlo Park, California: Stanford Research Institute, 1972.
(6) Environmental Protection Agency (Office of Water and Hazardous Materials,
Effluent Guidelines Div.). Development Document for Effluent Limitations
Guidelines and New Source Performance Standards for the Major Organic
Products Segment of the Organic Chemicals Manufacturing Point Source
Category. EPA 440/1-74-009-a. Washington, D. C.: 1974.
(7) Federal Energy Administration (Office of Economic Impact). Report to
Congress on Petrochemicals. Public Law 93-275, Section 23, (no date:
circa 1974).
(8) Garner, D. N. Radian Corporation, personal communication regarding
work done on EPA Contract 68-02-1319, Task 51 (March 1976).
(9) Greek, Bruce F. "Chemicals Again Lure the Oil Industry." Chemical &
Engineering News, 53(50) (15 December 1975), 12-14.
(10) Gloyna, E. F. and D. L. Ford. "The Characteristics and Pollutional
Problems Associated with Petrochemical Wastes." Prepared for FWPCA
Contract 14-12-461, Ada, Oklahoma: Robert S. Kerr Water Research Center,
February 1970.
(11) Hahn, A., A. Chaptal and J. Sialelli. "Why Olefin Specs Have Changed."
Hydrocarbon Processing, 54 (February 1975), 89-92.
(12) Hedley, W. H., et al. Potential Pollutants From Petrochemical Processes.
MRC-DA-406. Dayton, Ohio: Monsanto Research Corp., December 1973.
(13) Kent, James A., ed. Riegel's Handbook of Industrial Chemistry. 7th ed.
N.Y.: Van Nostrand Reinhold Company, 1974.
(14) Mencher, S. K. "Minimizing Waste in the Petrochemical Industry."
Chemical Engineering Progress, 63 (October 1967) 80-88.
20
-------
(15) Ockerbloom, N. E. "World Benzene Outlook." Hydrocarbon Processing, 51
(November 1972), 117-124.
(16) Ponder, T. C. "Petrochemicals—More for 1974." Hydrocarbon Processing,
53 (May 1974), 81-83.
(17) Sittig, Marshall. Pollution Control in the Organic Chemical Industry.
Park Ridge, N.J.: Noyes Data Corporation, 1974.
(18) Stanford Research Institute. Chemical Economics Handbook. Menlo Park
California.
(19) Stanford Research Institute. 1975 Directory of Chemical Producers, U.S.A.
Menlo Park, California: 1975.
(20) U. S. Bureau of the Census. Statistical Abstract of the United States:
1975. 96th edition. Washington, D. C.: 1975.
(21) "Xylene Output Seen Doubling." Chemical Marketing Reporter. (16 February
1975), 7.
(22) Zdonik, S. B., E. 0. Bassler and L. P. Hallee. "How Feedstocks Affect
Ethylene." Hydrocarbon Processing, 53 (February 1974), 73-75.
21
-------
INDUSTRY ANALYSIS
The basic petrochemicals industry is described by six operations composed
of related processes. Process descriptions and operations are somewhat gener-
alized in an effort to accomodate the many variations in modes of processing
that exist due to site-specific and economic factors. This was a desk-top
study of a very complex industry, and the prescribed brevity of process de-
scriptions has resulted in some oversimplification.
Each operation is described by a flow sheet indicating input materials
(brackets), processes (numbered rectangles), and product and by-product
streams (large circles). Solid, liquid, and gaseous waste streams are indi-
cated by the small squares, triangles and circles, respectively, attached
to the numbered process rectangles. Process descriptions follow the flow
sheets on which they are presented.
Data are given in metric units according to the System Internationale
described in the ASTM Metric Practice Guide. Preferred base units and rules
for rounding numbers converted from one system of units to another are de-
scribed therein.
The information used to prepare this catalog entry consisted of books,
encyclopedias, results of EPA supported investigations, consultations with
industry experts in olefin manufacture and refinery-associated petrochemical
operations, and several recently published trade journal articles. There
are additional sources of information such as the open literature, patent
literature, and publications of Stanford Research Institute's Process
Economics Program which were not utilized because of the limited resources
available for this study. The reader is advised to consult these additional
sources of information on subjects which were not treated in depth.
There are some recognized deficiencies and inconsistencies in the data
used to prepare this report. Since the data were originally collected for
other purposes, they were not entirely suitable. For example, there are
reporting problems in Tariff Commission data on chemicals with both petro-
chemical and fuel uses. As a result, utilization of natural gas liquids
and refinery products for consumption by basic petrochemical producers is
not accurately known.
22
-------
OLEFINS PRODUCTION PROCESSES
The Olefins Production Operation of the Basic Petrochemical Industry is
based on what is commonly called an ethylene plant. Because of the current
demand for ethylene, the olefins plants are usually operated for maximum
ethylene production, although propylene, d» compounds, fuel oil, pyrolysis
gasoline, methane, and hydrogen are also produced. The hydrogen and fuel
oil are commonly used captively; the propylene and ethylene are marketed as
products; the C^ compounds may be marketed or further processed in the
Butadiene operation; and the pyrolysis gasoline is further processed in the
BTX Production operation
The product-to-by-product ratios are dependent uoon feedstock as well
as on mode of operation. Common feedstocks for this operation include natural
gas liquids (ethane, propane, butane), refinery gases, naphtha, and gas-oil.
The heavier feedstocks (naphtha and gas-oil) and the refinery gases generally
produce more by-products.
Data for utilities for each separate process in this operation are
generally unavailable. Some data for an ethylene plant in its entirety are
available and are presented in Table 10.
Table 10. UTILITY REQUIREMENTS FOR AN ETHYLENE PLANT a'b
Fuel . 14 GJ (13.0 x 106 Btu)
Cooling Water 130 m3 (35,000 gal)
Eleqtrical Power 17 kWh
Boiler Feedwater 180 kg (400 Ib)
a Data are for high severity cracking with ethane recycle. No air-
fin cooling is assumed.
* b Per 1000 Ib ethylene. 1 Ib = 454g
Source: Chemical Engineering, ed, Sources and Production Economics of
Chemical Products, 1973-1974. 1st ed. N.Y.: McGrawHill, 1974,
Figure 5 is a flowsheet of the processing configuration presented here.
The processing sequence presented in this operation is considered to be a
typical thermal cracking process utilizing a tubular furnace. Other cracking
systems (pebble-bed heaters and fluidized-bed crackers) contribute very little
to the total ethylene production. The plant configuration presented is
characteristic of the industry. Processing sequences of specific plants may
differ somewhat due to locations, marketing factors, and feedstock avail-
abilities. The processes treated in this operation are 1) Thermal Cracking,
2) Oil Quenching, 3) Water Quenching, 4) Compression, 5) Acid Gas Removal,
6) Water Removal, 7) Demethanation, 8) C2 Separation, 9) C3 Separation,
10) C^ Separation, and 11) Heavy Fractionation.
23
-------
NATURAL OAS
L LIQUIDS
NAPHTHA AND
I GAS-OIL FROM
1 RfFINCRV
1
O
DEMETHANATfON
7
(3 Gaseous Emissions
/\ Liquid Waste
Figure 5. OLEFINS PRODUCTION PROCESSES
Solid Waste
-------
Information concerning emissions from the entire ethylene plant is also
available; whereas, waste stream information for the separate processes is
sparse. The characterization of waste streams from the entire plant is often
a useful tool in understanding the emissions problems of the industry. There-
fore, the emissions data for the entire plant are presented here. Hydrocarbon
losses from a 227 Gg/yr (500 million Ib/yr) ethylene plant have been esti-
mated based on emission factors for leaks from valves and seals and fugitive
gaseous emissions from storage vessels and liquid waste streams. Estimates
prepared using emission factors for a plant employing extensive control
measures are summarized in Table II. Fugitive emissions for such a plant
are less than one percent of throughput.
Table 11. ESTIMATED HYDROCARBON LOSSES FROM AN ETHYLENE
PLANT PRODUCING 22? Mj{500 MILLION LB)/YRa
Source
Valves
Pumps (mechanical
68g
1.5 kg
Loss Factor
(0.15 lb)/day/valve
(3.2 lb)/day/seal
Estimated
Emissions
kg/day (Ib/day)
306 675
218 480
seals)
Compressors (cen-
trifugal, me-
chanical seal)
Compressors (re-
ciprocal , packed
seal)
Cooling Water
Process Drains
and Wastewater
Separations
Slowdown
Relief Valves on
Operating
Vessels
Miscellaneous
Losses
Storage Vessels
1.5 kg
2.5 kg
(3.2 lb)/day/seal
(5.4 lb)/day/seal
29 64
0.7 kg/1000 m3 (60 lb/106gal) 195 430
68.1 kg/160 m3 (150 lb/42,000 gal) capacity 1400 3000
45 kg/160 m3 (100 lb/42,000 gal) capacity 900 2000
1.3 kg (2.9 lb)/day/valve 522 1150
4.5 kg/day/160m3(10 lb/day/42,000 gal)
capacity
90 200
1100 2400
Total
4730 10430
a These data apply to plants practicing extensive hydrocarbon control.
Source- Mencher, S.K., "Change Your Process to Alleviate Your Pollution
Problem", Petro/Chemical Engineer (21 May 1976), 21.
25
-------
Table 12 presents wastewater compositions for olefin production with
and without oil separation.
Table 12. WASTEWATER COMPOSITION FROM OLEFIN PLANTS
With Oil Separator
Alkalinity (g/m3) 1490
COD (g/m3) 500 - 1500
pH 9.8 - 10.0
Oil (g/m3)
Phenol (g/m3) 10-50
P04 (g/m3) 10
SO, (g/m3) 180
Sulfide (g/m3)
TOC (g/m3) 150 - 700
Nitrogen (g/m3) 60
Total Dissolved Solids (g/m3)
Total Solids (g/m ) 2140
Without Oil Separator
-
500 - 2000
4.0 - 8.5
10 - 300
10 - 50
-
-
0 - 1
-
-
5 - 100
-
Source: Gloyna, E. F. and D. L. Ford. "The Characteristics and Pollutional
Problems Associated with Petrochemical Wastes." Prepared for FWPCA
Contract 14-12-461, Ada, Oklahoma: Robert S. Kerr Water Research
Center, February 1970.
In addition to the data presented here, quantitative emissions data are
included in the process descriptions when available. Where quantitative data
are not readily available, a qualitative description of important waste
streams is presented.
The types of equipment encountered in this operation are indicatPrt in
Table 13 Knowledge of the industry's equipment is often useful "under-
standing the operations and the magnitude of their emissions. The equipment
recrements will vary from plant to plant, but the types of equipment ?e-
quired are basically the same. CHUlament re
26
-------
Table 13. TYPICAL EQUIPMENT REQUIREMENTS FOR A 500 Gg/YR
NAPHTHA CRACKER
Quantity
Cracking furnaces 16-18
Other furnaces 2-3
Reactors and dryers 11
Drums 105
Fractionating towers 12
Tanks 6
Pumps and motors 110
Compressors (multistage) and drivers 3
Heat exchangers 200
Miscellaneous (filters, etc.) 100
Piping 4 Gg
Source: Woodhouse, Gordon, et al. "The Economics and Technology of
Large Ethylene Projects." Chemical Engineering, 81 (June
1974), 73-85.
aContinual improvements are made in equipment design and fabrication
methods. These improvements generally result in the use of a smaller
number of larger equipment items. Generally, the number of components
is related to the age of the plant.
27
-------
OLEFINS PRODUCTION PROCESS NO. 1
Thermal Cracking
1. Function - A hydrocarbon feed stream (usually natural gas liquids,
naphtha, or gas-oil) from a refinery or natural gas processing plant is mixed
with steam and heated in a tubular furnace to form a mixed stream of gaseous
pyrolysis products. Different feedstocks are cracked in separate furnaces
when possible, so that temperatures and steam-to-hydrocarbon ratios can be
adjusted for maximum ethylene production.
The tubular furnace used in the majority of thermal cracking operations
contains both convection and radiant heating sections. The convection sec-
tion utilizes flue gas heat to preheat the feed stream while the radiant
heating section provides the remainder of the required heat energy. A common
arrangement for the radiant section of the furnace is a single row of
vertically hung tubes between two fired sidewalls. Horizontal tubes are also
common. High temperature alloys of Ni-Cr steel are often used in the radiant
section of the furnace because of the excessive temperatures.
The residence time for the gases in the furnance is very short. Older
furnances still in use have residence times of thirty (30) seconds; modern
furnance residence times may be less than a second. The shorter reaction times
favor the primary reactions of producing olefins and diolefins; whereas, longer
reaction times promote secondary reactions such as polymerization and aromatics
formation. Aromatics formation is especially avoided because the molecules
may condense to form polynuclear aromatics and dehydrogenate to form coke which
deposits in the tubes.
The pryolysis gases are quickly cooled by passing them through a transfer
line heat exchanger (usually of a fixed-tube sheet design, either vertical or
horizontal) and then through one or more quenching systems. The transfer line
heat exchanger recovers heat as high-pressure steam. If the feedstock is a
light stream such as natural gas liquids, the gases may be pumped directly to
water quenching (Process No. 3). Heavier feedstock pyrolysis products are
sent to oil quenching (Process No. 2).
2. Input Materials - Steam-to-hydrocarbon ratios are commonly adjusted for
maximum ethylene recovery. Table 14 gives these ratios for different feed-
stocks. The steam rate is set to minimize carbon formation in the tubes.
Table 14. STEAM-TO-HYDROCARBON MASS RATIOS
Feed Steam: Hydrocarbon
C2/ C3 0.2 - 0.4:1
Naphthas 0.3 - 0.6:1
Kerosenes & gas-oils 0.5 - 1.0:1
28
-------
Table 15 presents data concerning feedstock requirements and production
in an ethylene plant based on 454 Gg/yr (1 billion lb/yr) ethylene production.
Table 15. FEEDSTOCK AND PRODUCTION DATA
Product Yields
Feedstock
Feedstock Requirement
Ethane
Propane
n-Butane
Kuwait naphtha
Kuwait gas-oil
Gg/yr
568
1030
1240
1320
1570
10" lb/yr
1250
2270
2740
2900
3460
Ethylene
Gg/yr
454
454
454
454
454
10" lb/yr
1000
1000
1000
1000
1000
C3's
Gg/yr
14
160
227
178
166
10" lb/yr
31
353
499
392
365
CJs
Gg/yr
11
28
98
93
99
10" lb/yr
25
61
216
205
218
Gasoline and
Fuel Oil
Gg/yr
9
88
163
372
622
10" lb/yr
19
193
360
819
1371
3. Operating Parameters - Furnace temperatures inside the tubes depend some-
what on feedstock and are usually 800-900°C (1500 to 1600°F).
Typical residence times for modern furnaces are less than one second.
Furnace pressures are usually near atmospheric.
An ethylene plant designed by C. F. Braun & Company generates steam at
pressures up to 12 MPa (1800 psi) in the transfer line exchangers. Plants
have been designed to produce steam from 1-13 MPa (200-2,000 psi).
Table 16 indicates the heat recoveries possible in the transfer line
exchangers.
Table 16. HEAT ENERGY RECOVERED IN TRANSFER LINE HEAT EXCHANGERS
Feedstock
Ethane
Propane
Naphtha
MJ Recovered
2.2
3.5
3.6 - 4.2
Btu Recovered
2100
3300
3400 - 4000
29
-------
4. Utilities - See Page 32.
Seventy-five percent of the cost of utilities in an ethylene plant is
due to fuel consumed by the cracking furnaces.
5. Waste Streams - Combustion gases from the gas-fired furnaces may be
fairly high in N(T content because of high flame temperatures and non-
stoichiometric combustion control. NC) emissions are estimated at 54 kg (120
pounds) per hour. Most furnaces burn sulfur-free plant-produced fuel or
sweet natural gas, so that sulfur emissions are very low.
Decoking the furnaces is reported to cause intermittent hydrocarbon and
coke particulate emissions to the atmosphere. Coke burning is usually done
once a month for several hours. An average of 0.00001 kg of coke particulates
is emitted per kg of ethylene produced. Some ethylene plants report scrubbing
the decoking gases with water, creating an intermittent wastewater stream.
One plant reports a wastewater flow of 5.7 m3/min (1500 gal/min) from
this source.
In response to a questionnaire, one ethylene plant was reported to pro-
duce a solid waste stream of 2Mg (5000 lb)/yr of coke which was disposed of
in a sanitary landfill.
Emissions from steam generation operations are discussed in the Industry
Description. Combustion modifications involving control of fuel-air ratios may
be employed to reduce NO emissions from furnaces.
>\
6. EPA Source Classification Code - None exists
7. References -
(1) Baba, Theodore B. and James R. Kennedy, "Ethylene and its Coproducts:
The New Economics." Chemical Engineering (5 Jamuary 1976), 116-128.
(2) Brownstein, Arthur, M., Ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(3) Clancy, Gerald M. Radian Corporation, personal communication
(6 February 1976).
(4) Hahn, Albert V. The Petrochemical Industry, Market and Economics
N.Y.: McGraw-Hill Book Company, 1970.
(5) Kent, James A., ed. Riegel's Handbook of Industrial Chemistry
7th ed. N.Y.: Van Nostrand Reinhold Company, 1974.
(6) Pervier, J.W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958 ETA No
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and '
Chemicals, Inc., 1974.
30
-------
(7) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November
1975), 141-143.
(8) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
(9) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
(10) Woodhouse, Gordon, et al. "The Economics and Technology of Large
Ethylene Projects." Chemical Engineering, 81 (June 1974), 73-85.
(11) Zdonik, S. B., E. J. Bassler and L. P. Hallee. "How Feedstocks
Affect Ethylene." Hydrocarbon Processing, 53 (February 1974),
73-81.
(12) Zdonik, S. B., et al. Manufacturing Ehtylene. Tulsa, Oklahoma:
Petroleum Publishing Company, 1970.
31
-------
OLEFINS PRODUCTION PROCESS NO. 2
Oil Quenching
1. Function - Quenching is employed to provide the rapid cooling necessary
to retard the secondary reactions which decrease olefin yield and foul the
equipment. Quenching devices for naphtha cracking are often proprietary and
their mode of performance may be undisclosed. Pyrolysis gases from heavier
feedstocks are sometimes cooled by direct contact with quench oil. The gases
usually enter the bottom of a vertical quench tower where they are contacted
with a countercurrent flow of oil as they flow to the top of the tower. In
addition to cooling the gases the quench oil removes entrained hydrocarbon
liquids from the pyrolysis products.
The pyrolysis gases then go to a fractionator for removal of fuel oil.
The gases from the fractionator go overhead to the water quench tower, while
the bottoms are stripped of light oils which are recirculated to the quench
tower. The fuel oil is recovered as a by-product and may be used within the
plant for steam generation.
2. Input Materials - Pyrolysis gases from the transfer line heat exchangers
and quench oil form the input streams to this process.
3. Operating Parameters - For naphtha feedstocks the design outlet tempera-
ture of the oil quench tower is 360-520°C, depending on the condition of the
tubes (clean or fouled). For gas oil the outlet temperature is 500-650°C.
Mass velocities for pressures near 0.2.MPa (2 atm) in the quench tower are 50-70
kg/sec/m2. The fractionator operates at a pressure near atmospheric.
4- Utilities - See page 32 .
5. Waste Streams - Fugitive hydrocarbon emissions may occur at fittings,
valves, pumps, etc.
6. EPA Source Classification Code - None exists
7. References -
(1) Baba, Theodore B. and James R. Kennedy. Ethylene and its Co-
products: The New Economics." Chemical Engineering (5 January
(2) Clancy, Gerald M. Radian Corporation, personal communication
(6 February 1976).
(3) Mol, Alfred and Jan J. Westenbrink. "Steam Cracker Quench Coolers-
IQM'I Dfl^9n 3nd Locat1on'" Hydrocarbon Processing, 53 (February
32
-------
(4) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November
1975), 141-143.
(5) Radian Corporation. Program to Investigate Various Factors in
Refinery Siting. Final Report for Council on Environmental
Quality. Contract No. EQC 319. Radian Contract No- 100-029.
Austin, Texas: 1974.
(6) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
(7) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
33
-------
OLEFINS PRODUCTION PROCESS NO. 3
Water Quenching
1. Function - The pyrolysis gases from light hydrocarbon feedstocks are
quenched with water after the heat recovery in the transfer line heat ex-
changers. Heavy hydrocarbon feedstocks are usually cracked, oil quenched,
and then water quenched. Most operations involve a water quenching process
at some point. Water quenching cools the gases very rapidly by direct con-
tact with water in a vertical quench tower. Condensable hydrocarbons are
also removed in this step. The flow is countercurrent with the gases enter-
ing the bottom of the quench tower and cooling water entering the top. The
tower may have baffled and tray sections to provide a means of separation
of heavier components from the light gases.
The cool, washed gas goes overhead to the compressors, while the conden-
sate goes to a settling drum to effect the separation of quench water from
condensed distillate oils. The light oils are sent to further processing;
tars are taken out at the bottom for disposal; the hydrocarbon-saturated
Water is recycled to the quench tower, with the exception of a portion of
fouled condensate which is discharged. In many ethylene plants this fouled
condensate is stripped to provide a source of water for the dilution steam
required in the furnace. This operation reduces the volume of oily water
which must go to disposal, but not the total amount of hydrocarbons in the
waste stream.
2. Input Materials - Light hydrocarbon feedstock pyrolysis gases from the
tubular furnace or heavier hydrocarbon feedstock pyrolysis gases from the
fractionation column in the oil quenching process, and cooling water are in-
put materials to this process.
3. Operating Parameters - The following data are for an ethylene plant
cracking a C2/C3 feedstock to produce 200 Gg/yr (500 x 106 Ib/yr) with a
direct water quench.
Temperature - Inlet gases from the heat exchanger are about 300°C. The baf-
fled section of the vertical tower cools the gases to about 90°C; the gas
temperature in the tray section is about 40°C. Variability in water supply
will affect temperatures in the quench tower. The settling drum temperature
is about 80°C.
Pressure - The pressure at the bottom of the tower is about 159 kPa (8 psig)
The settling drum pressure is atmospheric.
Flow rates - The effluent from the heat exchangers enters the quench tower
at a rate of 85 Mg/hr (187,000 Ib/hr). The cooled gas leaves the tower at
a rate of 70 Mg/hr (153,500 Ib/hr). Cooling water enters the tower at a
rate of 730 Mg/hr (1,600,000 Ib/hr). The flow of condensate and water to
the settling drum is 750 Mg/hr (1,650,000 Ib/hr).
34
-------
4. Utilities - Make up water for the plant described above is required at
the rate of 5.61 Mg/hr (12,350 Ib/hr). See page 32.,
5- Waste Streams - For the plant described above, 19 Mg/hr (43,000 Ib/hr)
of fouled condensate is generated. If a stripping operation is included,
the resulting waste is 3 Mg (6000 lb)/hr as blowdown. One source reports
that the flow rate for untreated fouled condensate may be as high as several
thousand liters per minute (hundreds of gallons per minute). Most ethylene
plants degas the quenching wastewater stream. The recovered gases are re-
cycled, vented, or flared. When degassing is practiced, continuous atmospheric
emissions may result. The amount of tar produced in an ehtylene plant is
dependent on the feedstock in use. A naphtha cracking operation reports 0.5
Gg tar produced/Gg of ethylene produced. A non-naphtha cracker reports
0.001 Gg/Gg of ethylene. Some ethylene plants dispose of the tars by land-
filling.
6. EPA Source Classification Code - None exists
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No.
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
(3) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974-
(4) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publsihers,
1965.
35
-------
OLEFINS PRODUCTION PROCESS NO. 4
Compression
1. Function - The cooled, washed pyrolysis gases are compressed in sev-
eral stages using single-train certrifugal compressors. It is in this
section that refinery gases enter the plant, usually after the first stage
of compression. Refinery gas, composed of light ends from crude refining,
may contain significant amounts of ethane, ethylene, propane, propylene, and
four carbon compounds. The olefins can be recovered and the paraffins can
be recycled to the furnaces. This source of olefins is economically com-
petitive with cracking feedstocks if the refinery is located very near the
olefins plant.
A common arrangement for the compression train is five stages of com-
pression with an acid gas removal step between the third and fourth stages.
After the fifth stage, the gases are desiccated. Condensate from the com-
pression steps is sent to further processing in the fractionation train.
Polymer formation and fouling may occur, especially in the first two stages.
Some ethylene plants find it necessary to remove acetylenic compounds be-
tween the second and third stages. It may be necessary to flush the com-
pressors with a gas-oil to dissolve the polymeric materials formed. The
frequency of intermittent compressor cleaning varies with the feedstock.
In one plant processing a light hydrocarbon,compressor cleaning is done
at 12 to 18 month intervals.
2. Input Materials - Cooled, washed gases from the water quenching process
in th¥ ethylene plant are fed to this process. Refinery gas also enters the
plant here. The composition of refinery gas varies significantly with re-
finery feedstocks and operation. A refinery gas composition which would be
useful for a feedstock to the ethylene plant is shown in Table 17.
Table 17. COMPOSITION OF A REFINERY GASa
Component Mole
H2
N2
CO
C02
H2S
CH,,
C2H^
C2H6
C3H6
C3He
12.80
8.00
2.30
2.20
1.20
33.60
16.11
20.20
2.94
0.65
This refinery gas has had C3 and heavier compounds
removed.
36
-------
3. Operating Parameters - Two processes cited in the literature (USC and
Lummus) compress the gases to about 3.5-3.9 MPa (500-550 psig).
Compression requirements are approximately 800 W/kg (0.5 brake horse-
power/1 b) ethylene produced.
4. Utilities - See Page 32
5. Haste Streams - Fugitive emissions may result from compression especially
at the compressor seals. One source reports for a plant cracking gas oil and
producing 179 Gg/yr (395 x 106 Ib/yr) of ethylene, an estimated loss of 47
Mg/yr (103,500 Ib/yr) or 0.000262 kg emitted per kg of ethylene produced.
A water condensate stream from compressor intercoolers may be produced. This
aqueous stream contains dissolved hydrocarbons.
6. EPA Source Classification Code - None exists.
7. References -
j
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(3) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No.
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
(4) "Petrochemical Handbook." Hydrocarbon Processing, 50 (November
1971), 152-154.
(5) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November
1975), 141-143.
(6) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
(7) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
(8) Zondik, S. B., E. J. Bassler and L. P. Hallee. "How Feedstocks
Affect Ethylene." Hydrocarbon Processing, 53 (February 1974),
73-81.
37
-------
OLEFINS PRODUCTION PROCESS NO. 5
Acid Gas Removal
1. Function - Acid gas removal is employed in plants which process sulfur
containing feedstocks. Acid gases are removed from the gas stream to a con-
centration of less than 10 ppm by a combination of amine absorption and caus-
tic scrubbing. The regenerative ethanolamine sorbents have a temperature
dependent affinity for hydrogen sulfide. The hydrogen sulfude gas is absorbed
and is then released from the sorbent by increasing the temperature.
The compressed gases pass through an absorber tower and are contacted
countercurrently with the amine solution. Packed or tray towers are employed.
The washed gases go overhead to the caustic scrubber, while the amine solu-
tion is pumped to a stripper where the H2S is removed by heating the rich
solution. The amine is preheated by heat exchange with regenerated amine sor-
bent and is then processed in the stripper column provided with a steam re-
boiler. The acid gases removed may be flared or vented; very few ethylene
plants recover sulfur from the acid gas stream.
The amine-washed pyrolysis gases are scrubbed with a caustic solution by
direct countercurrent contact to remove acid gases not absorbed by the amine
treatment. This operation may be followed with a water washing step. The
scrubbing solution is usually neutralized before it is disposed of; the
caustic-washed gases are sent through another compression stage before they
are desiccated.
2. Input Materials - Compressed pyrolysis gases, steam, caustic solution and
amine sorbent are input materials to this process. Makeup rates for the amine
are very low, as it is regenerable.
3. Operating Parameters - The absorber temperature is about 70 to 80°C
(160°F to 180°F).The stripper is operated at temperatures about 90°C (200°F).
*• Utilities - See page 32.
5. Waste Streams - The hydrogen sulfide gas from the regenerated amine solu-
tion and from the neutralized caustic solution represents one of the biggest
pollution potentials for ethylene plants. Unless the plant is associated with
a refinery, the gases are usually flared; very few independent operations send
them to a sulfur recovery plant. Emissions of sulfur compounds have been repor-
ted as high as 0.0012 Mg S02/Mg of ethylene produced.
Liquid waste streams result from the caustic scrubbing and water washing
operations. The alkaline stream is usually neutralized and ponded Flow
rates of 0.060-0.075 m3/min (16-20 gal/min) have been reported for caustic
streams from ethylene plants. The waste caustic stream production rate has
also been reported as 0.063 m3/Mg (15 gal/ton) of ethylene produced A
typical composition is presented in Table 18.
38
-------
Table 18. WASTE CAUSTIC STREAM COMPOSITION
NaOH 2.5%
Na2S 1.0%
Phenols 6.6 ppm
COD 1000 - 2000 g/m3
Most ethylene plants degas waste caustic and water from the scrubber.
This gas may be recycled, vented, or flared and may become a continuous
atmospheric emission. Hydrocarbon emissions from the acid gas removal
process have been reported as 0.00001 kg/kg ethylene produced.
6. EPA Source Classification Code - None exists .
7. References -
(1) Bland, William F. and Robert L. Davidson, eds. Petroleum
Processing Handbook. N.Y.: McGraw-Hill Book Company, 1967.
(2) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No.
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
(3) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November
1975), 141-143.
(4) Radian Corporation. Program to Investigate Various Factors in
Refinery Siting. Final Report for Council on Environmental
Quality. Contract No- EQC 319. Radian Contract No. 100-029.
Austin, Texas: 1974.
(5) Standom, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
39
-------
OLEFINS PRODUCTION PROCESS NO. 6
Water Removal
1. Function - The gas from the acid gas removal section of the plant is
compressed in the final stage and is then sent to the driers. Dehydration
is accomplished by adsorption on alumina or molecular sieves. Typically,
two drying towers are onstream in series while a third is being regenerated
by heating. Gases (frequently off-qas from the demethanizer or other process
gases) are heated and passed through the regenerating bed. The regenerating
gases may be directly used as plant fuel. The gases may be cooled to con-
dense the water which becomes a liquid waste stream.
2. Input Materials - Treated pyrolysis gases from the acid gas removal
process and a source of regenerating gas are required for this process.
3. Operating Parameters - Not given in information available for this study.
4. Utilities - See page 32.
5. Waste Streams - The water from the driers forms a liquid waste stream
which is smaller in volume than that from the inter-stage cooling in the com-
pression process. No information was available concerning treatment or dis-
posal of this wastewater. Spent desiccant forms a solid waste stream which
is reported by one plant ot be landfilled at the rate of 30 Mg/yr (66,000
lb/yr).
6. EPA Source Classification Code - None exists.
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No.
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
(3) Processes Research, Inc. Screening Report, Crude Oil and Natural
Gas Production Processes. EPA-R2-73-285, PB-222 718, Contract No.
68-02-0242. Cincinnati, Ohio: 1972.
(4) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
40
-------
OLEFINS PRODUCTION PROCESS NO. 7
Demethanati'on
1. Function - In this process the dried gases are refrigerated, compressed
and heated in the first of a series of fractionation towers. There are many
possible configurations of the tower/refrigeration system. The demethanation
step is a determining factor in process efficiency due to ethyTene losses in
the tower overhead. This step also affects product purity due to the methane
content of the tower bottoms.
The chilling train is composed of several refrigeration stages. Refrigera-
tion is usually provided by a propylene-ethylene cascade system. The noncon-
densables form a hydrogen-rich off-gas which may be used for processing. Alter-
natively, the entire feed from the water removal process may enter the demetha-
nizer without separation of condensible liquids.
The condensed liquids or gas feed stream are pressured to the first
fractionation tower, the demethanizer. This process separates the C2 and
heavier molecules from a methane-rich overhead stream which may be used as
fuel after the refrigeration has been recovered by heat exchange or expansion.
The demethanizer tower is equipped with a condensing propylene reboiler, and
reflux is condensed with ethylene refrigeration. The bottom stream from this
tower is fractionated further in the deethanizer.
2. Input ^aterials - Dehydrated pyrolysis and refinery gases from the driers
are input streams to the demethanizer unit. Table 19 presents compositions
of typical demethanizer feeds.
Table 19. TYPICAL DEMETHANIZER FEEDS
Mole Percent
Component Feed 1 Feed 2
H2
N2, CO
CH4
CzH*
C2H6
C3H6
C3H8
-------
3. Operating Parameters - Information found in the literature indicates
that demetham'zer columns of 20-30 plates may be operated at pressures of
3.0-3.5 MPa (425-500 psig) at a temperature of -70 to -100°C (-100 to -150°F)
with a reboiler temperature of 2 to 18°C (35-65°F). Other sources of infor-
mation indicate a trend toward lower pressures of 280-340 kPa (25 to 35 psig)
and temperatures as low as -130°C (-205°).
4- Utilities - See page 32.
The refrigeration system for a naphtha cracker producing 450,000 Mg/yr
or ethylene requires 48 MW (65000 brake horsepower).
5. Waste Streams - Fugitive emissions of hydrocarbons may result from
seals, valves, and leaks. Intermittent emissions result from relief vents
on fractionation towers. The entire fractionation train emits an estimated
0.00050 kg of hydrocarbons per kg of ethylene produced (Processes 7-11).
Refrigeration system waste streams are discussed in the Industry
Description.
6. EPA Source Classification Code - None exists .
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(3) Nelson, W. L. Petroleum Refinery Engineering. 4th ed. N.Y.:
McGraw-Hill, 1958.
(4) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No.
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
(5) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers, 1965.
(6) Woodhouse, Gordon, et al. "The Economics and Technology of Large
Ethylene Projects." Chemical Engineering, 81 (June 1974), 73-85.
(7) Zdonik, S. B., et al. Manufacturing Ethylene. Tulsa, Oklahoma:
Petroleum Publishing Company, 1970.
42
-------
OLEFINS PRODUCTION PROCESS NO. 8
C2 Separation
1. Function - This process separates ethane and ethylene from the de-
methanizer bottoms in three processing steps: deethanizing, acetylene
conversion, and C2 splitting.
The deethanizer produces C2 compounds as an overhead stream and C3 and
heavier compounds as a bottom stream which is sent to the depropanizer for
C3 separation. This specific fractionation tower is usually equipped with a
low-pressure steam reboiler and a refrigerated propylene condenser.
The C2 fraction taken overhead is treated by selective catalytic hydro-
genation in a packed-bed reactor for conversion of acetylene to ethylene.
The acetylene concentration must be reduced to a maximum of 10 ppm. The
hydrogen necessary for the conversion is often obtained from the demethanizer
off-gases. A typical arrangement is two catalytic reactors in parallel, so
that one is onstream while the other is being regenerated by heating. Re-
generation is an intermittent operation. An alternate arrangement for acetylene
removal involves a single bed of a long-life catalyst which does not require
regeneration.
The effluent gases from the acetylene converter flow to another fraction-
ation tower in which ethane and ethylene are separated. The C2 splitter is
equipped with a propylene reboiler and a propylene condenser to effect this
separation. High purity ethylene (99.9+%) is taken overhead as a product,
while ethane is recycled to the cracking furnace. Typical ethylene product
specifications are listed in Table 20.
Table 20. TYPICAL ETHYLENE PRODUCT SPECIFICATIONS
Component Concentration
Ethylene 99.90 - 99.95 mo IX
Methane 0.01 - 0.1 mol%
Ethane 0.05 - 0.01 mo1%
C3 and heavier compounds less than 10 ppm by weight
Acetylene 5-10 ppm by weight
Total sulfur 1-10 ppm by weight
H2S 1 ppm by weight
H2 1 ppm by weight
CO 1-5 ppm by weight
C02 5-10 ppm by weight
Oa 2-5 ppm by weight
HzO 5-10 ppm by weight
43
-------
2. Input Materials - Demethanizer bottoms and hydrogen are input streams
to this process.
3. Operating Parameters - Operating conditions will vary from plant to
plant. The following data from the open literature are representative.
The deethanizer tower, characterized as a 30- to 40-tray tower by one
source and a 100-tray tower by another, operates at -12 to -1.1°C (10-30°F)
and 2.2-3.1 MPa (325-450 psia). The reboiler temperature is 68-88°C (155-I90°F)
Selective catalytic dehydrogenation is commonly accomplished at 0.5 to 2.5
MPa (50-350 psig) using a noble metal catalyst.
Representative conditions for the C2 splitter containing 50-65 trays are
1.9-2.4 MPa (275-350 psia), -18 to -29°C (0 to -20°F) tower temperature, and
-10 to 4°C (10-40°F) reboiler temperature.
4- Utilities - See page 32.
5- Waste Streams - Fugitive atmospheric emissions of hydrocarbons may
occur at seals, valves, vents, and leaks in equipment. Intermittent
hydrocarbon emissions are reported at relief vents on fractionation towers.
The entire fractionation train (Processes 7-11) emits an estimated 0.00050 kg
of hydrocarbons per kg of ethylene produced.
Acetylene converter regeneration has also been reported as a source of
intermittent atmospheric emissions containing C02 and coke fines.
The regeneration waste gases are sometimes scrubbed with water. The flow
rate may be as high as 5.7 nr/min (1500 gal/min). The operation frequency is
about twice yearly for a few days duration. This scrubbing water forms an
intermittent liquid waste stream.
Waste streams from refrigeration systems are discussed in the Industry
Description.
6. EPA Source Classification - None exists
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Nelson, W. L. Petroleum Refinery Engineering. 4th ed. NY-
McGraw-Hill, 1958.
(3) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
44
-------
(4) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
45
-------
OLEFINS PRODUCTION PROCESS NO. 9
C3 Separation
1. Function - This process isolates propane and propylene from the de-
ethanizer bottoms stream. There are three processing steps involved in
effecting this separation: depropanizing, catalytic hydrogenation, and
C3 splitting.
The fractional on tower (called the depropanizer) equipped with a steam
reboiler and a water condenser, separates C3 components from U and heavier
fractions which are taken as feed to the U separation process.
The overhead C3 compounds are passed through a selective hydrogenation
step in a packed-bed reactor similar to the acetylene converter in the C2
separation process. This catalytic reactor converts propadiene and methyl
acetylene to propylene. As in the case of the acetylene converter, there are
usually two reactors in parallel, so that one may be onstream while one is
being regnerated by heating. Alternatively, propadiene and methyl acetylene,
which have some commercial value, may be removed as an intermediate side-
stream in a fractionator. At this point the propylene content of the gas
may be 93%, depending upon the plant operation. A propylene gas of this purity
is suitable for chemical grade product and may be marketed. If polymer grade
is required, the gases are further processed.
After the alkynes have been removed, the C3 gases flow to the C3 splitter
equipped with a steam reboiler and a water condenser for separation of propane
and propylene. This separation is the most difficult one in the fractionation
train; the C3 splitter may require as many as 200 trays. Polymer grade (99+%)
propylene is taken overhead as product, and propane forms the bottoms stream
which is recycled to the cracking furnace.
2. Input Materials - Deethanizer bottoms and hydrogen are input streams to
this process.
3. Operating Parameters - Representative process conditions for the de-
propanizer were presented in the literature as 1.0-1.5 MPa (150-225 psia) and
24-43°C (75-110°F) with a reboiler temperature of 107-135°C (225-275°F).
The catalytic converter utilizes a noble metal catalyst to perform the
required hydrogenation.
The C3 splitter may contain up to 200 trays and is operated at 1.9 MPa
(260 psig).
i -?
4. Utilities - See page 32-
5. Waste Streams - Fugitive atmospheric emissions of hydrocarbon gases may
result at valves, seals, and vents. The entire distillation train emits an
estimated 0.00050 kg of hydrocarbons per kg of ethylene produced. Inter-
mittent emissions may occur at the relief vents on the fractionation towers.
Catalyst regeneration is reported to cause intermittent atmospheric emissions
of C02 and coke fines. If these gases are scrubbed with water a liquid waste
stream results.
46
-------
Emissions from cooling towers and steam generation boilers are discussed
in the Industry Description.
6. EPA Source Classification Code - None exists.
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Considine, Douglas M., ed. Chemical and Process Technology
Encyclopedia. N.Y.: McGraw-Hill Book Company, 1974-
(3) Nelson, W. L. Petroleum Refinery Engineering. 4th ed. N.Y.:
McGraw-Hill, 1958.
(4) Pervier, J. W., et al. Survey Reports on Atmospheric Emissions
from the Petrochemical Industry, Vol. II. PB-244 958. EPA No.
450/3-37/005-b. Marcus Hook, Pennsylvania: Air Products and
Chemicals, Inc., 1974.
(5) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
47
-------
OLEFINS PRODUCTION PROCESS NO. 10
Ci» Separation
1- Function - In this process a mixed Ci» stream is isolated from the de-
propanizer bottoms in a fractionation tower equipped with a steam reboiler
and a water condenser. The tower bottoms are pumped to heavy fractionation,
while the overhead C., stream may be sold to a chemical company or is processed
further in the butadiene segment.
2. Input Materials - Depropanizer bottoms form the input to this process.
3. Operating Parameters - Not given in information consulted for this study.
4. Utilities - See Page 32
5, Waste Streams - Fugitive emissions may occur at seals, valves, and vents.
The entire fractionation chain emits an estimated 0.00050 kg of hydrocarbons
per kg of ethylene produced.
Emissions from cooling towers and from steam generation boilers are
discussed in the Industry Description.
6. EPA Source Classification Code - None exists
7. References -
(1) Chemical Technology: An Encyclopedic Treatment, Vol. 4. N.Y.:
B&N Import Division, Harper and Row Publishers, Inc., 1972.
(2) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 3. 2nd ed. N.Y.: Interscience Publishers,
1965.
(3) Van Winkle, Matthew. Distillation. U.S.A.: McGraw-Hill Book
Co., 1967.
48
-------
OLEFINS PRODUCTION PROCESS NO. 11
Heavy Fractional on
1. Function - The last process in the fractionation chain is the heavy
fractionation. Equipped with a steam reboiler and a water condenser, this
tower effects the separation of pyrolysis gasoline from pjrolysis fuel-oil.
The Ryroljpls Msoline, taken overhead, is sent to the BTX Production
operation of the Petrochemical Industry for further processing. The bottoms
contain pyrolysis fuel oil which is recovered and used as fuel.
2. Input Materials - The bottoms stream from the debutanizer forms the
input to this process.
3. Operating Parameters - Not given in information consulted for this
study.
4. Utilities - See page 32
5. Waste Streams - Spills and leaks at vents, valves, and seals in equipment
are potential sources of emissions in this process. The fractionation train
is responsible for an estimated 0.00050 kg of hydrocarbon emissions per kg
of ethylene produced.
Waste streams from cooling towers and from steam generation processes
are discussed in the Industry Description.
6- EPA Source Classification Code - None exists .
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Considine, Douglas M., ed. Chemical and Process Technology
Encyclopedia. N.Y.: McGraw-Hill Book Company, 1974.
(3) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers,
1965.
49
-------
BUTADIENE PRODUCTION PROCESSES
Although butadiene is produced in the industrial organic chemical industry,
the importance of production in the petrochemical plant is indicated by the
amount of the total production that is recovered from thermal cracking in ethy-
lene plants. Capacities for coproduct recovery in 1976 are 40% of the total
capacity for butadiene and are expected to reach 60% by 1980 as more and more
cracking of heavier feedstocks is practiced. Producers of butadiene include
petrochemical companies as well as chemical and rubber companies. With
these facts in mind the decision was made to include an operation for butadiene
production in this industry.
Some of the process descriptions were written in a very general manner
in an attempt to describe a large number of possible variations in processing
methods. This is particularly true in the separation and purification process,
which is often more variable than consistent from plant to plant.
Much of the information in the open literature describes post-World War II
technology, some of which is considered archaic and is not widely used.
The differences in that technology and today's technology lie mainly in the
solvent systems and in improved catalysts. These considerations eliminated
the discussion of acetonitrile and cuprous ammonium acetate extractive
distillation and selective absorption from this treatment, as they are
outdated.
This operation, then, is the treatment of a unit called a butadiene
plant within a petrochemical complex which produces butadiene by recovery
from ethylene plant Ci/s and by dehydrogenation of butenes and n-butanes.
By-products from the processing include fuel gas, butenes, and isobutylene.
The processes necessary for isolating and producing these products are
1) Separation and Purification, 2) Butane Dehydrogenation, and 3) Butenes
Dehydrogenation. Figure 6 is a flowsheet of this segment which is included
as an aid in understanding the sequence of processes involved.
Quantitative data were not always readily available for operating para-
meters, utilities, and waste streams. An attempt was made to give a qualita-
tive description of emissions, even though quantifying information was not
always found.
One source of information presented the liquid waste composition from one
butadiene plant of undesignated processing type in Table 21. Because this
table is assumed to include waste streams from the entire plant, it is in-
cluded here.
50
-------
TO SALES
C4 CUT FROM
ETHYLENE PLANT
BUTADIENE
PRODUCT
en
J Q
TO SALES
O Gaseous Emissions
Q Solid Waste
Liquid Waste
SOLVENT
ACID
SEPARATION
AND
PURIFICATION
BUTENES
FROM
REFINERY
BUTANE FROM
NATURAL GAS
PLANT
REGENERATION
GASES-
BUTANE
DEHYDROGENATION
13
BUTENES
DEHYDROGENATION
14
DILUTION STEAM
AND AIR
CATALYST
REGENERATION
GASES
Figure 6. BUTADIENE PRODUCTION PROCESSES
-------
Table 21. COMPOSITION OF WASTE FROM A BUTADIENE PLANT3
pH 8-9
TOC 100 - 200 g/m3
filtered COD 200 - 375 g/m3
suspended solids 200 - 500 g/m3
total solidsb 3000 - 4000 g/m3
Flow rate 0.417 m3/Mg (100 gals/ton of product)
Mostly sulfates and chlorides
Source: Gloyna, E. F. and D. L. Ford. "The Characteristics
and Pollutional Problems Associated with Petro-
chemical Wastes." Prepared for FWPCA Contract 14-
12-461, Ada, Oklahoma: Robert S. Kerr Water Research
Center, February 1970.
52
-------
BUTADIENE PRODUCTION PROCESS NO. 12
Separation and Purification
1. Function - A mixed d, stream is transferred from the olefins plant to
be separated into products for further processing in the butadiene plant.
Reaction products from the dehydrogenation reactors are also fractionated
and purified in this process. There are three main processing steps in-
volved: 1) separation of butane, butenes, and butadiene, 2) isobutylene
removal, and 3) acetylenics removal. The butane and butenes produced in
this process are sent to dehydrogenation (Processes 13 and 14) and butadiene
and isobutylene are recovered for sales.
The boiling point temperatures of four carbon compounds are too close
together to allow separation by regular fractional distillation. A series
of extractive distillations and selective absorptions is required. A num-
ber of solvents have been used to aid fractionation by modifying the
volatilities of the Ci» compounds. There are many possible variations in
separation processing sequences depending ort the solvent selected and the
composition of the input streams. The inherent complexity and possible
variability is indicated by describing the separation process using fur-
fural as the solvent.
A distillation tower splits the feed into butadiene and 1-butene
overhead and n-butane-butenes mixture as bottoms. The overhead streams
are sent to an extractive distillation column in which a butadiene solvent
mixture forms the tower bottoms. The solvent is stripped, and another
distillation column removes the final traces of solvent from the butadiene
product. The n-butane-butenes bottoms stream from the feed splitter is
fed to another series of extractive and conventional distillation columns.
Some solvent systems require a water washing step to free the stream from
solvent. The absorbers and strippers which accompany the distillation
columns allow solvent recovery and recycle. Recovered butadiene may be
further purified in a molecular sieve bed. The isolated butenes may be
sold as a chemical product, but most of the butenes and the butane are
consumed in butadiene manufacture.
The removal of isobutylenes is necessary as they will not dehydrogenate
in the reactors and the concentration will continually build in the plant
stream. Separation is accomplished by extraction with 60-65% cold sulfuric
acid. The acid is regenerated either by stripping the isobutylenes, which
may be sold as a chemical product, or by oligomerization of the hydrocarbon
to an acid-insoluble product useful for gasoline blending.
The tendency of acetylenics to coke and form deposits in the catalyst
beds makes their removal necessary. The extraction distillation system
employing dimethylformamide eliminates the need for this operation, but
other solvent systems require selective catalytic hydrogenation to convert
the acetylenics to olefins. A vapor-phase process is generally used.
53
-------
2- Input Materials - The C,, stream from ethylene plants and the recycle
dehydrogenation products are feed streams to this process. Yields of
butadiene from thermal cracking vary with the feedstock in use as shown in
Table 22. Hydrogen is required as a feed stream to the catalytic hydro-
genation of the acetylenic compounds. The content of acetylenic molecules
of various streams is illustrated in Table 23. Makeup requirements for
acid and extractive solvents are probably low, since recycle methods are
practiced. Some of the common solvents in current use are dimethylacetamide,
dimethylformamide, acetonitrile, N-methylpyrrolidone, and furfural.
Table 22. BUTADIENE YIELDS FROM THERMAL CRACKING3
kg Butadiene per 100 kg
Feedstock of Ethylene Produced
Ethane 2.5
Propane 7.1
n-Butane 8.7
Medium range naphtha 13.6
Reformer raffinate (Ce-Ce) 16.8
Atmospheric gas-oil 17.6
Light vacuum gas-oil 24.7
a Data are based on production of 454 Gg/yr (1 x 109 Ib/yr) of
ethylene with high severity cracking and ethane recycle.
Table 23. ACETYLENICS CONTENT OF VARIOUS C* STREAMS
Acetylenics Concentration
Source in ppm by Weight
Thermal cracking 2500 - 5000
Dow B Butene dehydrogenation 1000 - 3000
Shell 205 Butene dehydrogenation 500 - 750
Houdry n-Butane dehydrogenation 200 - 500
54
-------
3. Operating Parameters - The important operating parameters are temperature,
pressure, and solvent system. Different combinations of these parameters
effect different separations. Specific data concerning operating parameters
were not available in the references consulted for this study. A wide range
of conditions is expected.
4. Utilities - Quantitative utility requirements are unavailable in the
sources consulted for this study. Steam is required for reboilers and strip-
pers; energy is required for pumping various plant streams; and cooling water
is required for condensers.
5. Waste Streams - Wastewater is generated in some plants in the solvent
recovery operation, notably in furfural solvent systems. Wastewater
characteristics of several different butadiene plants are presented in
Table 24. The wastewater characteristics from dehydrogenation and from re-
covery of butadiene from ethylene by-products are essentially the same. The
variation in total wastewater flows is due to the use of steam ejectors with
barometric condensers to produce reactor vacuum. Plants 1 and 2 use processes
which operate at low pressures (see Process 13, Houdry Process).
Table 24. WASTEWATER FROM BUTADIENE PLANTS
Process
Plant 1
mVMg
9.67
Flow
(gal/1000 Ib)
(1160)
COD(g/m3) BOD5(g/m3)
334 306
TOC(g/m3)
—
Dehydrogenation,
extractive
distillation
Plant 2
dehydrogenation,
extractive
distillation
Plant 3
Coproduct of
ethylene, ex-
tractive
Plant 4
Coproduct of
ethylene, ex-
tractive
distillation
12.1
(1451)
20,200
5,960
0.734
1.53
(88)
(183)
1,525
683
745
102
755
205
55
-------
Fugitive and intermittent hydrocarbon emissions in gaseous and liquid
form may occur in absorbers, fractionaters, and strippers at valves, vents,
pump seals, compressor seals, and leaks in the equipment. Hydrocarbons may
be composed of feed or product stream components as well as solvent degrada-
tion products.
Emissions from cooling towers and from steam boilers are discussed in
the Industry Description.
6. EPA Source Classification Code - None exists.
7. References -
(1) "Butadiene," 620.5022 A. Chemical Economics Handbook. Menlo Park,
California: Stanford Research Institute, 1974.
(2) Environmental Protection Agency (Office of Water and Hazardous
Materials, Effluent Guidelines Div.). Development Document for
Effluent Limitations Guidelines and New Source Performance
Standards for the Major Organic Products Segment of the Organic
Chemicals Manufacturing Point Source Category. EPA 440/1-74-009-a.
Washington, D.C.: 1974.
(3) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(4) Hedley, W. H., et al. Potential Pollutants from Petrochemical
Processes. MRC-DA-406. Dayton, Ohio: Monsanto Research Corp.,
December 1973.
(5) Kent, James A., ed. Riegel's Handbook of Industrial Chemistry.
7th ed. N.Y.: Van Nostrand Reinhold Company, 1974.
(6) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
(7) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 3. 2nd ed. N.Y.: Interscience Publishers,
1965.
56
-------
BUTADIENE PRODUCTION PROCESS NO. 13
Butane Dehydrogenatlon
1. Function - Butane feed separated from the mixed ethylene plant C* stream
is supplemented with butane from a natural gas plant to be catalytically de-
hydrogenated in a one- or two-step process.
The Houdry Catadiene process is a one-step dehydrogenation process pro-
ducing a mixture of butadiene and butenes whose composition can be varied
by varying the operating conditions. This type of processing sequence re-
quires banks of three to eight brick-lined reactors filled with a catalyst of
aluminum oxide carrying chromium oxide mixed with alumina particles acting
as heat carriers. The reactors operate on cycles of reaction, regeneration,
and purge. Regeneration is accomplished with steam and heated air, while the
purging cycle utilizes fuel gas to treat the catalyst under reducing conditions,
The resulting gases contain unreacted butane, butenes, butadiene, and by-
product gases.
The Phillips two-stage process dehydrogenates butane to butenes in one
stage, utilizing a second stage (Process No. 14) to convert the butenes to
butadiene. After thorough drying of the input stream, the isothermal de-
hydrogenation of butane is accomplished in tubular reactors filled with
alumina-chromia catalyst. As in the Houdry process, the operation is cyclic,
so that a parallel arrangement is advantageous with one reactor onstream
while another is being regenerated with a mixture of air and flue gas. The
product gases from the reactor contain butenes and unreacted n-butane along
with some by-product gases.
The gases from the reactor are quenched with oil (See Process No. 2) and
compressed. The (\ compounds are separated from light gases (H2, CO, C02,
CH,,, C2's, and C3's) by fractional distillation using one or more towers.
The off-gases are generally used for fuel, as they amount to about 20% of
the reactor gases. Another possibility is that hydrogen may be recovered for
use in hydrogenating acetylenics before the gas is used as fuel. Propylene
is recovered from this stream in at least one installation. The ultimate
usage of the gas must be dictated by local operations and economics. The
mixed Ci, stream is returned to the separation and purification process
(Process No. 12) for isolation of the U products.
2. Input Materials - The Houdry process requires 1.7 to 1.9 kg of 95+%
butane feed per kg of butadiene produced. The yield is 57-63%. Steam, hot
air, and fuel gas are required for regeneration of the catalyst beds.
The Phillips process requires a desiccant, often bauxite. The preferred
feed material is 98% n-butane which is 30% converted with 80% selectivity
toward butene and butadiene.
3. Operating Parameters - The Houdry dehydrogenation process requires a
temperature of 600°C (1100°F), a pressure of 10-20 kPa (2-3 psia) with a
space velocity of 2 (liquid volume/hr/volume of catalyst). Onstream time is
4-10 minutes; the total reaction and regeneration cycle requires about 15
minutes.
57
-------
Operating conditions for the Phillips process are 560-590°C (1050-
noO°F) and 100-200 kPa (1-20 psig) with a space velocity of 700 liquid
volume/hr/volume of catalyst. The onstream time is approximately one hour
with a one-hour regeneration cycle. Regeneration takes place at 800 kPa
(100 psig) with an air-flue gas mixture containing 2-3% oxygen.
Both processes use chromium oxide/aluminum oxide catalysts.
4. Utilities - Utility requirements for a Houdry Catadiene process treating
normal butane or isobutane to produce 993 m3/stream day (6250 bbl/stream day)
of 55% butylenes are summarized as follows:
Electricity: 150 kWh/m3 product (24 kWh/bbl product)
Steam: 340 kg/m3 (120 Ib/bbl)
Fuel: 730 MJ/m3 (110 x 103 Btu/bbl)
Cooling water: 52.2 m3/m3 (2190 gal/bbl)
5. Waste Streams - Catalyst regeneration causes intermittent emissions of
C02 and coke and catalyst fines. It is assumed that spent catalyst is land-
filled. When regeneration gases are scrubbed with water, an intermittent
wastewater stream results.
Steam ejectors with barometric condensers may be used to produce a
vacuum in the reactor. These systems generate a huge wastewater stream
which may be eliminated by the use of vacuum pumps.
Fugitive hydrocarbon emissions may result at vents, valves, seals, and
leaks in equipment. Intermittent hydrocarbon emissions may occur at emergency
relief vents on fractionation towers.
Waste streams from steam generation are discussed in the Industry
Description.
6. EPS Source Classification Code - None exists.
7. References
(1) Bland, William F. and Robert L. Davidson, eds. Petroleum
Processing Handbook. N.Y.: McGraw-Hill Book Company, 1967.
(2) "Catadiene." Hydrocarbon Processing, 49 (September 1970),
265.
(3) Environmental Protection Agency (Office of Water and Hazardous
Materials, Effluent Guidelines Div.). Development Document for
Effluent Limitations Guidelines and New Source Performance
Standards for the Major Organic Products Segment of the Organic
Chemicals Manufacturing Point Source Category. EPA 440/1-74-009-a
Washington, D.C.L 1974.
(4) "Petrochemical .Handbook." Hydrocarbon Processing, 50 (November
1971), 136-137.
58
-------
(5) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
(6) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 3. 2nd ed. N.Y.: Interscience Publishers,
1965.
59
-------
BUTADIENE PRODUCTION PROCESS NO. 14
Butenes Dehydrogenation
1. Function - Butenes may be catalytically dehydrogenated to butadiene in
fixed-bed reactors. In plants installed prior to 1970 catalytic dehydro-
genation of n-butenes is accomplished via endothermic processes. The puri-
fied butene feed is mixed with steam to achieve the high temperature required
and to minimize coke formation. Two commonly used catalysts are Shell 205
and Dow B. Regeneration of the Shell 205 catalyst is with superheated steam;
regeneration of Dow B is accomplished with a mixture of steam and air. If
a Dow B catalyst is used, special purification equipment may be required
to remove acetylenics and carbonyl by-products which are toxic and may re-
quire special treatment before disposal. Recoverable quantities of acetone
and methylethyl ketone are produced.
Recently, exothermic oxidative dehydrogenation processes have been de-
veloped including the Petrotex process and the second stage of the Phillips
process, which employs a halogen promoted catalyst. The butenes from the
separation process are mixed with compressed air and steam and passed over
the catalyst bed to effect the conversion to butadiene. A process licensed
by BP International utilized multitubular reactors filled with mixed oxide
catalyst. The heat developed is used in making steam. The reported on-
stream time is several thousand hours.
The dehyrogenation reaction gases are quenched with oil (Process 2),
compressed, and the light gases are removed from the Ci» compounds which are
recycled to the separation and purification process (Process No. 12) for
isolation of the C4 compounds. The light gases are generally used as fuel;
hydrogen may be recovered for use in acetylenics removal by hydrogenation.
2. Input Materials - Butenes from the separation process and from refineries
along with steam and air are feed streams to this process. Catalyst makeup
rates are assumed to be very low.
Shell 205 catalyst requires 8 moles of dilution steam per mole of butene;
Dow B requires 18-20 moles dilution steam per mole of butene.
3. Operating Parameters - Table 25 contains operating parameters for de-
hydrogenation with Dow B and Shell 205 catalysts. Operating conditions for
the oxidative dehydrogenation were not readily available in the information
consulted for this study.
60
-------
Table 25. OPERATING PARAMETERS FOR DEHYDROGENATION OF BUTENES
Temperature
Space velocity
Operating pressure
Shell 205
620 - 680°C
500/ hrs
atmospheric
Dow B
590 - 680°C
125 - 175/hrs
170 - 200 kPa
Regeneration pressure
Catalyst type
Regeneration frequency
% conversion
% selectivity5
450 kPa (50 psig)
ferric oxide, chromium
oxide, potassium oxide
1 hr/day
26 - 28
73 - 75
(10-15 psig)
calcium nickel
phosphate stabilized
with chromium oxide
15 min/30 min
up to 45
90
(butene disappearing/butene feed/pass) X100
(moles butadiene produced/moles butene disappearing) X100
4- Utilities^ - The endothermic dehydrogenation process requires about 1.7
MJ/kg (720 Btu/lb) of converted butenes as heat energy.
Utilities for an endothermic process for dehydrogenating butenes are
given below based on 45 Mg/yr (100,000 Ib/yr) capacity.
Cooling water - 163 m3/min. (43,130 gal/min)
Process and makeup water - 7.1 m3/min (1,870 gal/min)
Power - 10.9 MW (14,600 hp)
Water refrigeration - 801 W (2,735 tons)
Ammonia refrigeration - 533 W (1,820 tons)
Steam (4.2 mPa, 400°C) - 10.9 Mg/hr (24,000 Ib/hr)
Natural gas - 8,660 m3/hr (306,000 ftVhr)
5. Waste Streams - No quantitative data were available for emissions from
the dehydrogenation of butenes in the literature consulted for this study.
Catalyst regeneration causes intermittent emissions of C02, coke fines,
and catalyst fines. If the regeneration gases are scrubbed with water, an
intermittent wastewater stream results.
61
-------
It is assumed that spent catalyst is land-filled.
Toxic oxygenated by-products of some catalyst systems may be vented to
the atmosphere or discharged with wastewater unless a treatment method is
utilized.
Emissions from steam generation processes are discussed in the Industry
Description.
6. EPA Source Classification Code - None exists
7. References -
(1) "Butadiene," 620.5022 A. Chemical Economics Handbook. Menlo Park,
California: Stanford Research Institute, 1974.
(2) Environmental Protection Agency (Office of Water and Hazardous
Materials, Effluent Guidelines Div.). Development Document for
Effluent Limitations Guidelines and New Source Performance
Standards for the Major Organic Products Segment of the Organic
Chemicals Manufacturing Point Source Category. EPA 440/1-74-009-a.
Washington, D.C.: 1974.
(3) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(4) Hedley, W. H., et al. Potential Pollutants from Petrochemical
Processes. MRC-DA-406. Dayton, Ohio: Monsanto Research Corp.,
December 1973.
(5) "Petrochemical Handbook." Hydrocarbon Processing, 50 (November
1971), 136-137.
(6) Slttig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
(7) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 3. 2nd ed. N.Y.: Interscience Publishers, 1965.
62
-------
BTX PRODUCTION PROCESSES
This operation of the basic petrochemicals industry is composed of processes
which produce benzene, toluene, mixed xylenes, and the separate xylene isomers
for use as solvents, chemical intermediates, or gasoline blending stocks. The
two feedstocks processed in this industry operation are the C6-C9 fraction of
catalytic reformate from refineries and the pyrolysis gasoline by-product of
olefins production by thermal cracking. Although a few companies produce BTX
from purchased coke oven light oil, benzene, toluene, and xylenes are produced
from coal tar and coke oven by-products in a separate industry. BTX production
processes utilizing coal-derived feedstocks are not included in this industry.
Figure 7 illustrates the nine processes utilized in BTX production from
catalytic reformate and pyrolysis gasoline. The first three processes include
(1) hydrotreating of pyrolysis gasoline, (2) extraction of aromatics from re-
formate and pyrolysis gasoline, and (3) fractionation of the aromatic extract
to produce pure benzene, toluene, and a mixture of C8 aromatics.
Further processing of toluene and mixed xylenes includes a number of
alternatives. One source indicates that of thirty-three companies producing
BTX, twelve also produced one or more separate isomers from mixed C8 aromatics
by employing some combination of Processes 18 through 21. For illustrative
purposes all four processes are shown in the combination in Figure 7. In
practice various combinations are employed in order to maximize production
of a particular isomer. Para-xylene and ortho-xylene have the largest market
for chemical intermediate use, but meta-xylene occurs naturally in the highest
concentration. Mixed xylenes are widely used as solvents and in gasoline
blending. Thus, the processing scheme employed depends on the value of solvent
xylenes or gasoline blending components as well as the cost of isomerization
and separate isomer recovery for chemical intermediate use. Technology is
still in the early years of commercialization for some isomer separation methods.
Complexation processes employing nickel thiocyanate/g-picoline, Ni(4-methyl-
pyrideneK (SCN)a> metal adducts, and carbon tetrachloride are mentioned in
the literature, but there is insufficient information for preparation of pro-
cess descriptions. Processes also exist involving selective sulfonation and
hydrolysis and three-phase crystallization. The extent of application of
these processes is not evident.
Toluene processing options include gasoline blending, production of
benzene by dealkylation (Process 23), production of mixed xylenes by dispro-
portionation (Process 22), and limited markets for chemical intermediate use.
Dealkylation capacity exists but may not be current use. It is not clear
whether disproportionate capacity is available in the U.S. As in the case
of mixed xylenes, further toluene processing depends on the.comparative
economics for producing and selling the possible products.
63
-------
PYROL
OASOLINf-
FHOM
PROCESS
[_TO STORAGE J
O Gaseous Emissions
D Solid Waste
/\ Liquid Waste
^_
HYDRODEALKYtATION
23
TO THERMAL CRACKING
TO CHEMICAL PRODUCTION
OR SOLVENT USE
TO FUEL I
TO CHEMICAL PRODUCTION 1
OR SOLVENT USE I
TO SOLVENT, GASOLINE
•LENDING. OR
CHEMICAL PRODUCTION
TO SOLVENT UWE
OR QA3OUME
BLEMOMQ
TO CHEMICAL PRODUCTION
TO CHEMICAL PRODUCTION
TO SOLVENT USE
TO CHEMICAL PRODUCTION
TO CHEMICAL PRODUCTION
TO CHEMICAL PRODUCTION
Figure 7. BTX PRODUCTION PROCESSES
-------
BTX PRODUCTION PROCESS NO. 15
Hydrotreating
1. Function - This catalytic hydrogenation process treats raw pyrolysis
gasoline from thermal cracking to produce a stabilized mixed aromatics
stream for input to mixed aromatics extraction. Pyrolysis gasoline con-
tains mono-olefins, diolefins, and sulfur and nitrogen compounds which are
removed by hydrotreating in such processes as Unifining (U.O.P.) and HPG
(Houdry-Gulf). Two hydrotreating stages are employed. The first involves
a low temperature reaction in which gumforming diolefins are saturated.
In the conventional second-stage hydrotreater, mono-olefins are saturated,
and sulfur and nitrogen compounds are converted to H2S and NH3.
Processing steps and equipment include the following:
. Hydrogen and pyrolysis gasoline feedstock are preheated by steam
or by exchange with reactor effluent.
First-stage liquid or gas-phase hydrotreating is accomplished,
probably in a fixed-bed catalytic reactor.
. The first-stage effluent is heated. A furnace (fired heater)
is employed in one process.
. The second-stage hydrotreater employs conventional refinery
hydrotreating technology.
. The second-stage hydrotreater effluent is cooled. One
process employs a water-cooled heat exchanger.
. A gas-liquid separator is employed to produce a hydrogen-
rich stream for recycle. Caustic scrubbing may be employed
for purification of the hydrogen recycle stream.
. The liquid stream from the separator is treated in a
stabilizer-stripper which removes dissolved inorganic gases
and light hydrocarbons. This may be accomplished by reduced
pressure or steam stripping.
. If water is injected to remove ammonium bisulfate salts and
coke particles, a coalescer is employed to separate the
wastewater.
2. Input Materials - Pyrolysis gasoline, which may contain up to 80%
aromatics, and hydrogen are the input materials. The composition of pyro-
lysis gasoline from thermal cracking depends on the cracking feedstock and
the process conditions. Table 26 shows the hydrocarbon analysis for a
typical pyrolysis gasoline. Table 27 illustrates feed and product com-
positions for a published design case. Stoichiometric hydrogen requirements
for the design case were 48.9 normal m3/m3 (300 scf/bbl) pyrolysis gasoline.
An empirical correlation of stoichiometic hydrogen consumption with pyrolysis
gasoline properties such as Diene Value, specific gravity and bromine number
is available in the literatuere.
65
-------
Table 26 HYDROCARBONS IN TYPICAL PYROLYSIS GASOLINE
CONTAINING 70% AROMATICS
Component
Diolefins
Mono-olefins
Saturates
Benzene
Toluene
C8 Aromatics
C9+ Aromatics
Weight Percent of
Total Hydrocarbons
15
8
7
32
14
11
13
100
Source: Brownstein, Arthur M., ed. U.S. Petrochemicals,
Technologies, Markets, and Economics. Tulsa,
Oklahoma: Petroleum Publishing Company, 1972.
Table 27. DESIGN CASE COMPOSITION OF FEED AND PRODUCT FROM
TWO-STA«E HYDR06ENATION OF PYROLYSIS GASOLINC
FOR SULFUR AND GUM REMOVAL
Component (wt %)
Benzene
To! uene
Ethyl benzene
Meta-, para-xylene
Ortho-xylene
Styrene
Sulfur (wt ppm)
Gum (kg/ 100m3)
Feed
37.2
21.2
1.5
4.4
1.2
4.6
150
<10
Product
37.3
21.1
6.0
4.5
1.2
not given
<1
0
Source: Kubo, Haruo, Shinobu Masamune and Ryoji Sako. "Make
B.T.X. From Cracker Gasoline." Hydrocarbon Processing,
49 (July 1970), 111. y
66
-------
3. Operating Parameters - The first-stage hydrotreater is operated at
150-200 C° (300-400°F) with nickel sulfide or platinum catalysts. The
second-stage hydrotreater temperature range is 300-400°C (600-800°F). A
cobalt-molybdenum catalyst is used.
4- Utilities - The design case process described in Table 27 employs steam
preheating; a low-temperature, liquid-phase first-stage hydrotreating process;
a furnace for heating first-stage hydrotreater effluent; a water-cooled heat
exchanger for cooling second-stage hydrotreater effluent; and a compressor
for recycle hydrogen. Utility requirements for a plant of this design with
a capacity of 182,000 Mg/yr are given in Table 28.
Table 28. UTILITY REQUIREMENTS FOR 182,000 METRIC TON/YR TWO-
STAGE PYROLYSIS GASOLINE HYDROTREATER
Value Per Barrel of
Utility Pyrolysis Gasoline
Electric Power 2.96 kWh
500 kPa (60 psig) Saturated Steam 17.9 kg (39.2 Ib)
Fuel 42.8 MJ (40.5X103 Btu)
Cooling Water (AT-10°C=18°F) 4.527m3 (1196 gal)
Source: Kubo, Haruo, Shinobu Masamune and Ryoji Sako. "Make B.T.X.
From Cracker Gasoline." Hydrocarbon Processing, 49
(July 1970), 111.
5. Waste Streams - Intermittent waste streams originate from catalyst cleaning.
Relatively frequent catalyst fouling in the first-stage hydrotreater is a prob-
lem and accounts for some of the variations in the available processes. Wash
oil is used to dissolve polymerized material from the catalyst in the HPG
process. Hydrogen stripping and steam-air decoking, which are employed in
other processes, produce gaseous emissions containing carbon monoxide. Steam-
air decoking may be required at four-month intervals, while a six- to nine-
month regeneration cycle has been estimated for other processes. One process
claims a two- to three-year catalyst life on the basis of pilot plant operations.
Dissolved NH3, H2S, and light hydrocarbons are separated from the
hydrotreated liquid in the stabilizer-stripper section. If a low-pressure
separator is used, a gaseous waste stream is produced. Neither the concentra-
tions of pollutants nor the disposition of this gas stream were evident from
the literature. In refinery hydrodesulfurization (see Chapter 3, Process
No. 16), this stream is treated by amine scrubbing for H2S removal and then
used as fuel. Alternatively, steam stripping may be employed to remove H2S
1n the stabilizer section. This operation produces a sour water waste stream.
In refinery operations (see Chapter 3) this stream is treated in a sour water
stripper.
67
-------
Additional intermittent wastewater streams may be produced. Water may
be used for alkaline scrubbing of the hydrogen recycle stream. Blowdown
will produce wastewater. The hydrotreated liquid may be washed to remove
ammonium salts originating from hydrogenation of nitrogen compounds and coke
particles from pyrolysis. Wash water will be separated from the liquid pro-
duct by a coalescer.
Table 29 shows wastewater characteristics which resulted from measurements
on process streams at a pyrolysis gasoline hydrotreating facility. These
characteristics were proposed as representative of the industry.
Table 29. CHARACTERISTICS OF WASTEWATER FROM TWO-STAGE
HYDROTREATING OF PYROLYSIS GASOLINE
Concentration Volume or Weight per
Characteristic
Wastewater Flow
Five-day BOD
COD
TOC
g/m3
914
2755
306
Mq of Product
0.114m?
0.10 kg
0.31 kg
0.03 kg
Source: Environmental Protection Agency (Office of Water
and Hazardous Materials, Effluent Guidelines Div.).
Development Document for Effluent Limitations Guide-
lines and New Source Performance Standards for the
Major Organic Products Segment of the Organic Chemicals
Manufacturing Point Source Categoy. EPA 440/1-74-009-a.
Washington, D. C.: 1974.
6. EPA Source Classification Code - None exists.
7. References -
(1) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Considine, Douglas M., ed. Chemical and Process Technology
Encyclopedia. N.Y.: McGraw-Hill Book Company, 1974.
(3) Environmental Protection Agency (Office of Water and Hazardous
Materials, Effluent Guidelines Div.). Development Document for
Effluent Limitations Guidelines and New Source Performance
Standards for the Major Organic Products Segment of the Organic
Chemicals Manufacturing Point Source Category
EPA 440/1-74-009-a. Washington, D. C.: 1974*
68
-------
References (Cont'd)
(4) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(5) Kubo, Haruo, Shinobu Masamune and Ryoji Sako. "Make B.T.X. From
Cracker Gasoline." Hydrocarbon Processing, 49 (July 1970), 111.
(6) "Refining Handbook." Hydrocarbon Processing, 53 (September 1974),
153
(7) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
69
-------
BTX PRODUCTION PROCESS NO. 16
Aromatlcs Extraction
1. Function - This process extracts aromatics from hydrocarbon mixtures such
as catalytic reformate and pyrolysis gasoline. The technology was first em-
ployed in refineries to produce nitration grade aromatics from catalytic
reformate. The Udex process, employing di-, tri-, or tetra-ethylene glycol-
water mixtures, and the Sulfolane process are the methods most commonly used.
Approximately equal numbers of Udex and Sulfolane units were in operation in
1972. The products are a mixed aromatics extract, which is stored, and
raffinate, containing mainly paraffins, which may be treated by thermal
cracking or used as a solvent or jet fuel component.
Udex Process - Udex processing steps include countercurrent extraction
in a trayed or rotating disk contactor, separation of solvent from aromatics
in the extractor bottoms stream by steam stripping, condensation of stripped
aromatic vapors in an extract receiver, and water washing of both the extractor
overhead (raffinate) and the extract to recover traces of glycols. Wash water
is treated in a water-solvent still and recycled. The separated solvent is
regenerated and recycled. Regeneration produces a sludge waste stream.
Sulfolane Process - The Sulfolane process also employs countercurrent
extraction. Rich solvent is treated in an extractive stripper. Stripper over-
head vapors are condensed, and the hydrocarbon components are separated from
the aqueous solvent and recycled to the extractor. Stripper bottoms and
aqueous solvent are charged to an extract recovery column. Lean solvent from
the recovery column is recycled. Solvent-free extract is condensed from the
extract recovery column overhead stream. Using water from the extract accumu-
lator, raffinate is water washed to remove solvent.
2. Input Materials - Input materials are mixed aromatics and solvent. There
are two primary sources of mixed aromatics, catalytic reformate and stabilized
pyrolysis gasoline. Coke oven light oil may also be processed. The C5+
fraction of high octane reformate typically contains 45 to 70 volume percent
aromatics, some normal and isoparaffins, small quantities of naphthenes and
less than one percent olefins. Sulfur and nitrogen are removed in reforming.
Table 30 describes a typical aromatics content in reformate.
The aromatic content of pyrolysis gasoline is described in Tables 26 and
27 in Process No. 15.
Solvents employed in the Udex process are di-, tri-, and tetra-ethylene
glycols mixed with 8 to 12% water. Tetrahydrothiophenedioxide, (CH2KS02 is
th?.solvent in the Sulfolane process. Other processes employ dimethyl sulf-
oxide, diglycolamine, or N-methylpyrrolidone. Solvent to feed weight ratios
for treating reformate are 20:1 for diethylene glycol and 7:1 for Sulfolane
Solvent to feed ratios increase with higher aromatic content of feed Solvent
makeup rates are 30 kg/Gg feed for the Sulfolafte process and 0.9 g/m3 feed
(.03 Ib/bbl feed) for the Udex process. 9
70
-------
TABLE 30. TYPICAL AROMATICS CONTENT IN REFORMATE
Constituent Volume % of Reformate
Benzene 5
Toluene 24
Ethyl benzene 4
Para-xylene 4
Meta-xylene 9
Ortho-xylene 5
C9 and CIQ aromatics _4
55
Source: Brownstein, Arthur M., ed. U.S. Petrochemicals.
Technologies, Markets, and Economics. Tulsa,
Oklahoma: Petroleum Publishing Company, 1972.
3. Operating Parameters - Table 31 compares operating parameters for
Sulfolane and Udex processes. These data were based on an early Sulfolane
process design, and more recently published data may be more accurate.
Heat is supplied by steam for the Udex process and by direct-fired re-
boilers for the Sulfolane process described in this example.
Table 31. OPERATING PARAMETERS FOR UDEX AND SULFOLANE
AROMATICS EXTRACTION PROCESSES
Operating Condition
Stripping steam ratio, wt
Stripper bottom temperature,
Extractor top temperature,
Extractor pressure,
kPa (psig)
Feed temperature, °C(°F)
Udex Process
.6
140 (290)
140 (290)
860 (110)
115 (240)
Sulfolane
Process
.13
190 (375)
100 (212)
207 (15)
115 (240)
Source: Deal, G. H., Jr., et al. "A Better Way to Extract
Aromatics." Petroleum Refiner, September 1959, 195.
71
-------
Process descriptions published in 1972 indicated that Udex unit
capacities ranged from 30 to 4500 m3/stream day (180 to
28,000 bbl/stream day), while Sulfolane unit capacities ranged
from 50 to 7000 cmVstream day (300 to 45,000 bbl/stream day).
4. Utilities - Table 32 describes utility requirements for the same
early Udex and Sulfolane processes described in Table 31.
Table 32. UTILITY REQUIREMENTS FOR UDEX AND SULFOLANE
AROMATICS EXTRACTION PROCESSES
Utility Per Liter Feed
(per bbl feed)
Steam, kg (Ib)
Fuel, MJ (103 Btu)
Cooling Water, m3 (gal )
Electric Power,., kWh
Udex Process
180 (400)
-
4.5 (1,200)
1.3
Sulfolane
Process
1.1 (2.5)
200 (190)
2.0 (530)
0.8
Source: Deal, G. H., Jr., et al. "A Better way to Extract
Aromatics." Petroleum Refiner, September 1959, 195.
A more recently published study indicates that solvent regeneration
is done under vacuum. Steam requirements for one Sulfolane process design
were around 286 kg/m3 (100 Ib/bbl) feed.
5- Waste Streams - Sources of waste streams include solvent regeneration,
cooling water, and process leaks. Solvent regeneration is required due
to formation of thermal degradation and polymerization products. The
sludge produced in regeneration is disposed of by landfill. The production
of vacuum for regeneration results in an oily waste stream.
Cooling water may be contaminated with aromatics due to heat exchanger
leaks. One estimate indicated such leaks produced 50-200 ppm COD in cooling
water.
Wastewater from the Udex process is reported to be produced at the
rate of 0.504 m3/Mg (60.4 gal/103 Ib) of BTX extract produced. Total organic
carbon in the wastewater is reported to be 0.144 kg/103 kg BTX extract pro-
duced.
The solvent makeup rates given in Section 2 indicate the amount of
solvent that could appear in waste streams.
6. EPA Source Classification Code - None exists.
72
-------
7. References -
(1) Bland, William F. and Robert L. Davidson, eds. Petroleum Processing
Handbook. N.Y.: McGraw-Hill Book Company, 1967.
(2) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(3) Deal, G. H., Jr., et al. "A Better Way to Extract Aromatics."
Petroleum Refiner, September 1959, 195
(4) Environmental Protection Agency (Office of Water and Hazardous
Materials, Effluent Guidelines Div.). Development Document for
Effluent Limitations Guidelines and New Source Performance
Standards for the Major Organic Products Segment of the Organic
Chemicals Manufacturing Point Source Category. EPA 440/1-74-009-a.
Washington, D. C.: 1974.
(5) Gloyna, E. F. and D. L. Ford. "The Characteristics and Pollutional
Problems Associated with Petrochemical Wastes." Prepared for
FWPCA Contract 14-12-461, Ada, Oklahoma: Robert S. Kerr Water
Center, February 1970.
(6) Nelson, W. L. Petroleum Refinery Engineering. 4th ed. N.Y.:
McGraw-Hill, 1958.
(7) "Refining Handbook." Hydrocarbon Processing, 51 (September 1972),
203-204.
(8) "Refining Handbook." Hydrocarbon Processing, 53 (September 1974),
192.
(9) Sittig, Marshall. Pollution Control in the Organic Chemical
Industry. Park Ridge, N.J.: Noyes Data Corporation, 1974.
73
-------
BTX PRODUCTION PROCESS NO. 17
Ce-C9+ Aromatics Separation
1. Function - This process separates 99% pure mixed C5-C9+ aromatic extract
into pure benzene, toluene, mixed C8 aromatics, and in some cases a C9+
fraction. Benzene is sold for use as a chemical intermediate. Toluene is
used in fuels, as a chemical intermediate, or as a solvent. Part may be
further processed in this industry to produce benzene or xylenes by de-
al kylati on and disproportionation (Processes 22 and 23). The C8 mixture
is used for gasoline or solvent or further processed to separate the
isomers (Processes 18 through 21).
The extract is first preheated and treated in clay towers for trace
olefin and sulfur removal. Separation is accomplished in conventional
overhead refluxed fractionation columns.
2. Input Materials - Aromatic extract produced as described in Process 16
is the input material. Relative proportions of the Ce, Cv, Ca, and Cg
fractions depend on the source of the extract. The aromatic content of
pyrolysis gasoline is described in Process 15 and that of reformate in
Process 16. Clay is also an input material. One process requires 0.6 kg
of clay per m3 (1 ton/10,000 barrels) of extract treated.
3. Operating Parameters - Information describing operating conditions
was not found. Boiling points of the products are 78.8°C for benzene,
109.4°C for toluene, 137-142°C for the C8 mixture, and 161-216°C for the
C9+ fraction.
4. Utilities - Requirements include fuel or steam for preheating the
extract and for the reboilers, cooling water for condensation, and power
for pumping. Quantitative data were not found in the literature.
5. Waste Streams - Intermittent hydrocarbon emissions occur at relief
vents. Fugitive hydrocarbon emissions may occur at valves and pump seals.
Emissions from cooling water system operation and process heaters are dis-
cussed in the Industry Description.
Spent clay containing olefin polymerization products is discarded in
one operation. Solid waste from this source amounts to 0.6 kg per m3 extract
treated (one ton of clay per 10,000 barrels of extract).
6. EPA Source Classification Code - None exists.
74
-------
7. References -
(1) Bland, William F. and Robert L. Davidson, eds. Petroleum
Processing Handbook. N.Y.: McGraw-Hill Book Company, 1967.
(2) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(3) Hedley, W. H., et al. Potential Pollutants From Petrochemical
Processes. MRC-DA-406. Dayton, Ohio: Monsanto Research Corp.,
December 1973.
(4) Kerns, Gordon D. "Operating Cost Lowest in the Industry."
Oil and Gas J., 58 (September 1960), 91.
(5) "Toluene," 696.5032 A. Chemical Economics Handbook. Menlo
Park, California: Stanford Research Institute, 1972.
(6) "Xylenes," 699.5021 E. Chemical Economics Handbook. Menlo
Park, California: Stanford Research Institute, 1971.
75
-------
BTX PRODUCTION
PROCESS NO. 18
C8 Aromatics'Fractionation
1. Function - The purpose of this process is to separate ortho-xylene and
ethylbenzene from C8 aromatics mixtures. Both C8 isomers are recovered for
use as chemical intermediates. Separation is itocomplished by fractional
distillation for ortho-xylene and by superfractionation for ethylbenzene.
Ortho-xylene is produced as the bottoms product of a 100- to 150-tray
fractionation tower operated with a reflux ratio of 5-8 to 1. Ethylbenzene
separation is more difficult and requires 350 to 400 trays with a reflux
ratio of 25-50 to 1. A series of three columns may be employed. The re-
maining C8 aromatics mixture is usually treated further for separation of
other isomers. Depending on the feed material, this process may employ
another step to separate ortho-xylene from C9 and heavier aromatics.
2. Input Materials - Feed materials to this process are various mixtures
of the aromatic C8 isomers ethylbenzene, ortho-xylene, meta-xylene, and
para-xylene. Sources of mixed C8 aromatics include the C8+ fraction of
extract from catalytic reformate or pyrolysis gasoline (Process 17), the
equilibrium mixture from isomerization (Process 21), streams from other Cs
aromatic separation processes, and the product stream from toluene dispro-
portionation (Process 22). The composition of C8 isomers in input streams
is shown in Table 33.
Table 33. TYPICAL COMPOSITION OF C8 AROMATICS MIXTURES FROM
VARIOUS SOURCES
Component
Ethylbenzene
Para-xylene
Meta-xylene
Ortho-xylene
Catalytic
Reformate
21
18
39
22
Pyrolysis
Gasoline
53
10
25
12
Source: Atkins, R. S. "Which Process for Xylenes?"
Processing, 49 (November 1970), 127-136.
Tol uene
Dispropor-
tionation
—
26
50
24
Hydrocarbon
3. Operating Parameters - Information describing operating conditions
was not found. The boiling point of ethylbenzene is 136.2 °C, and that
of ortho-xylene is 144.4 °C. Typical plant sizes are in the range of
45-90 Gg/year. (100-200 X106 pounds per year).
76
-------
4- Utilities - Requirements include steam or fuel for reboilers, cooling
water for condensers, and power for pumping. Consumption rates were not
found in the literature. One source indicated that utilities for ethyl-
benzene superfractionation are prohibitively expensive at some locations.
5. Waste Streams - Intermittent hydrocarbon emissions occur at relief
vents. Fugitive hydrocarbon emissions may occur at valves and pump seals.
Emissions from cooling water system operation are discussed in the Industry
Description.
6. EPA Source Classification Code - None exists.
7. References -
(1) Atkins, R. S. "Which Process for Xylenes?" Hydrocarbon Processing
49 (November 1970), 127-136.
(2) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(3) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(4) Stobaugh, Robert B. "Xylenes: How, Where, Who—Future."
Hydrocarbon Processing, 45 (April 1966), 149.
77
-------
BTX PRODUCTION PROCESS NO. 19
Para-Xylene Crystallization
1. Function - This process separates 99+% pure para-xylene from other
aromatic isomers by fractional crystallization. Recovery of para-xylene
is limited to about 60% due to formation of eutectics with ortho- and
meta-xylene. A number of processes are available, and most include the
following steps:
1) Drying - Feedstock water content must be reduced to about
10 ppm. Drying is done in alumina or silica gel beds. Dual
bed operation is practiced. Regeneration is accomplished with
electric heaters or jacketed steam. Distillation is an alter-
native drying procedure.
2) Crystallization - Two crystallization stages are employed in
most processes. First-stage crystals are remelted and re-
crystallized. Scraped surface tubular exchangers or tank
crystallizers are used.
3) Cooling - First-stage crystallizer feed is partially cooled by
heat exchange with filtrate from the second-stage crystallizer.
Indirect refrigeration is usually employed. Propane,
ethylene, propylene, ammonia, or a fluorocarbon are
common refrigerants. One process employs direct
refrigeration with an immiscible coolant.
4) Solid-Liquid Separation - Continuous-solid bowl centrifuges or
rotary drum suction filters are employed in most modern plants.
Second-stage filtrate is recycled to the first-stage crystallizer.
First-stage crystal!izer mother liquor is a product stream which
is treated by isomerization or fractionation to separate other
Ce isomers.
2. Input Materials - Feed materials to this process are the same as those
to fractionation (Process 18). Crystallization processes which treat C8
fractions of unextracted reformate may be available, but it is not evident
whether such plants are operating in the U.S. Since only two-thirds of the
para-xylene present can be recovered by crystallization, about 0.1-0.15 kg
of para-xylene is produced per kg of typical mixed xylenes containing 12
to 22% para-xylene.
3. Operating Parameters - The first-stage crystallizer operates in the
temperature range -60 to -70 °C (-80 to -90°F). Second-stage crystal!izer
temperature is -32 °C (-25°F). Significant operating parameters for the
centrifuge are bowl revolution speed, bowl differential, and slurry pool
depth. Values for these parameters were not found in the literature.
4- Utilities - Utility requirements for a 45 Gg/year (50,000 ton/yr)
para-xylene crystallization facility are given in Table 34.
78
-------
Table 34. UTILITY REQUIREMENTS FOR PARA-XYLENE CRYSTALLIZATION
UtilityConsumption Per Mg of Para-Xylene
Electric power, kWh 380
Steam, kg (ton) 230 (0.25)
Cooling water, m3(gal) 100 (26,500)
Source:"Xylene Isomers Separated by New Process."Oil and Gas Journal,
15 December 1969, 82.
5. Waste Streams - Little information was found in the literature describing
waste stream origin, volume, or composition. Waste streams probably originate
from regeneration of dessicant, from refrigerant and pump seal leaks, and
from refrigeration and cooling water system operations. Cooling is appar-
ently the only water use in the process. One reference states that
crystallization and accumulated wastes from drains or bottoms produce sludge
in the amount of 0.4 to 2 m3/Mg of product (100 to 500 gallons/ton of product).
Since crystallizer mother liquor is recirculated, it is not clear how the
sludge is produced. The sludge is said to contain 3-5,000 g/m3 of organics.
Wastes from cooling water and refrigeration system operations are discussed
in the Industry Description.
6. EPA Source Classification Code - None exists .
7. References-
(1) Aalund, Leo R. "Xylene Boom Spawning New Processes." Oil and
gas J., 27 November 1967,48.
(2) Atkins, R. S. "Which Process for Xylenes?" Hydrocarbon Processing,
49 (November 1970), 127-136.
(3) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(4) Desiderio, R. J. "Single-Stage Crystallization Can Cut Paraxylene
Production Cost." Oil and Gas J., 8 July 1974, 116-117.
(5) Gloyna, E. F. and D. L. Ford. "The Characteristics and Pollutional
Problems Associated with Petrochemical Wastes." Prepared for FWPCA
Contract 14-12-461, Ada, Oklahoma: Robert S. Kerr Water Research
Center, February 1970.
(6) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(7) "Petrochemical Handbook." Hydrocarbon Processing, 52 (November
1973), 195.
79
-------
(8) Stobaugh, Robert B. "Xylenes: How, Where, Who—Future." Hydro-
carbon Processing, 45 (April 1966), 149.
(9) "Xylene Isomers Separated by New Process." Oil and Gas J., 15
December 1969. 82.
(10) "Xylenes," 699.5021 E. Chemical Economics Handbook. Menlo Park,
California: Stanford Research Institute, 1971.
80
-------
BTX PRODUCTION
PROCESS NO. 20
Para-Xylene Adsorption
1. Function - Para-xylene is separated from a mixture of C8 aromatic
isoraers by selective adsorption in a fixed bed of porous solid adsorbent.
In the Parex process the adsorbed para-xylene is desorbed by washing with
a hydrocarbon of boiling point different from those of the aromatics.
Raffinate and para-xylene are separated from the desorbent by fraction-
ation. Equipment includes a single bed of adsorbent with a multiport
rotary distributing valve. The arrangement simulates countercurrent flow
of adsorbent and liquid without solid conveyance.
2. Input Materials - This process treats the same mixed xylene streams
as the fractionation and crystallization processes (Processes 18 and 19).
The unextracted C8 fraction of reformate is also treated effectively in
this process. Solid adsorbent and liquid desorbent makeup requirements
were not found in the literature. Para-xylene recovery efficiencies of
95 to 99% are reported. At 95% recovery, assuming 20% para-xylene in the
mixed xylene feed, 5.25 kg feed would be required per kg para-xylene pro-
duced.
3. Operating Parameters - The adsorption temperature is in the range of
120 to 150°C (250 to 300°F). Moderate pressures are employed. Operating
conditions for fractionation were not found.
4. Utilities - Data have been published for the Japanese Aromax process
which differs from the Parex process in the type of valve employed to
simulate countercurrent flow of solid and liquid. Table 35 summarizes
utility requirements for a combined Aromax adsorption-isomerization process.
(Isomerization is described in Process 21.) The process treats 116 Gg/year
of mixed xylenes and produces 100 Gg/year of para-xylene.
Tl&le 35. UTILITY REQUIREMENTS FOR COMBINED ADSORPTION
(AROMAX PROCESS) AND ISOMERIZATION PROCESS
PRODUCING 100 Gg/YEAR PARA-XYLENE
Utility
Steam
Absorbed Heat Duty
Electric Power
Cooling Water
Consumption Rate
12 Mg/hr
230 GJ/hr
3,900 kW
136 Mg/hr
Source: '"Petrochemical Handbook." Hydrocarbon Processing, 52
(November 1973), 196.
81
-------
5. Waste Streams - Very little information was found in the literature
describing this relatively new process. Slowdown from regeneration of
adsorbent and desorbent and hydrocarbon leaks from vents, valves, and
pump seals are possible sources of waste streams. Waste streams resulting
from operation of cooling water and power and steam generation systems are
discussed in the Industry Description.
6. EPA Souce Classification Code - None exists.
7. References -
(1) Atkins, R. S. "Which Process for Xylenes?" Hydrocarbon Pro-
cessing, 49 (November 1970), 127-136.
(2) Brownstein, Arthur M., ed. U.. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(3) Otani, Seiya. "Adsorption Separates Xylenes." Chemical Engineer-
ing, 80 (September 1973), 106-107.
(4) "Petrochemical Handbook." Hydrocarbon Processing, 52 (November
1973), 196.
(5) "Petrochemical Handbook." Hydrocarbon Processing, 52 (November
1973), 198.
82
-------
BTX PRODUCTION PROCESS NO. 21
C8 Aromatics Isomerization
1. Function - This process changes the composition of mixtures of C8
aromatic isomers to the equilibrium composition at the operating conditions.
The process is used to treat mixtures from which one or more of the isomers
have been removed as described in Processes 18, 19, and 20. Isomerization
is generally employed to convert the naturally most abundant meta-xylene
isomer to ortho- and para-xylene, which are more widely used as chemical
intermediates. Isomerization processes also convert some of the ethyl-
benzene to xylenes or to benzene and toluene by disproportionate.
A number of isomerization processes are offered. They differ primarily
in the type of catalyst employed and in the resulting isomerization reactor
operating conditions. Processing steps include the following:
Feed is preheated by exchange with reactor effluent and further
heated in a fired heater. Some processes employ hydrogen which
is mixed with feed liquor after preheating.
. Isomerization occurs over a fixed bed of catalyst with hydrogen
or steam.
. Gaseous and liquid isomerization products are separated in a
flash drum. The hydrogen-rich gas stream is recycled to the
reactor in processes which employ hydrogen. A purge gas stream
is used to maintain hydrogen purity.
Liquid isomerizate is fractionated, and benzene and tolune are
recovered overhead. A fuel gas may be separated when light
aromatics are condensed. Bottoms are fractionated in a rerun
column which produces a £9+ bottoms stream and the equilibrium
xylene mixture for further treatment. By-products from this
process include the C9+ heavy aromatics fraction which may be
input to toluene transalkylation (Process 22), some benzene and
toluene, and a mixed-xylene solvent slip stream.
2. InputMaterials - The feedstock, a mixture of C8 isomers, usually
contains a high proportion of meta-xylene and ethyl benzene and unrecovered
amounts of ortho and para isomers. Mother liquor from para-xylene
crystallization or adsorption, or overhead product from ortho-xylene
fractionation are used. One Japanese process extracts meta-xylene with
HF3-BF3 and employs the extract as feed to isomerization. Hydrogen is
also an input material. Concentration in the feed can be as high as a
10 to 1 mole ratio.
3. Operating Parameters - Table 36 summarizes operating parameters for
a number of isomerization processes. Not all of the processes listed in
Table 36 are commercialized in the United States. Isomerization reactor
size and yield depends on the amount of ethylbenzene in the feedstock and
on the catalyst employed.
83
-------
Table 36. OPERATING CONDITIONS FOR COMMERCIAL CB AROMATICS ISOMERIZATION PROCESSES
Licensor
Atlantic Richfield
Engelhard, Octaflnlng
ESSO, Isoformlng
Imperial Chemical
Industries
Japan Gas, HF,-BF3
Extraction
Isomerlzatlon
Maruzen, XIS
U.O.P., Isomar
Mobil, LTI
Temperature
"C °F
ing 400-500
370-450
400-500
-I to 10
66-93
460-560
ZOO- 300
800-900
700-850
750-930
30-50
150-200
860-1040
Moderate
400-500
Pressure
kPa Atm Catalyst
100
>1000
>1000
100
100
100
Conditions
2000
1 Nonnoble metal
>10 Platinum, requires
hydrogen
>10 Nonnoble metal ,
requires hydrogen
1 Nonnoble metal
1 HFj-BFs
1 Silica-Alumina
Noble metal , re-
quires hydrogen
20psig Zeolite, requires
toluene diluent
Sources: Atkins, R. S. "Which Process for Xylenes?" Hydrocarbon Processing, 49 (November 1970), 127-136
Grandio, P. and F. H. Schneider, "AP-Catalyst Processes Make Aromatics at Low Temperature."
Oil and Gas J., 29 November 1971, 62.
"Petrochemical Handbook." Hydrocarbon Processing, 52 (November 1973), 195
4. Uti1ities - Table 37 gives utility requirements for a combined process
employing para-xylene crystallization and isomerization by the process
licensed by Maruzen Oil Company. Isomerization is accomplished using silica-
alumina catalyst with addition of steam at atmospheric pressure. Utilities
for a combined adsorption-isomerization process are given in Process 20.
Table 37. UTILITY REQUIREMENTS FOR COMBINED XYLENE
CRYSTALLIZATION-ISOMERIZATION PROCESS
Utility
Steam
Electricity
Cooling Water
Fuel Oil
Consumption Per Mg of
Para-Xylene Produced
160 kg
463 kWh
98 Mg
16 GJ
Scarce: "Petrochemical Handbook.1* Hydrocarbon Processinq
52 (November 1973), 195.
84
-------
5. Waste Stream - Two gas streams are produced by isomerization processes.
Indications are that both the purge from the recycle hydrogen stream from
the flash drum and the vent gas produced during separation and condensation
of light aromatics are used as fuel gas.
Although no information was found describing waste streams in the
literature consulted for this study, it is probable that they arise from
periodic catalyst regeneration; disposal of spent catalyst; leaks at valves,
vents, and pump seals; and operation of cooling water, steam generation,
and power generation systems. The latter category is discussed in the
Industry Description. Catalyst regeneration is accomplished by steam-air
decoking in one process.
6. EPA Source Classification Code - None exists.
7. References -
(1) Aalund, Leo R. "Xylene Boom Spawning New Processes." Oil and Gas
J., 27 November 1967, 48.
(2) Atkins, R. S. "Which Process for Xylenes?" Hydrocarbon Processing,
49 (November 1970), 127-136.
(3) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(4) Grandio, P. and F. H. Schneider. "AP-Catalyst Processes Make
Aromatics at Low Temperature." Oil and Gas J., 29 November 1971, 62.
(5) Hedley, W. H., et al. Potential Pollutants From Petrochemical
Processes. MRC-DA-406. Dayton, Ohio: Monsanto Research Corp.,
December 1973.
(6) "Petrochemical Handbook." Hydrocarbon Processing, 52 (November 1973),
195, 196.
(7) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November 1975),
197.
(8) Stobaugh, Robert B. "Xylenes: How, Where, Who—Future." Hydrocarbon
Processing, 45 (April 1966), 149. ,
(9) "Xylenes," 699.5021 E. Chemical Economics Handbook. Menlo Park,
California: Stanford Research Institute, 1971.
85
-------
BTX PRODUCTION
PROCESS NO. 22
To!une Pi sproportionation/Transal kyl ation
1. Function - This vapor-or liquid-phase catalytic process converts
toluene (C7) to a mixture of xylene isomers (C8) and benzene by the
following disproportionation reaction:
CH3
If C9 aromatics are present in the feed, they are also converted to
xylenes by a transalkylation reaction:
H3C
CH:
CHc
2
-------
Tafble 38. VARIATIONS OF DISPROPORTIONATION/TRANSALKYLATION
PRODUCT RATIOS WITH C9 CONTENT OF FEED
Feed Composition
100% toluene
67% toluene
33% C9 aromatics
50% toluene
50% C9 aromatics
Benzene
37%
13%
9%
Products
Xylenes
55%
62%
87%
Xylene/
Benzene
1.5
6.2
10
Source: Brownstein, Arthur M., ed. U.S. Petrochemicals.
Technologies, Markets, and Economics. Tulsa,
Oklahoma: Petroleum Publishing Company, 1972.
Table 39. UTILITY REQUIREMENTS FOR VAPOR PHASE CATALYTIC
TOLUENE DISPROPORTIONATE WITH C9 RECYCLE
Consumption per
Utility Mg Toluene Feed
Electric Power 73 kWh
Steam 1400 kg
Cooling water (At = 10°C) 2400 kg
Fuel 30 MJ
Source: "Petrochemical Handbook." Hydrocarbon Processing. 50
(November 1971), 133.
87
-------
5. Waste Streams - Waste streams result from leaks at valves and pump seals;
periodic catalyst regeneration; disposal of spent catalyst; process heaters;
and operation of cooling water, steam and power generation systems. Emissions
from the latter category are discussed in the Industry Description.
Two hydrocarbon waste streams are produced by disproportionation processes.
A light ends off-gas stream containing paraffins and olefins is produced by
the Tatoray process in the amount of 19 kg per 1000 kg feed. Heavy ends con-
taining Cio+ aromatics such as biphenyl and cyclic nonaromatics are produced
in quantities of about 10 kg per 1000 kg feed. For the liquid phase disproportion-
ation process, the products include about 0.5% Cio+ hydrocarbons and 0.1%
nonaromatics. These products may be ultimately disposed of as waste streams.
6. EPS Source Classification Code - None exists.
7. References -
(1) Brownstein, Arthur M. ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(2) Grandio, P. and F. H. Schneider. "AP-Catalyst Processes Make
Aromatics at Low Temperature." Oil and Gas J., 29 November 1971, 62.
(3) "Petrochemical Handbook." Hydrocarbon Processing, 50 (November 1971),
133.
(4) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November 1975),
115.
(5) "Xylenes," 699.5021 E. Chemical Economics Handbook. Menlo Park,
California: Stanford Research Institute, 1971.
88
-------
BTX PRODUCTION PROCESS NO. 23
Hydrodealkylation
1. Function - Benzene is produced from toluene by catalytic or thermal
dealkylation, as shown in the following reaction:
C6H5CH3 + H2 -* C6H6 + CH4
Excess hydrogen is added to prevent coking and cold hydrogen is employed
as a quench for the highly exothermic reaction. Xylenes or other alkyl-
aromatics may also be dealkylated to benzene by this process, but increased
polymer and coke formation become problems.
Catalytic processes include the Hydeal (U.O.P.) and Detol (Houdry)
processes. The HDA process (Atlantic Richfield - HRI) and the THD process
(Gulf) are thermal processes. Common processing steps in producing benzene
from toluene are described as follows:
Reactor feed and compressed recycle and makeup hydrogen are preheated
by exchange with process streams and in a fired heater. Dealkylation is
accomplished in a fixed-bed catalytic or thermal reactor. Reactor effluent
is cooled using a waste heat boiler in some process designs, by exchange
with fresh feed, and in water-cooled exchangers.
Dealkylation product is treated in a flash drum where a recycle
hydrogen-rich gas stream is separated. A fuel gas purge stream is withdrawn.
Liquid from the separator is treated in a stabilizer where dissolved hydro-
carbons with boiling points below that of benzene are separated. A fuel
gas stream is produced in this step also. Benzene is separated from stabi-
lizer liquid effluent by distillation. Benzene column bottoms are
recirculated to the dealkylation reactor. Clay treating may be required as
a purification step in processes which treat unrefined starting materials.
2. Input Materials - Toluene, or mixtures of toluene and xylenes, and
hydrogen are input materials to this process. Hydrodealkylation can also
be used to produce benzene directly from impure or unrefined hydrocarbon
mixtures containing alkyl aromatics such as pyrolysis gasoline, unextracted
reformate cuts, or coke oven light oil fractions. Process 25 describes
naphthalene production by hydrodealkylation. Table 40 shows typical input
stream compositions used as the basis for a description of utility require-
ments for the Houdry process.
A 100 percent efficient toluene conversion process would yield 84.7 weight
percent or 83 volume percent benzene. One source reported that practical
efficiencies are around 97 percent, so that about 80 weight percent of the feed
is converted to benzene. Industry estimates from another source are that 1.22
to 1.28 volumes of toluene are consumed for each volume of benzene produced.
Toluene content of the Udex grade feedstock is about 92 to 95 percent. In some
cases an 85-90 percent toluene/10-15 percent xylenes mixture may be used.
Hydrogen-toluene mole ratios of 8 to 1 employed.
89
-------
Table 40. TYPICAL COMPOSITION OF FEEDSTOCKS FOR
HOUDRY HYDRODEALKYLATION PROCESS
Feedstock
C6- C9 Fraction of
Products from C6-C9 Fraction of
Component (Percent) Toluene Thermal Cracking Coke Oven Light Oil
C5+ .Paraffins,
iNaphthenes, and olefins
Benzene
Toluene 100
C8 Aromatics
Styrene
C9+ Aromatics
Source- Chemical Engineer! no
Chemical Products, 1
32
33
14
13
2
6
, ed. Sources and
973-1974. 1st ed.
3
74
15
4
2
2
Production Economics of
N.Y.: McGraw-Hill, 1974.
Operating Parameters - Catalytic processes (Detol, Hydeal) typically operate
K) to 6506C (1000 to 1200°F). Thermal processes (THD, Hydrodealkylation)
3.
at 540~
are conducted at temperatures as high as 760°C (1400°F). Pressures in the range
from 3.5 to 8.4 MPa (500-1200 psig) are employed in both processes. The catalyst
employed in the Detol process is in the form of cylindrical pellets of unreported
composition. A description of the catalyst used in the Hydeal process was not
,found in the literature.
4. Utilities - Table 41 shows estimated utility consumption for conversion of
160 m3 (1000 bbl)/stream day of Udex grade toluene by a Hydeal process including
a heater, a reactor, a recycle gas compressor, a hydrogen generator, clay
treating, and product fractionation. Cooling water system, power generation,
utilities distribution and waste disposal are not included. Table 42 summarizes
utility requirements for the Houdry process based on the input compositions
described in Table 40.
90
-------
Table 41. UTILITY CONSUMPTION RATES FOR BENZENE PRODUCTION
FROM TOLUENE BY THE HYDEAL PROCESS
Utility Consumption Rate
(1.1 MPa) Steam, kg/hr (Ib/hr) 2900 (6300)
(4.2 MPa) Steam, kg/hr (Ib/hr) 1400 (3000)
Fuel, GJ/hr (Btu/hr) 13.2 (12.5 x 106)
Electricity, kW 800
Cooling Water, dm3/s (gal/min) 0.789 (12.50)
Source: Asselin, G. F. and R. A. Erickson. "Benzene and Naphthalene
from Petroleum by the Hydeal Process." Chemical Engineering
Progress, 58 (April 1962), 47.
Table 42. UTILITY REQUIREMENTS FOR THE HOUDRY
CATALYTIC HYDRODEALKYLATION PROCESS
Quantity Required Per Mg Benzene
Produced From
Coke Oven
Uti1ity To!uene Pyrolysis Gasoline Light Oil
Electric Power, GO (Wh) 0.194 (54.0) 0.187 (52.0) 0.163 (45.2)
Steam Consumed, kg 44 970 150
Steam Produced, kg - 905 537
Net Steam, kg -44 -65 +387
Boiler Feedwater, kg - 3 16.3
Cooling Water, kg 16,900 43,500 28,600
Fuel Consumed, GJ (106 Btu) 2.63 (2.49) 3.49 (3.30) 3.91 (3.70)
Fuel Produced, GJ (106 Btu) 11.6 (11.0) 29.1 (27.5) 5.70 (5.40)
Net Fuel, GJ (106 Btu) +9.00 (8.52) +25.4 (24.0) +1.79 (1.69)
Source: Chemical Engineering, ed. Sources and Production Economics of Chemical
Products, 1973-1974. 1st ed. N.Y.: McGraw-Hill, 1974.
91
-------
5. Waste Streams - Little information was found in the literature describing
waste streams. It is probable that waste streams originate from periodic
catalyst regenerating; fugitive emissions from valves and pump seals; discarding
spent clay; and operating power generation and cooling water systems, gas
compressors, and process heaters. These systems are discussed in the Industry
Description.
Catalyst regeneration in the Detol process involves occasional burning
of coke deposits in a preheated inert gas with controlled quantities of air.
Descriptions of the Hydeal process indicate that about one percent of aromatics
in the feed may be converted to heavy aromatics such as biphenyl, methylbi-
phenyls and fluorene through condensation of aromatic nuclei. Ultimately,
these heavy aromatics must be found in waste streams.
6. EPA Source Classification Code - None exists.
7. References -
(1) Asselin, G. F. and R. A. Erickson. "Benzene and Naphthalene from
Petroleum by the Hydeal Process." Chemical Engineering Progress,
58 (April 1962), 47.
(2) Brownstein, Arthur M., ed. U.S. Petrochemicals, Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(3) Chemical Engineering, ed. Sources and Production Economics of
Chemical Products, 1973-1974. 1st ed. N.Y.: McGraw-Hill, 1974.
(4) Erskine, Mimi G. "Benzene." 618.5021 A. Chemical Economics
Handbook. Menlo Park, California: Stanford Research Institute, 1972.
(5) Petroleum Refiner, 40 (November 1961), 236, 251, 252, 298.
92
-------
NAPHTHALENE PRODUCTION PROCESSES
This operation of the basic petrochemical industry produces naphthalene
from heavy reformate, catalytic cycle oils, or by-products from steam cracking
to produce olefins. Although naphthalene is also produced from coal tar,
this treatment is restricted to production from petroleum sources.
Figure 8 shows the required processes which include aromatics extraction
for those feeds with relatively low aromatics content (Process No. 24) and
dealkylation of alkyl naphthalenes (Process No. 25). The major by-product
is an aromatics-rich naphtha which may be used in blending gasolines or from
which benzene may be separated.
93
-------
CATALYTIC LIGHT
CYCLE OIL OR
STEAM CRACKING
BY-PRODUCTS
~""""\o
C
EXTRACTION
OF DICYCLIC
AROMATICS
24
)
HY
DROGEN
i WATER r
* 1
HYDROOEALKYLAT1ON
TO PRODUCE
NAPHTHALENE
•.
LJ \
ALTERNATE
CHARGING STOCK
HEAVY REFORMATE
25 -I
O Gaseous Emissions
Solid Waste
Liquid Waste
HIGH CETAN
DIESEL FUEL
TO SALES
/ ACID \ ^
I GAS f=^
TO SULFUR
RECOVERY
—I
NAPHTHA
RICH IN
AROMATICS
OR
BENZENE
TO
GASOLINE
BLENDING
OR SALES
w
Figure 8, NAPHTHALENE PRODUCTION PROCESSES
-------
NAPHTHALENE FROM PETROLEUM PROCESS NO. 24
Extraction of Pi cyclic Aromatics
1. Function - Dicyclic (and higher) aromatic compounds are extracted from
catalytic gas oil or other materials of similar composition. The aromatic
rich product is dealkylated to produce naphthalene and the dearomatized
product is a high cetane number diesel fuel.
Dicyclic aromatics are selectively adsorbed from the liquid phase onto
fixed beds of adsorbent (silica gel). Desorption is effected by elution
with solvent with a boiling range different from that of the desired product.
Product and desorbent are separated by fractional distillation. Some sources
indicate that removal of water and compounds containing nitrogen, sulfur or
oxygen is required before the extraction step. Other sources indicate
hydrodesulfurization of the aromatic extract after separation.
Hydrodesulfurization and Acid Gas Removal are described as Processes
No. 4 and 16 in the Petroleum Refining Industry Chapter of this catalog.
2. Input Materials - The process is designed to extract aromatics from a
complex mixture. The extraction technique is flexible and different relative
amounts of dicyclic and monocyclic aromatics can be extracted from a given
feed by varying the nature of the adsorbent used and the operating conditions.
One source indicates stream compositions listed in the table below for a
catalytic gas oil (bp 226-268°C) feed and for the product streams derived
from it.
Table 43. STREAM COMPOSITIONS FOR EXTRACTION PROCESS
Composition of Streams (weight percent)
Catalytic Gas
Oil Feed Aromatic Lean
Compound Type bp 226-268°C Extract Stream
Total Aromatics 53.7 100 25.8
Dicyclic Aromatics 25.7 62 4.0
Monocyclic Aromatics 28.0 38 21.8
Source: Barbor, R. P. "Naphthalene from Catalytic Gas Oil."
Oil and Gas J., 21 May 1962, 123.
3. Operating Parameters - Temperatures do not exceed the atmospheric bubble
points of the charge stocks. Pressures are moderate, basically those required
to pump the feed through the adsorbent beds, and generally do not exceed 1.4 MPa
(200 psi). The commercial installation described in the literature is designed
to provide feed for a plant capable of producing 68 Gg (150xl06 pounds) of
naphthalene per year. Each kilogram of aromatic extract yields 0.4 kilogram of
naphthalene, so 170 Gg of aromatic extract would be required to operate the
95
-------
naphthalene plant at full capacity. The naphthalene plant can operate on
other feeds which do not require aromatic extraction so the actual capacity
of the aromatic extraction complex is probably somewhat below the figure cited.
4- Utilities - No information was available which gave utility requirements
for aromatic extraction of alkyl naphthalenes directly. One source gave
utility requirements for processing both heavy reformate and a catalytic
cycle stock containing 14.6% by weight dicyclic aromatics. The difference
between the utility requirement for the two stocks is in feed pretreatment
which includes aromatic extraction, hydrodesulfurization and acid gas removal.
The values given are listed in the table below on a per kilogram naphthalene
produced basis. The difference should be taken as a very crude estimate of
an upper limit for utility requirements.
Table 44. UTILITY REQUIREMENTS FOR EXTRACTION OF ALKYL NAPHTHALENES
FROM DIFFERENT STOCKS
Electric Power
Fuel
Steam
Circulating Water
Utility
Catalytic
Cycle Stock
Per kg
Naphthalene
8.2 watts
29.5 MO
zero
106 liters
Requirements
Heavy
Reformate
Per kg
Naphthalene
5.5 watts
13.1 MJ
0.56 kg
63 liters
For:
Difference
Per kg
Naphthalene
2.7 watts
16.4 MJ
not calculated
43 liters
Source: "Hydrodealkylation Processes." Industrial and Engineering Chemistry,
54 (February 1962), 28-33.
5. Waste Streams - Available process descriptions do not address the subject
of waste streams; however, several observations can be made.
Emissions of hydrocarbons to the atmosphere can be expected from vents of
distillation units and from fugitive sources such as pump seals and flanges.
Atmospheric emissions from process heaters are described as Process 31 for the
Petroleum Refining Industry. Waste streams resulting from cooling water treat-
ment are discussed in the Industry Description. Costs for chemicals are listed
in economic descriptions of these processes but the process descriptions give
little information as to the type of chemicals or their fate. Waste from acid
gas removal are discussed in Chapter 3, The Refining Industry, and in Process
No. 5 of this entry.
Spent sorbent represents a solid waste material, presumably to be disposed
of by landfill. However, the sorbent is reported to have a long life so only
a small amount of material is involved.
6. EPA Source Classification Code - None exists.
96
-------
7. References -
(1) Barbor, R. P. "Naphthalene from Catalytic Gas Oil." Oil and Gas
J., 21 May 1962, 123.
(2) Bland, William F. and Robert L. Davidson, eds. Petroleum Processing
Handbook. N.Y.: McGraw-Hill Book Company, 1967.
(3) Broughton, D. B. and L. C. Hardison. "Unisorb Extracts Naphthalene
Homologs.: Hydrocarbon Processing and Petroleum Refiner, 41
(May 1962), 125.
(4) "Hydrodealkylation Process." Industrial and Engineering Chemistry,
54 (February 1962), 28-33.
(5) Stanford Research Institute. 1975 Directory of Chemical Producers,
U.S.A. Menlo Park, California: 1975.
97
-------
NAPHTHALENE FROM PETROLEUM
PROCESS NO. 25
Hydrodealkylation to Produce Naphthalene
1. Function - Feed materials rich in alkyl naphthalenes are dealkylated in
the presence of hydrogen to produce naphthalene. In addition to high purity
naphthalene the process yields fuel gas, a light naphtha high in benzene
(or benzene), and a heavy component used for fuel. Hydrogen, and in some
processes water, is required in addition to the charging stock. The process
involves dealkylation, separation and product purification. Different pro-
cesses differ in the order in which these process steps are carried out and
in the specific types of separation and purification methods used. The charge
may be fed directly to the dealkylation unit and the dealkylated product
separated by fractional distillation. Alternatively, naphthalene may be
separated from the charge by distillation before dealkylation. In the latter
case the dealkylated product is recycled to the fractionating tower. Dealky-
lation may be carried out catalytically or noncatalytically (thermally).
Other separations may be carried out in high-pressure separators or in low-
pressure separators. Purification may involve sorption of impurities on acid
treated clay, further fractionation, and/or fractional crystallization.
2. Input Materials - Charging stock, hydrogen and sometimes water are required
input materials. SlTitable charging stocks include catalytic reformate bottoms
(bp 210-290°C 410-560°F ), or aromatic extract from catalytic cycle oil
(bp 226-268°C 440-515°F ), or by-products from steam cracking operations in
which olefins are made. Middle oil or crude naphthalene from coal tar may
be partially refined by this process. Typical compositions presented in one
source are given in Table 45 below.
Table 45. TYPICAL COMPOSITION OF NAPHTHALENE CHARGE STOCKS
Catalytic
Reformates
Total Aromatics (wt %)
Aromatics Composition (wt %)
Alkyl benzenes
Indans and Tetralins
Indenes
Alkyl Naphthalenes
Biphenyls and Acenaphthenes
Tricyclics
90-95
20
15
2
55
6
2
Catalytic
Light
Cycle Oil
45-65
25
25
7
35
6
2
Steam
Cracking Coal
By-Products Tars
70-95
20
10
18
45
5
2
95-100
5
5
3
75
10
2
Source: Asselin, G. F. and R. A. Erickson. "Benzene and Naphthalene
from Petroleum by the Hydeal Process." Chemical Engineering
Progress, 58 (April 1962), 47.
98
-------
Other literature sources indicate that heavy catalytic reformates contain
approximately 10% naphthalene in addition to 55% alkyl naphthalenes. In this
case the percentage of other components would be reduced.
In general it will be economically advantageous to extract aromatics from
a feed containing less than 70% aromatics before charging the feed to the deal-
kylation unit and economically disadvantageous to extract them from feeds
containing 95% or more aromatics. The economics of aromatics extraction have
to be studied on an individual basis for feeds in the range of 70-95% aromatics.
Aromatics extraction (Process 24) is described earlier in this catalog entry.
Table 46 presents the product yields for the Hydeal Process (UOP) processing
a heavy reformats feed which is 100% aromatics. Hydrogen makeup gas (90% by
Volume H2) requirements are 860 m3/m3 feed (4,815 scf/bbl feed).
Table 46. PRODUCT YIELDS FROM THE HYDEAL PROCESS
Yield of Products Yield of Products
Per m3 Feed Per Barrel Feed
Naphthalene 400 kg 140 Ibs
Benzene 0.20 m3 0.20 bbl
Heavy Product 0.04 m3 0.04 bbl
Off-Gas 730 m3(standard conditions) 4,105 scf
(Heating value 37 MG/m3;
1000 Btu/ft3
Source:Asselin, G.F. and R.A. Erickson."Benzene and Naphthalene from
Petroleum by the Hydeal Process." Chemical Engineering Progress,
58 (April 1962), 47.
3. Operating Parameters - The range of operating temperatures is 540-760°C
(1000-1400"F), and operating pressures range from 3.5 to 7.0 MPa (500-1200 psig).
Capacities of plants producing naphthalene from petroleum products range from
45 to 68 Gg per year (100-150xl06 pounds/year). Some processes do not use
catalysts; for those which do, it can be assumed that a catalyst of the same
general type used for toluene dealkylation (nonoble metal compounds) is used.
4. Utilities - Utility requirements for the Hydeal Process using a heavy
reformate (100% aromatic) feed to produce naphthalene are listed below in
Table 47.
Table 47. UTILITY REQUIREMENTS FOR HYDEAL PROCESS
Utility Utility Required
Required Per Kilogram Per Pound
Naphthalene Produced Naphthalene Produced
Fuel
Electricity
Cooling Water
23.2 MO
0.47 KWh
0.20 m3 (
10,000 Btu
0.21 KWh
23 gallons
Source: Same as Table 46.
99
-------
No steam requirements were listed for this process in the literature
consul ted,although high-pressure steam and low-pressure steam requirements
were listed for the same process optimized for benzene production.
5. Waste Streams - Available process descriptions do not address the subject
of waste streams; however, several observations can be made concerning poten-
tial problems.
Emissions of hydrocarbons to the atmosphere can be expected from
distillation unit vents and from pump seals and flanges. For processes
which use catalysts, catalyst decoking operations can be expected to release
particulates, sulfur oxides and carbon monoxide to the atmosphere. Atmospheric
emissions from process heaters are described in Process 31 for the Petroleum
Refining Industry. Waste streams resulting from cooling water treatment
are discussed in the Industry Description. Costs for chemicals are listed
in economic descriptions of these processes but the process descriptions
give no information as to the type of chemicals used or their fate.
Spent catalyst and acid treated clay used in purification form solid
waste streams. Landfill is the usual method of disposal. The pH and heavy
metal content of leachates from these materials would be of interest. The
nature of the substances sorbed by the clay has not been of concern to
developers of these processes. It is possible that some of the sorbed mate-
rials are toxic and could be mobilized to the environment by leaching of
landfill. Benzene purification processes consume 0.0002 to 0.0004 kilograms
clay per kilogram benzene purified.
6. EPA Source Classification Code - None exists.
7. References -
(1) Asselin, G. F. and R. A. Erickson. "Benzene and Naphthalene from
Petroleum by the Hydeal Process." Chemical Engineering Progress,
58 (April 1962), 47.
(2) Barbor, R. P. "Naphthalene from Catalytic Gas Oil." Oil and Gas
1 ( J., 21 May 1962, 123.
(3) Bland, William F. and Robert L. Davidson, eds. Petroleum Processing
Handbook. N.Y.: McGraw-Hill Book Company, 1967.
(4) Brownstein, Arthur M., ed. U.S. Petrochemicals. Technologies,
Markets, and Economics. Tulsa, Oklahoma: Petroleum Publishing
Company, 1972.
(5) Chemical Engineering, ed. Sources and Production Economics of
Chemical Products, 1973-1974. 1st ed. N.Y.: McGraw-Hill, 1974.
(6) Considine, Douglas M., ed. Chemical and Process Technology
Encyclopedia. N.Y.: McGraw-Hill Book Company, 1974.
100
-------
References (continued) -
(7) Erskine, Mimi G. "Naphthalene," 677.5020 G. Chemical Economics
Handbook. Menlo Park, California: Stanford Research Institute, 1970.
(8) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(9) Hawley, Gessner G. The Condensed Chemical Dictionary. 8th ed.
Revised by G. G. Hawley. N.Y.: Van Nostrand Reinhold Co.
(1971), 603.
(10) Hedley, W. H., et al. Potential Pollutants From Petrochemical
Processes. MRC-DA-406. Dayton, Ohio: Monsanto Research Corp.,
December 1973.
(11) Industrial and Engineering Chemistry, 54 (February 1962), 28.
(12) Petroleum Refiner, 40 (November 1961), 236, 251-2, 298.
(13) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 8. 2nd ed. N.Y.: Interscience Publishers, 1965.
(14) Stanford Research Institute. 1975 Directory of Chemical Producers,
U.S.A. Menlo Park, California: 1975.
(15) Stobaugh, Robert B. "Naphthalene: How, Where, Who—Future.'"
Hydrocarbon Processing, 45 (March 1966), 149-
101
-------
CRESOLS AND CRESLYIC ACIDS PRODUCTION PROCESSES
This operation includes the recovery of cresols and cresylic acids from
refinery waste streams but does not include coal tar processing methods, even
though most plants process both feedstocks. Also excluded from this dis-
cussion are synthetic methods of manufacture.
The operations are presented in two process descriptions: 26) Acidification
and 27) Separation. Each process encompasses several processing steps, and
the general processing scheme is illustrated in Figure 9. Quantitative infor-
mation was not readily available for utilities and emissions. Qualitative
descriptions are offered for waste stream information.
102
-------
Gaseous Emissions
Solid Waste
Liquid Waste
CAUSTIC WASTE
FROM REFINERY
O
GO
-1 \ SOLUTION
TO INCINERATION \ / | TO INCINERATION
J
TREATMENT
OR DISPOSAL
I C
SOLVENT
MAKEUP I
i
SEPARATION
IMPURITIES
CONTANNG
TH1OPHENE
DERIVATIVES
TO SALES
TO SALES
TO SALES
]
TO SALES
[
TO SALES
TO FURTHER
PROCESSING
OR DISPOSAL
Figure 9. CRESOLS AND CRESYLIC ACIDS PRODUCTION PROCESSES
-------
CRESOLS AND CRESYLIC ACIDS PRODUCTION PROCESS NO. 26
Acidification
1. Function - This process acidifies caustic petroleum refinery wastes to
convert the alkoxides to hydroxyl groups. There may be three processing
steps involved: preparation, springing, and separation.
The preparation step is variable and depends on the feed and the process
design. The feed stream may be devolatilized to remove the remaining hydro-
carbon gases which may be vented or flared. In some installations the
mercaptans and thiols are oxidized under alkaline conditions with air and
steam to separate the sulfur compounds as disulfides. The products of this
step are pumped into a settling tank from which the separation is made by
decanting. The disulfide layer is incinerated. Other cresol recovery plants
do not have preparation steps, using the raw refinery stream as feed to
springing instead.
The prepared stream is pumped to a packed springing tower in which the
actual acidification takes place. The aqueous feed stream is contacted
countercurrently with C02, often in the form of flue gas. This step converts
the sodium phenates and cresylates to phenol and cresols. To minimize cresol
solubility, the flue gas composition is carefully controlled for an optimum
carbonate-bicarbonate level.
The acids are decanted from the water in settling tanks. They may be
further dried by distillation before they are fractionated. The phenolic
layer enters a fractionation column in which light and heavy ends are removed
and incinerated, while the mid-boiling range material is sent to processing
in the solvent extraction unit. The aqueous sodium carbonate layer contains
phenols whose concentrations may be reduced by absorption and stripping.
Resultant wastewater contains phenols in quantities great enough to necessitate
careful disposal and/or treatment.
2. Input Materials - Caustic waste from refineries is the feed stream to this
process. This waste stream may contain 6-50% tar acids along with 10% thiols.
Table 48 presents the composition of a typical spent caustic stream.
104
-------
Table 48. TYPICAL COMPOSITION OF CAUSTIC STREAM FROM REFINERY
Compound
Phenol
o-cresol
m-cresol
p-cresol
2,4-& 2,5-xylenols
3,4-xylenols
2,3-& 3,5-xylenols
Higher phenolics
Mercaptans
Sodium hydroxide
Napthenic acids
Carboxylic acids
Neutral oil
Water
Composition (%)
~20
18
22
9
25% 8
8
12
3
•^•w*
10
10
0.2
0.2
1.0
54
Source: Chemical Engineering, 20 August 1962, 66.
Other required input materials are flue gas (8-14% C02) or C02, and air
and/or steam for oxidizing the feed.
3. Operating Parameters - The fractionating column separates substances that
distill below 100°C as light ends and substances boiling above 235°C as heavy
ends.
On plant reports a bubble-cap column of 11 meters (35 ft) by 0.91 meters
(3 ft) diameter for the separation step. The same plant utilized an 18 meter
(60 ft) by 1.8 meter (6 ft) diameter springing tower packed with Raschig rings.
4- Utilities - Steam is required for oxidation and for rebelling; cooling
water is required for condensing; energy is required for pumps.
5. Waste Streams - The aqueous solution resulting from springing has the
potential for being a pollution problem. The phenol content of this stream
may be as high as 2 to 6 % of the original feed concentration. Concentrations
of some aqueous wastes from springing are presented in Table 49.
105
-------
Table 49. PHENOL CONTENT OF AQUEOUS WASTES FROM EIGHT SPRINGING PROCESSES
Stream
1
2
3
4
5
6
7
8
Concentration of Phenols
(ppm)
8,000
7,000
2,000
400
2,600
3,000 - 10,000
1500
12,000
Source: Beycbok, Milton R. Aqueous Wastes from Petroleum and Petrochemical
Plants. Great Britain: John Wiley & Sons, 1967.
If solvent extraction is used to recover phenols from this stream, the
concentration may be reduced to 100 ppm. Biological treatment methods have
been reported for further reducing phenol concentrations. One plant reports
disposal of waste containing 100 ppm phenols in subsurface strata. Emissions
from cooling water and steam generation systems are discussed in the Industry
Description.
6. EPA Source Classification Code - None exists.
7. References -
(1) Beychok, Milton R. Aqueous Wastes from Petroleum and Petrochemical
Plants. Great Britain: John Wiley & Sons, 1967.
(2) Chemical Engineering, July 1957, 228.
(3) Chemical Engineering, 20 August 1962, 66.
(4) Hahn, Alvert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(5) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical Tech-
nology, Vol. 6. 2nd ed. N.Y.: Interscience Publishers, 1965.
106
-------
CRESOLS AND CRESYLIC ACIDS PRODUCTION PROCESS NO. 27
Product Recovery
1. Function - The tar acids from the acidification process (Process No. 26)
are separated into marketable products in this process. Two processing steps
are identified: solvent extraction and fractionation.
Solvent extraction is typically done with aqueous methanol and naphtha.
The phenols are concentrated in the methanol layer, while the naphtha removes
most of the impurities including thiophenols. The naphtha stream is
stripped for recycle of the naphtha. Thiophenols and thiocresols may be
recovered from the impurities, but in many instances the impurities are
incinerated. The methanol stream is stripped before the phenolic stream
is pumped to a separating tank where water is removed. The acid stream is
then fed to a series of fractional distillation columns for separation of
phenol, o-cresol, m-& p-cresol and mixed xylenols. A mixed cresylic acids
cut may be taken. Cresylic acid product is defined as a mixture of cresols,
xylenols, and phenols, 50% of which boil above 204°C. There may be an
ion-exchange column present in this section of the plant to remove traces
of mercaptans and bases from the phenolic compounds.
2. Input Materials - Typical tar acids contain 20% phenol, 18% o-cresol,
22% m-cresol, 9% p-cresol, 28% xylenols, and 3% higher phenolics. Makeup
requirements for solvents are assumed to be low because of recycle techniques.
3. Operating Parameters - Pitt Consol's Newark plant utilizes an 18 meter
(60 ft) by 0.9 meter (3 ft) diameter Scheibel extractor for the solvent
extraction step. The methanol and naphtha flow countercurrently; the acid
stream flows cocurrently with the methanol. The fractionation takes place
in 0.9 meter (3 ft) diameter bubble-cap columns 18-23 meters (60 to 75 ft)
tall. The settling tanks have a reported capacity of 30.3 m3 (8000 gal).
Fractionation equipment for this process is usually of stainless steel
or stainless-clad mild steel, as regular steel causes discoloration of
product.
4. Utilities - Quantitative data are not readily available in the literature
consulted. Steam and cooling water are required for fractionation columns.
Energy for pumping various plant streams is required.
5. Waste Streams - Wastewater contaminated with phenolic compounds is
generated from the aqueous methanol extraction. No information was found
on the final disposition or treatment of this wastewater.
Fractionation columns are sources of intermittent and fugitive hydrocarbon
emissions.
Incineration of impurities from the naphtha stream is a potential source
of S0x emissions.
107
-------
Emissions from cooling water and steam generation systems are discussed
in the Industry Description.
6. EPA Source Classification Code - None exists
7. References
(1) Beychok, Milton R. Aqueous Wastes from Petroleum and Petrochemical
Plants. Great Britain: John Wiley & Sons, 1967.
(2) Chemical Engineering, July 1957, 228.
(3) Chemical Engineering, 20 August 1962, 66.
(4) Hahn, Albert V. The Petrochemical Industry, Market and Economics.
N.Y.: McGraw-Hill Book Company, 1970.
(5) Standon, Anthony, ed. Kirk-Othmer Encyclopedia of Chemical Technology,
Vol. 6. 2nd ed. N.Y.: Interscience Publishers, 1965.
108
-------
NORMAL PARAFFIN PRODUCTION PROCESSES
In this operation normal paraffins are separated from branched and
cyclic compounds. The separation is effected by sorption of the normal
paraffins onto molecular sieves followed by recovery from the sieves.
The boiling range of the normal paraffin product is determined by the
boiling range of the feed material. Naphthas, kerosenes, or light gas-oils
may be used as feeds. The most important applications of this process
are to kerosenes and light gas-oils to produce normal paraffins which are
used in the manufacture of biodegradable detergents. The literature
contains descriptions of a urea process, but no commercial installations
using this process are being operated in the United States.
The flowsheet in Figure 10 describes normal paraffin production.
109
-------
NAPHTHA
KEROSENE OR
LIGHT GAS-OIL
O Gaseous Emissions
Solid Waste
-to
SEPARATION
OF
NORMAL
PARAFFINS
28
TO GASOLINE
BLENDING
OR CATALYTIC
CRACKING
TO STORAGE
Liquid Waste
Figure 10. NORMAL PARAFFIN PRODUCTION PROCESSES
-------
NORMAL PARAFFIN PRODUCTION PROCESS NO. 28
Separation of Normal Paraffins
1. Function - In this process normal paraffins as a class are separated
from branched and cyclic hydrocarbons. The feed may be a naphtha, kerosene
or light gas-oil. The two product streams consist of normal paraffins in
one stream and a raffinate essentially free (less than 1%) from normal
paraffins in the other stream. The raffinate from light naphthas is used
as a component of gasoline. The raffinate from kerosene feed is suitable
only as a catalytic cracker feedstock.
The separation is effected by adsorption of the normal paraffin portion
of the feed onto synthetic zeolites (molecular sieves). The adsorption
phase of the process may be carried out with the feed in the vapor phase
or the liquid phase depending on the exact process. Branched and cyclic
compounds are not adsorbed and become the raffinate. The normal paraffin
product is removed from the artificial zeolite by a reduction in pressure,
by elution with a recycle stream of light normal paraffins, or by heating.
Adsorption-desorption may be carried out in a series of vessels cyclically
or in a single vessel continuously. Separation of product from the elution
stream may be effected by distillation.
The uses of the product depend on the nature of the feed. A light
naphtha yields normal paraffins in the C5-C7 range for use as hydrocarbon
specialty solvents. A kerosene feed yields normal paraffins in the C10-Ci3
or Cio-Cis range depending on the breadth of the cut of the feedstock.
2. Input Materials - Naphthas, kerosenes, and light gas-oils are used as
feedstocks. The boiling fraction used will depend on the product desired.
The yield of normal paraffins depends on the normal paraffin content of
the feed. The separation is quite effective. The normal paraffin product
typically contains no more than 1 to 2% branched and cyclic compounds and
the raffinate typically contains no more than 1 to 2% normal compounds.
Feeds containing 20 to 40% normal paraffins are typical. Coking consumes
a small fraction of the feedstock, especially in those processes which
use adsorption from the vapor phase.
3. Operating Parameters - The capacity of units reported to be in operation
in 1971 ranged from 27 to 110 Gg/year (60-240xl06 Ibs/yr). Precise operating
conditions were not available but were reported to be within the temperature
and pressure ranges common to refinery and petrochemical operations.
4. Utilities - Utility requirements vary according to process and feed-
stock. Typical requirements for the Iso Siv (Union Carbide Corporation,
111
-------
Linde Division) process for naphtha feeds and for kerosene feeds are listed
in Table 50 below.
Table 50. UTILITY REQUIREMENTS FOR ISO SIV PROCESS
Naphtha Feed
Process Heat
Electric Power
Cooling Water
MJ/kg rv-paraffin product
Btu/lb jvparaffin product
kWh/kg iT-paraffin product
kWh/kg n-paraffin product
m3/kg n-paraffin product
gallons/1 b n-paraffin product
1.3
560
0.066
0.030
0.0267
3.2
Kerosene Feed
6.9
2,960
0.053
0.024
0.0876
10.5
Source: "Petrochemical Handbook." Hydrocarbon Processing, 54 (November
1975), 167.
"Refining Handbook." Hydrocarbon Processing, 49 (September 1970),
271, 273.
"Refining Handbook." Hydrocarbon Processing, 53 (September 1974),
199, 203.
5. Waste Streams - This is primarily a separation process and there are
no waste streams as such. Coking occurs in the vapor-phase adsorption
processes, and the de-coking operation can be expected to release parti-
culates, sulfur oxides and carbon monoxide to the atmosphere. Fugitive
emissions of light hydrocarbons can be expected from pump seals, valves
and relief vents. Atmospheric emissions from process heaters are described
in Process 31 for the Petroleum Refining Industry. Waste streams resulting
from cooling water treatment are discussed in the Industry Description.
Costs for chemicals are listed in economic descriptions of this process,
but the process description gives no information as to the type of chemicals
used or their fate. Spent sorbent represents a solid waste which is land-
filled.
6. EPA Source Classification Code - None exists.
7. References -
(1) Considine, Douglas M., ed. Chemical and Process Technology
Encylcopedia. N.Y.: McGraw-Hill Book Company, 1974.
(2) Hahn, Albert V. The Petrochemical Industry, Market and Economics,
N.Y.: McGraw-Hill Book Company, 1970.
(3) Hedley, W. H., et al. Potential Pollutants from Petrochemicals
Processes. MRC-DA-406. Dayton, Ohio: Monsanto Research Corp.,
December 1973.
112
-------
(4) "Petrochemical Handbook." .Hydrocarbon Processing, 50 (November
1971), 184.
(5) "Petrochemical Handbook." Hydrocarbon Processing, 52 (November
1973), 154.
(6) "Petrochemical Handbook." Hydrocarbon Processing, 54 (November
1975), 167.
(7) "Refining Handbook." Hydrocarbon Processing, 49 (September 1970),
271, 273.
(8) "Refining Handbook." Hydrocarbon Processing, 53 (September 1974),
199, 203.
113
-------
APPENDIX A
RAW MATERIALS
115
-------
Table A-l HYDROCARBON RAW MATERIALS FOR
THE BASIC PETROCHEMICALS INDUSTRY
Raw Material
Description
Naphtha
Kerosene
Gas Oil
Natural Gas Liquids
Refinery Gases
Butylenes
Heavy Feedstocks
Caustic Extract
Catalytic Reformate
Pyrolysis Gasoline
Mixed Ct, Stream
Catalytic Cycle Oil
Thermal Cracking Bottoms
petroleum fraction boiling in the approximate
range of 90 to 200°C (200-400 F).
petroleum fraction with boiling range of 180 to
300°C (360-570°F)
petroleum distillate with boiling range of 230
to 430°C (450-800°F)
ethane, ethane/propane, propane, butane and higher
products from Oil and Gas Production Industry
gases from cracking, light ends from crude
distillation, etc. Composition variable
C
-------
APPENDIX B
PRODUCTS
117
-------
Table B-l PRODUCTS AND BY-PRODUCTS OF THE
BASIC PETROCHEMICALS INDUSTRY
Operation
Products
By-products
Olefins Production
Butadiene Production
BTX Production
Naphthalene Production
Production of Cresols and
Cresylic Acids
Separation of Normal
Pafaffins
ethylene
propylene
normal butenes
butadiene
isobutylene or poly-
merized product
benzene
toluene
mixed or solvent xylenes
ethyl benzene
ortho-xylene
para-xylene
meta-xylene
naphthalene
meta-, para-cresol
mixture
ortho-cresol
xylenols
phenol
cresylic acids
C5-C7 normal paraffins
o-Cia or Cio-Cj 5
normal paraffins
pyrolysis gasoline
mixed C^ stream
hydrogen
methane
fuel oil
C9 aromatics
fuel gas (methane)
raffinate containing
paraffins and naph-
thenes suitable for
cracking feedstock
fuel gas
high octane naptha
or benzene
heavy oil rich in
aromatics
thiocresylic acids
and derivatives of
thiophenol
gasoline blending
stock containing
branched chain and
cyclic compounds
catalytic cracking
feedstock containing
branched chain and
cyclic compounds
118
-------
APPENDIX C
PRODUCERS OF BASIC PETROCHEMICALS AND PRODUCTION LOCATIONS
119
-------
Table C-l. BENZENE PRODUCERS
Company
Allied Chemical
Corporation
Amerada Hess
Corporation
American Petro-
fina, Inc.
Ashland Oil , Inc.
Atlantic Richfield
Company
Atlantic Richfield
Co. /Union Oil
Company of Calif.
Charter Inter-
national Oil Co.
Cities Service
Co. , Inc.
Coastal States Gas
'reducing Co.
Location
Winnie, Texas
St. Croix.
Virgin Islands
Port Arthur,
Texas
Ashland (Catletts-
burg) , Kentucky
Tonawanda (Buffalo),
New York
Houston, Texas
Wilmington,
Delaware
Bethlehem,
Pennsylvania
Lackawanna,
New York
Sparrows Point,
Maryland
Nederland, Texas
Houston, Texas
Lake Charles,
Louisiana
Corpus Christi,
Texas
1975 Capacity
Gg (106 lb)a
10 (20)
50 (110)
50 (110)
166 (365)
50 (110)
148 (325)
54 (120)
9 (20)
25 (55)
50 (110)
68 (150)
16 (35)
84 (185)
234 (515)
Uses
Styrene; phenol ;
synthetic detergents;
cyclohexane for nylon;
aniline; DDT; maleic
anhydride; dichloro-
benzene; benzene
hexachloride; nitro-
benzene; diphenyl ;
insecticides,
fumigants; solvent;
paint remover; rubber
cement; antiknock
gasoline.
120
-------
Table C-l. (Cont'd) BENZENE PRODUCERS
Company
Location
1975 Capacity
Gg (106 lb)d
Uses
Commonwealth Oil
Refining Company
Cosden Oil &
Chemicals
Crown Central
Petroleum Corp.
The Dow Chemical
Company
Exxon Corp.
Gulf Oil Corp.
Kerr-McGee Corp.
Marathon Oil Co.
Mobil Oil Corp.
Monsanto Company
Penzoil United,
Inc.
Phillips Petroleum
Company
Penuelas,
Puerto Rico
Big Spring, Texas
Pasadena, Texas
Bay City, Michigan
Freeport, Texas
Baton Rouge,
Louisiana
Baytown, Texas
Alliance, Louisiana
Philadelphia,
Pennsylvania
Port Arthur, Texas
Toledo, Ohio
Corpus Christi,
Texas
Detroit, Michigan
Texas City, Texas
Beaumont, Texas
Alvin (Chocolate
Bayou), Texas
Shreveport,
Louisiana
Sweeny, Texas
Guayama, Puerto Rico
121
617 (1360)
100 (220)
66 (145)
100 (220)
134 (295)
241 (530)
207 (455)
234 (515)
109 (240)
127 (280)
2 (5)
27 (60)
23 (50)
20 (45)
200 (440)
250 (550)
41 (90)
73 (160)
367 (810)
-------
Table C-l. (Cont'd) BENZENE PRODUCERS
Company
Location
1975 Capacity
Gg (106 lb)a
Uses
Shell Oil Company
Skelly Oil Company
Southwestern Oil
& Refining Co.
Standard Oil Com-
pany of California
Standard Oil Com-
pany of Indiana
Standard Oil Com-
pany (New Jersey)
Standard Oil Com-
pany (Ohio)
Sun Oil Company
Tenneco, Inc.
Texaco, Inc.
Union Carbide
Corporation
Deer Park, Texas
Odessa, Texas
Wilmington, Calif.
Wood River, Illinois
El Dorado, Kansas
Corpus Christi
Texas
El Segundo,
California
Texas City, Texas
Baton Rouge,
Louisiana
Baytown, Texas
Port Arthur, Texas
Marcus Hook,
Pennsylvania
Corpus Christi, Texas
Tulsa, Oklahoma
Chalmette, Louisian
Port Arthur, Texas
Westville, New Jersey
Taft, Louisiana
250 (550)
16 (35)
66 (145)
134 (295)
48 (105)
30 (65)
50 (110)
284 (625)
222 (490)
222 (490)
57 (125)
50 (110)
100 (220)
79 (175)
34 (75)
150 (330)
116 (255)
166 (365)
122
-------
Table C-l. (Cont'd) BENZENE PRODUCERS
Company
Union Oil Company
of California
Union Pacific
Corporation
Location
Lemont, Illinois
Corpus Christi,
Texas
1975 Capacity
Gg (106 lb)a
109 (240)
34 (75)
Uses
Total capacity 1975
6.11 Tg/yr (13,670 x 106 Ib/yr)
a Estimates assumed accurate to the nearest 5 x 106 Ib. Conversions made to the
same number of significant figures or to the nearest Gg.
This compares favorably with total production reported in Chemical and Engineering
News for benzpe iM!Z3J5.*42.J.ft« llJQjLiQ6 jb) and inj.974 (5.65 Tg,
T2^ * lp6 If). Of the 1974 total. 57672 Ta_Q«0 x 106 Jb) was produced from
coke batteries, coTe Wen'materials~smppecTto p'e'trbTeurirreriheries and coal tar
distillation plants.
Source: Monsanto Research Corporation
123
-------
Table C-2. BUTADIENE PRODUCERS
Company
Arco Chemical
Company
Copolymer Rubber
& Chemical Corp.
Dow Chemical
U.S.A.
El Paso Natural
Gas Co.
Exxon Corp.
The Firestone
Tire and Rubber
Co.
Getty Oil Co.
Mobile Oil Corp.
Monsanto Co.
Neches Butane
Products Co.
Northern Natural
Gas
Petro-Tex Chemical
Corp.
Phillips Petroleum
Co.
Puerto Rico
Olefins Co.
Shell Chemical Co.
Standard Oil
(Indiana)
Location
Channelview,
Texas
Baton Rouge,
Louisiana
Bay City,
Michigan
Freeport, Texas
Odessa, Texas
Baton Rouge,
Louisiana
Orange, Texas
Delaware City,
Delaware
Beaumont, Texas
Chocolate Bayou,
Texas
Port Neches, Texas
Morris, Illinois
Houston, Texas
Phillips, Texas
Penuelas,
Puerto Rico
Deer Park, Texas
Chocolate Bayou,
Texas
Capacity
Gg (106lb)/yra
127 (280)
58 (130)
11 (25)
39 (85)
91 (200)
154 (340)
100 (220)
9 (20)
36 (80)
55 (120)
290 (640)
30 (65)
450 (990)
130 (290)
90 (200)
120 (265)
41 (90)
Uses
Styrene-butadiene
rubber, polybuta-
diene and nitrile
elastomers; adipo-
nitrile (Nylon 66);
latex paints; resins;
organic intermediates;
ABS plastics.
124
-------
Table C-2. (Continued) BUTADIENE PRODUCERS
Company
Union Carbide
Corp.
Location
Seadrift, Texas
Taft, Louisiana
Texas City, Texas
Penuelas,
Puerto Rico
Capacity
Gg (10 lb)/hra
20 (45)
41 (90)
20 (45)
70 (155)
Uses
Total
1985 (4375)
a Estimates assumed accurate to the nearest 5 x 106 Ibs. Conversions made
to the same number of significant figures or to the nearest Gg.
Source: Monsanto Research Corporation
125
-------
Table C-3. CRESOLS AND CRESYLIC ACIDS PRODUCERS4
Company
Merichem Co.
Northwest
Petroleum
Pitt-Consol
Products Chem.
Co.
Location
Houston, Texas
Anacortes,
Washington
Newark,
New Jersey
Santa Fe Springs,
California
Capacity13
G,g (106lb)/yr
45 (100)
7 (15)
23 (50)
14 (30)
Uses
Phosphate esters,
magnet wire, anti-
oxidants, resins,
cleaning and dis-
infectant, ore
flotation.
Total
89 (195)
Recovery from petroleum sources. Some synthetic production reported at
Pitt-Consol.
Estimates assumed accurate to the nearest 5 x 106 Ibs. Conversions made to
the same number of significant figures or to the nearest Gg.
Source: Medley, W.H., et al. Potential Pollutants From Petrochemical Processes
MRC-DA-406. Dayton, Ohio: Monsanto Research Corp., Decmeber 1973.
126
-------
Table C-4. ETHYLENE PRODUCERS
Comp.an.y
Allied Chemical
Corp., BASF
Wyandotte Corp.,
Borg-Warner Corp.
Arco Chemical
Company
Arco/ Polymers,
Inc.
Chemplex Company
Cities Service
Company, Inc.
Conoco Chemicals
Dow Chemical
U.S.A.
E.I. du Pont de
Nemours & Co.,
Inc.
Eastman Chemical
Products, Inc.
El Paso Products
Co., Dart
Industries, Inc.
Exxon Chemical
Company, U.S.A.
B.F. Goodrich
Chemical Company
Location
Geismar, Louisiana
Wilmington,
California
Houston, Texas
Clinton, Iowa
Lake Charles,
Louisiana
Lake Charles,
Louisiana
Bay City/Midland,
Michigan
Freeport/ Oyster
Creek, Texas
Plaquemine,
Louisiana
Orange, Texas
Long view, Texas
Odessa, Texas
Baton Rouge,
Louisiana
Bay town, Texas
Calvert City,
Kentucky
Capacity as ofa
31 December 1974
Gg (106 lb)/yr
340 (750)
45 (100)
227 (500)
277 (500)
426 (940)
295 (650)
77 (170)
1.1 Tg (2500)
499 (1100)
340 (750)
363 (800)
234 (517)
771 (1700)
32 (70)
159 (350)
Uses
Manufacture of ethyl
alcohol , ethyl ene
glycols, ethyl ene
dichloride, aluminum
alkyls, vinyl chloride,
ethyl chloride, ethyl -
ene oxide, ethyl ene
chlorohydrin, acetal-
dehyde, linear alcohols,
polystyrene, styrene,
polyethylene, poly-
vinyl chloride, SBR,
polyester resins,
trichloroethylene,
etc.; refrigerant;
cryogenic research;
agricultural chemistry;
welding and cutting
of metals, anesthetic.
127
-------
Table C-4. (Continued) ETHYLENE PRODUCERS
Company
Location
Capacity as of
31 December 1974
Gg (106 lb)/yr
Uses
Gulf Oil
Chemicals Company
Jefferson
Chemical Company,
Inc.
Mobil iChemical
Company
Monsanto Company
National Distil-
lers & Chemical
Corp.
Northern Petro-
chemical Company
01 in Corporation
Petro Gas
Producing Co.
Phillips Petro-
leum Company
Puerto Rico
Olefins Company
Shell Oil Company
Sunolin Chemical
Company
Union Carbide
Corporation
Cedar Bayou, Texas
Port Arthur, Texas
Port Neches, Texas
Beaumont, Texas
Alvin (Chocolate
Bayou), Texas City,
Texas
Tuscola, Illinois
East Morris
(Joliet), Illinois
Brandenburg,
Kentucky
Port Arthur, Texas
Sweeney, Texas
Penuelas, Puerto
Rico
Deer Park, Texas
Norco, Louisiana
Claymont, Delaware
Seadrift, Texas
Taft, Louisiana
190 (420)
522 (1150)
239 (525)
213 (470)
363 (800)
159 (350)
363 (800)
54 (120)
9 (20)
517 (1140)
454 (1000)
680 (1500)
249 (550)
102 (225)
549 (1210)
186 (410)
128
-------
Table C-4. (Continued) ETHYLENE PRODUCERS
Company
Union Carbide
Corporation
(Continued)
Union Carbide
Caribe, Inc.
Location
Texas City, Texas
Torrance,
California
Whiting, Indiana
Penuelas, Puerto
Rico
Capacity as ofa
31 December 1974
Gg (106 lb)/yr
77 (170)
77 (170)
68 (150)
351 (775)
Uses
Total 11.242 Tg (24,780)b
a Estimates assumed accurate to the nearest 5 x 106 Ibs. Conversions made
to the same number of significant figures or to the nearest Gg.
This is comparable to production figures reported by Chemical and Engineering
News for 1973 (10.128 Tg (22,329 x 10? lb)) and 1974 (10.669 Tg (23,522 x 106 lb))
Source: Monsanto Research Company
129
-------
Table C-5. NAPHTHALENE PRODUCERS'
Company
Ashland Oil , Inc.
Getty Oil Co.
Kewanee Oil Co.
Monsanto Co.
Sun Oil Co.
Location
Ashland, Kentucky
Delaware City.
Delaware
Solon, Ohio
Chocolate Bayou,
Texas
Toledo, Ohio
Capacity h
Gg (106 lb)/yr
45 (100)
45 (100)
Not Available
45 (100)
68 (150)
Uses
Phthalic anhydride
manufacture; in-
secticides; dyestuffs;
synthetic tanning
agents.
From Petroleum Sources
Estimates assumed accurate to the nearest 5 x 106 Ibs. Conversions made
to the same number of significant figures or to the nearest Gg.
Source: Stanford Research Institute. 1975 Directory of Chemical Producers, U.S.A.
Menlo Park, California: 1975.
130
-------
Table C-6. MIXED XYLENES PRODUCERS*
Company
American Petrofina
Inc.
Ashland Oil, Inc.
Atlantic Richfield
Company
Atlantic Richfield
Co., Union Oil
Company of
California
Charter Interna-
tional Oil Co.
Cities Service
Company, Inc.
Coastal States
Gas Producing Co.
Commonwealth Oil
Refining Co., Inc.
Crown Central
Petroleum Co.
Marathon Oil
Company
Monsanto Company
Phillips Petro-
leum Company
Shell Oil Company
Southwestern Oil
& Refining Co.
Location
Big Springs, Texas
Ashland, Kentucky
Buffalo (Tonawanda),
New York
Houston, Texas
Nederland, Texas
Houston, Texas
Lake Charles,
Louisiana
Corpus Chris ti,
Texas
Penuelas,
Puerto Rico
Houston, Texas
Detroit, Michigan
Texas City, Texas
Alvin (Chocolate
Bayou), Texas
Guayama ,
Puerto Rico
Deer Park (Houston),
Texas
Corpus Christi,
Texas
Capacity as of
1 July 1971 ,
Gg. (10* lb)/yrb
59 (130)
81 (180)
50 (110)
196 (430)
81 (180)
72 (160)
236 (520)
77 (170)
259 (570)
45 (100)
16 (35)
45 (100)
134 (295)
327 (720)
229 (505)
59 (130)
Uses
Aviation gasoline;
protective coatings;
solvent for alkyd
resins, lacquers,
enamels, rubber cements;
synthesis of organic
chemicals.
131
-------
Table C-6. (Continued) MIXED XYLENES PRODUCERS'
Company
Location
Capacity as of
1 July 1971 .
Gg (10* lb)/yrD
Uses
Standard Oil of
California
Standard Oil Co.
(Indiana)
Standard Oil Co.
(New Jersey)
Sun Oil Company
Tenneco, Inc.
Union Carbide
Corp.
Union Oil Co. of
California
Union Pacific
Railroad Co.
El Segundo,
California
Pascagoula,
Mississippi
Richmond, California
Texas City, Texas
Baytown, Texas
Marcus Hook,
Pennsylvania
Corpus Christi,
Texas
Chalmette, Louisiana
Taft, Louisiana
Lemont, Illinois
Corpus Christi,
Texas
75 (165)
211 (465)
159 (350)
488 (1075)
390 (860)
98 (215)
114 (250)
163 (360)
32 (70)
32 (70)
59 (130)
Total
3.79 Tg (8340)(
a Production from petroleum.
Estimates assumed accurate to the nearest 5 x 106 Ibs. Conversions made
to the same number of significant figures or to the nearest Gg.
c According to Chemical and Engineering News, production for 1973 (2.56 Tg
[5635 x 106 lb]) and 1974 (5770 x 10b Ib [2.62 Tg]) was down somewhat from
1970-1971.
Source: Monsanto Research Corporation
132
-------
Table C-7. NORMAL PARAFFINS PRODUCERS9
Company
Continental Oil
Co.
Exxon Corp.
Shell Chem. Co.
South Hampton
Co.
Union Carbide
Corp.
Location
Baltimore,
Maryland
Westlake,
Louisiana
Bay town, Texas
Deer Park, Texas
Silsbee, Texas
Texas City, Texas
Capacity .
Gg (106 lb)/yrb
Not Available
102 (225)
100 (220)
45 (100)
27 (60)
109 (240)
Uses
C5- C7 used for
speciality solvents;
Cio- Cis used for
manufacture of bio-
degradable detergents,
plasticizers, alcohols,
fatty acids, proteins,
fire retardants.
Cio- Cis range capacity data.
Estimates assumed accurate to the nearest 5 x 106 Ib. Conversions made to
the same number of significant figures or to the nearest Gg.
Source: Chemical Marketing Reporter, 18 February 1974.
Hedley, W.H., et al. Potential Pollutants From Petrochemical Processes,
MRC-DA-406. Dayton, Ohio: Monsanto Research Corp., December 1973.
133
-------
Table C-8. PROPYLENE PRODUCERS
Company
Allied Chemical
Corp., BASF Wyan-
dotte Corp., Borg-
Warner Chemicals
Amerada Hess
Corporation
Amoco Chemicals
Corp.
Ashland Oil , Inc.
Atlantic Richfield
Co.
Charter Inter-
national Oil Co.
Chemplex Co.
Chevron Chemical
Co.
Location
Geismar, Louisiana
Port Reading,
New Jersey
Alvin (Chocolate
Bayou), Texas
Texas City, Texas
Whiting, Indiana
Wood River, Illinois
Ashland (Catletts-
burg), Kentucky
Louisville, Kentucky
Tonawanda, New York
Channel view, Texas
Wilmington,
California
Houston, Texas
Houston, Texas
Clinton, Iowa
El Segundo, v
California I
Lake Charles, /
Louisiana
Capacity as of
1 May 1975
Gg (106 lb)/yr
23 (50)
(chemical grade)
59 (130)
(polymer grade)
179 (395)
(chemical grade)
166 (365)
(chemical &
polymer grade)
91 (200)
59 (130)
75 (165)
14 (30)
23 (50)
98 (215)
(chemical &
refinery grade)
77 (170)
(chemical grade)
54 (120)
(chemical grade)
34 (75)
(chemical grade)
59 (130)
(chemical grade)
95 (210)
(chemical grade)
Uses
Isopropyl alcohol ,
polypropylene, syn-
thetic glycerol,
acrylonitrile, pro-
pylene oxide, heptene7
cumene, polymer gaso-
line, anticipated
use in acrylic acid
and in vinyl resins
134
-------
Table C-8. (Continued) PROPYLENE PRODUCERS
Company
Location
Capacity as of{
1. May 1975
Gfl (10* lb)/yr
Uses
Chevron Chemical
Company
Clark Oil & Refin-
ing Corporation
Cosden Oil &
Chemical Company
Dart Industries,
Inc., Rexene
Polymers Co./
El Paso Products
Co.
Dow Chemical
U.S.A.
E.I. du Pont de
Nemours & Co.
Exxon Chemical
Company, U.S.A.
B.F. Goodrich
Chemical Co.
Lake Charles,
Louisiana
Blue Island,
Illinois
Big Spring, Texas
El Dorado, Kansas
Mt. Pleasant
Odessa, Texas
Bay City/Midland,
Michigan
Freeport, Texas
Plaquemine,
Louisiana
Orange, Texas
Baton Rouge,
Louisiana
Baytown, Texas
Bayway, New Jersey
Calvert City,
Kentucky
240 (530)
(polymer grade)
32 (70)
59 (130)
16 (35)
25 (55)
79 (175)
(polymer grade)
45 (100)
(chemical grade)
272 (600)
(chemical grade)
95 (210)
(chemical grade)
61 (135)
(chemical grade)
508 (1,120)
(chemical grade)
249 (550)
(polymer grade)
145 (320)
(polymer grade)
64 (140)
(chemical grade)
135
-------
Table C-8. (Continued) PROPYLENE PRODUCERS
Company
Location
Capacity as ofa
I-May 1975
Gg (10* lb)/yr
Uses
Gulf Oil Corp.
Jefferson Chemi-
cal Company, Inc.
Marathon Oil Co.
Mobile Oil Corp.
Monsanto Company
Northern Petro-
chemical Co.
Petro Gas
Producing Co.
Phillips Petro-
leum Company
Puerto Rico
Olefins Company
Shell. Oil Company
Sun Oil Company
Cedar Bayou, Texas
Port Arthur, Texas
Port Neches, Texas
Detroit, Michigan
Texas City, Texas
Beaumont, Texas
Alvin (Chocolate
Bayou) Texas City,
Texas
Joliet (near East
Morris), Illinois
Port Arthur, Texas
Sweeney, Texas
Penuelas,
Puerto Rico
Deer Park, Texas
Norco, Louisiana
Corpus Christi,
Texas
57 (125)
(polymer grade)
168 (370)
(polymer grade)
59 (130)
(chemical grade)
45 (100)
(chemical grade)
91 (200)
(chemical grade)
109 (240)
(chemical &
polymer grade)
249 (550)
(chemical grade)
91 (200)
(polymer grade)
29 (65)
(chemical grade)
59 (130)
(polymer grade)
295 (650)
(polymer grade)
431 (950)
(chemical grade)
100 (220)
(chemical. &
polymer grade)
50 (110)
(chemical grade)
136
-------
Table C-8. (Continued) PROPYLENE PRODUCERS
Company
Sun Oil Company
Texas City
Refining, Inc.
Texas Eastman
Company
Union Carbide
Corp.
Vistron
Corporation
Total
Location
Marcus Hook,
Pennsylvania
Texas City, Texas
Long view, Texas
Seadrift, Texas
Taft, Louisiana
Texas City, Texas
Whiting, Indiana
Ponce (Penuelas)
Puerto Rico
Lima, Ohio
Capacity as of
1 May 1975
Gq (106 lb)/yr
154 (340)
(polymer grade)
45 (100)
(chemical grade)
>181 (>400)
(chemical &
polymer grade)
50 (110)
(chemical grade)
91 (200)
(chemical grade)
109 (240)
(chemical grade)
125 (275)
(chemical grade)
209 (460)
(chemical grade)
122 (270)
(chemical grade)
Uses
5.915 Tg (13,040)
a Estimates assumed accurate to the nearest 5 x 106 Ib. Conversions made to
the same number of significant figures or to the nearest Gg.
Source; Monsanto Research Corporation
137
-------
Table C-9. TOLUENE PRODUCERS'
Company
Amerada Hess
Corporation
American Petrofin
Inc.
Ashland Oil , Inc.
Atlantic Richfiel
Company
Charter Inter-
national Company
Coastal States
Gas Producing Co.
Commonwealth Oil
Refining Co., Inc
Crown Central
Petroleum Corp.
The Dow Chemical
Company
Gulf Oil Corp.
,
Marathon Oil Co.
Mobil Oil Corp.
Location
St. Croix,
Virgin Islands
Big Spring, Texas
Ashland (Catletts-
burg), Kentucky
Tonawanda (Buffalo)
New York
Houston, Texas
Wilmington,
California
Houston, Texas
Corpus Chris ti,
Texas
Penuelas,
Puerto Rico
Houston, Texas
Bay City,
Michigan
Philadelphia,
Pennsylvania
Port Arthur, Texas
Detroit, Michigan
Texas City, Texas
Beaumont, Texas
Capacity as of
1 September 1972
Cg (106 lb)/yrb
130 (290)
50 (110)
98 (215)
66 (145)
118 (260)
73 (160)
52 (115)
98 (215)
66 (145)
46 (100)
59 (130)
66 (145)
27 (60)
50x (110)
43 (95)
229 (505)
Uses
138
-------
Table C-9. (Continued) TOLUENE PRODUCERS3
Company
Location
Capacity as of
1 September 1972
Gg (106 lb)/yrb
Uses
Monsanto Company
Phillips Petroleum
Company
Shell Oil Company
Southwestern Oil
& Refining Co.
Standard Oil Co.
of California
Standard Oil Co.
(Indiana)
Standard Oil Co.
(New Jersey)
The Standard Oil
Company (Ohio)
Sun Oil Company
Swi'ft and Company
Tenneco, Inc.
Texaco, Inc.
Alvin (Chocolate
Bayou), Texas
Sweeney, Texas
Guayama, Puerto Rico
Deer Park, Texas
Corpus Christi,
Texas
El Segundo,
California
Texas City, Texas
Baton Rouge,
Louisiana
Baytown, Texas
Marcus Hook,
Pennsylvania
Port Arthur, Texas
Marcus Hook,
Pennsylvania
Tulsa, Oklahoma
Corpus Christi,
Texas
Potwin, Kansas
Chalmette,
Louisiana
Westville,
New Jersey
147 (325)
32 (70)
263 (580)
163 (360)
66 (145)
66 (145)
524 (1155)
213 (470)
213 (470)
27 (60)
59 (130)
100 (220)
66 (145)
79 (175)
39 (85)
50 (110)
98 (215)
139
-------
Table C-9. (Continued) TOLUENE PRODUCERS3
Company
Union Carbide
Corporation
Union Oil of
California
Union Pacific
Corporation
Location
Taft, Louisiana
Letnont, Illinois
Beaumont, Texas
Corpus Christi,
Texas
— j
Capacity as of
1 September 1972
Gg (106 lb)/yr*>
66 (145)
59 (130)
66 (145)
43 (95)
Uses
...-
Total 3.71 Tg (8175) C
Petroleum producers only
Estimates assumed accurate to the nearest 5 x 106 Ib. Conversions made to
the same number of significant figures or to the nearest Gg.
c Chenrical and Engineering News production figures for 1973 were 3.13 Tg
(6915 x 10b Ib), and in 1974 were 3.40 Tg (7495 x 106 Ib).
Source: Monsanto Research Corporation
140
-------
Table C-10. BASIC PETROCHEMICAL PRODUCTION SITES DIRECTLY ASSOCIATED
WITH PETROLEUM REFINERIES (CLASSES 2, 3, and 4A)1'2
Classification2
2
3
2
4A
4A
4A
4A
3
2
4A
4A
2
4A
3
4A
4A
4A
4A
4A
3
3
2
4A
4A
4A
4A
4A
2
4A
4A
2
Company
Allied Chemical Corp.
Amerada Hess Corp.
Amerada Hess Corp.
American Petrofina, Inc.
Arco Chemical Co.
Arco Chemical Co.
Ashland Chemical Co.
Ashland Chemical Co.
Ashland Chemical Co.
Charter Chemicals
Chevron Chemical Co.
Chevron Chemical Co.
Chevron Chemical Co.
Cities Service Co., Inc.
Clark Chemical Co.
Coastal States Gas Co.
Commonwealth Oil Refining Co.
Continental Oil Co.
Cosden Oil and Chemical Co.
Cosden Oil and Chemical Co.
Cosden Oil and Chemical Co.
Crown Central Petroleum Corp.
El Paso Natural Gas Co.
Exxon Chemical Co.
Exxon Chemical Co.
Exxon Chemical Co
Getty Oil Co.
Gulf Oil Co.
Gulf Oil Co.
Gulf Oil Co.
Hercor Chemical Corp
Site
Winnie, TX
Port Reading, NJ
St. Croix, VI
Port Arthur, TX
East Chicago, IN
Houston, TX
Ashland, KY
Louisville, KY
North Tonawanda, NY
Houston, TX
El Sequndo, CA
Pascogoula, MS
Richmond, CA
Lake Charles, LA
Blue Island, IL
Corpus Christ!, TX
Penuelas, PR
Westlake, LA
Big Spring, TX
El Dorado, KA
Mt. Pleasant, TX
Pasadena, TX
Odessa, TX
Baton Rouge, LA
Baytown, TX
Baytown, NJ
Delaware City, DE
Alliance, LA
Philadelphia, PA
Port Arthur, TX
Penuelas, PR
Product3
B, NP
P
B, T, X
B, T
P
B, EB, E, P, T, X, OX, PX
B, N, P, T, X
P
B, P, T, X
B, EB, P, T, X, PX
B, P, T, PX
T, PX
BT, P, OX, PX, NP
B, E, P, X, OX, PX
P
B, P, T, X, OX
B, EB, T, X, OX
OC, C, CA, E, P, NP
B, EB, BT, P, T, X, OX
P
P
B, T, X, OX
BT, EB, E, P
B, BT, E, P
B, E, BT, P, OX, PX, NP
BT, P, T
BT, N, P
B, X
B, P, T
B, E, P, T
PX
141
-------
Table C-10.(Continued) BASIC PETROCHEMICAL PRODUCTION SITES DIRECTLY ASSOCIATED
WITH PETROLEUM REFINERIES (CLASSES 2, 3, and 4A)1'2
Classification2
Company
3
4A
4A
4A
3
4A
3
2
2
4A
4A
4A
4A
4A
2
2
4A
4A
2
4A
4A
4A
4A
4A
4A
2
3
4A
4A
4A
4A
Marathon Oil Co.
Marathon Oil Co.
Marathon Oil Co.
Mobil Oil Corp.
Mobil Oil Corp.
Northern Natural Gas Corp.
Oil Shale Corp.
Penzoil Co.
Phillips Petroleum Co.
Phillips Petroleum Co.
Phillips Petroleum Co.
Puerto Rico Olefins Co.
Shell Oil Co.
Shell Oil Co.
Shell Oil Co.
Shell Oil Co.
Shell Oil Co.
Skelly Oil Co.
South Hampton Co.
Standard of Indiana
Standard of Indiana
Standard of Indiana
Standard of Indiana
Standard of Indiana
Standard of Ohio
Standard of Ohio
Standard of Ohio
Sunoco
Sunoco
Sunoco
Sunoco
Site
Detroit, MI
Robinson, IL
Texas City, TX
Beaumont, TX
Paulsboro, NJ
Morris, IL
El Dorado, AR
Shreveport, LA
Borger, TX
Guayama, PR
Sweeny, TX
Penuelas, PR
Deer Park, TX
Norco, LA
Odessa, TX
Wilmington, CA
Wood River, IL
El Dorado, KA
Silsbee, TX
Chocolate Bayou, TX
Decature, AL
Texas City, TX
Wood River, IL
Yorktown, VA
Lima, OH
Marcus Hook, PA
Toledo, OH
Corpus, Christi, TX
Duncan, OK
Marcus Hook, PA
Toledo, OH
Product?
P
AN
B, P, T, X
B, BT, CA, E, P, T
CA
BT, E, P
P
B, NP
P
B, T, X, OX, PX
B, E, P, T
BT, E, P
jBj BT, E, P, T, X, OX, PX,
E, P
B
B
B
B, P, T
NP, X
BT, E, P
PX
B, EB, BT, P, T, X, PX
BT, P
H
P
T
P
B, EB, P, T, X, OX, PX
P
B, P, T, X
N, P
142
-------
Table C-10. (Continued) BASIC PETROCHEMICAL PRODUCTION SITES DIRECTLY ASSOCIATED
WITH PETROLEUM REFINERIES (CLASSES 2, 3, and 4A)1'2
Classification2
2
4A
4A
2
3
4A
2
4A
Company
Sunoco
Tenneco Chemicals, Inc.
Texaco, Inc.
Texaco, Inc.
Texas City Refining
Union Oil of California
Union Oil of California
Union Pacific Corp.; Champ!in
Site
Tulsa, OK
Chalmette, LA
Port Arthur, TX
Westville, NJ
Texas City, TX
Beaumont, TX
Lemont, IL
Corpus Christi, TX
Product3
B, T
B, EB, T, X, OX, PX
P, T
P, T
P
B, P, T, X
B, T, X
B, T, X
1 This list was prepared under EPA contract 68-02-1319, Task 51, using information
from the 1975 Directory of Chemical Producers and the April 7, 1975 issue of The Oil
and Gas Journal. Modifications were made based on production sites for normal paraffins
from A.V. Hahn. The Petrochemical Industry, p. 562.
2 Class Two represents refinery associated company sites producing basic petrochemicals
only and utilizing only separation techniques for the petrochemical production. An
example of this category would be a refinery producing BTX by distilling these products
from an aromatic rich stream.
Class Three represents refinery associated company sites which produce basic petro-
chemicals only, but also enhance feedstock yield by some initial processing (such as
a refinery utilizing an olefins plant to increase ethylene/propylene production).
Class Four represents chemical production sites which produce both basic petrochemicals
and industrial organic chemicals. This classification has been further subdivided
with regard to refinery association such that Class 4A is a refinery associated site
and Class 4B is not a refinery associated site.
3 The following codes are used to indicate products produced at the site
AN alkylnaphthalenes
B benzene
BT Cn olefins & diolefins
C mixed cresols
CA cresylic acids
E ethylene
EB ethyl benzene
H heptene
MX meta-xylene
N naphthalene
NP normal paraffins
OC ortho-cresol
OX ortho-xylene
P propylene
PC para-cresol
PX para-xylene
T toluene
X mixed xylenes
143
-------
Table C-ll. BASIC PETROCHEMICAL PRODUCTION SITES NOT DIRECTLY
ASSOCIATED WITH A PETROLEUM REFINERY (CLASS 4B)lt?
Company
Allied Chemical Corp.
American Cyanamid Corp
Arco Chemical Co.
Arco Chemical Co.
BASF Wyandotte Corp.
Chemplex Co.
Dow Chemical Co.
Dow Chemical Co.
Dow Chemical Co.
Dow Chemical Co.
E. I. du Pont de Nemours & Co.
Eastman Kodak Co.
Foster-Grant Co., Inc.
GAF Corp
BF Goodrich Chemical Co.
Gulf Oil Co.
Jefferson Chemical Co.
Kewanee Oil Co.
Merichem Co.
Monsanto Co.
Monsanto Co.
National Distillers and
Chemical Corp.
01 in Corp.
Petrogas Producing Co.
Petro-Tex Chemical Corp.
Productol Chemical Co.
Shell Oil Co.
Sherwin Williams Co.
Standard Chlorine Chemical Co.
Standard Chlorine Chemical Co.
Site
Geismar, LA
Boundbrook, NJ
Channel view, TX
Wilmington, CA
Geismar, LA
Clinton, IA
Bay City, MI
Freeport, TX
Midland, MI
Plaquemine, LA
Orange, TX
Longview, TX
Baton Rouge, LA
Joliet, IL
Calvert City, KY
Cedar Bayou, TX
Port Neches, TX
Solon, OH
Houston, TX
Chocolate Bayou, TX
Texas City, TX
Tuscula, IL
Brandenburg, KY
Groves, TX
Houston, TX
Santa Fe Springs, CA
Dominguez, CA
Chicago, IL
Delaware City, DE
Kearny, NJ
Product3
E
PC
BT, P, MX
B, E, P, T, X, NP
E, P
E, P
B, BT, E, P
B, BT, EB, E, P
EB, T
E, P
E, P
E, P
EB, T
N
E, P
BT, E, P
E, P
N
OC, C, CA
B, BT, EB, E, N, P, T, OX
EB, E, T
E
E
E, P
BT
OC, C, CA
P
PC
N
N
144
-------
Table C-ll.(Continued) BASIC PETROCHEMICAL PRODUCTION SITES NOT DIRECTLY
ASSOCIATED WITH A PETROLEUM REFINERY (CLASS 4B)1'2
Company
SunOlin Chemical Co.
Union Carbide Corp.
Unior Carbide Corp.
Union Carbide Corp.
Union Carbide Corp.
Union Carbide Corp
Union Carbide Corp.
Site
Claymont, DE
Penuelas, PR
Sea drift, TX
Taft, LA
Texas City, TX
Torrance, CA
Whiting, IN
Product3
E
BT, E, P, X
BT, EB, E, P, T
B, BT, E, P, T
BT, E, P, NP
E, P
E, P
1 This list was prepared under EPA contract 68-02-1319, Task 51, using information
from the 1975 Directory of Chemical Producers and the April 7, 1975 issue of The
Oil a n d Ga s Journal. Modifications were made based on production sites for normal
paraffins from A.V. Hahn. The Petrochemical Industry. P. 562.
2 Class Two represents refinery-associated company sites producing basic petro-
chemicals only and utilizing only separation techniques for the petrochemical
production. An example of this category would be a refinery producing BTX by
distilling these products from an aromatic rich stream.
Class Three represents refinery-associated company sites whicn produce basic petro-
chemicals only, but also enhance feedstock yield by some initial processing (such
as a refinery utilizing an olefins plant to increase ethylene/propylene production).
Class Four represents chemical production sites which produce both basic petro-
chemicals and industrial organic chemicals. This classification has been further
subdivided with regard to refinery association such that Class 4A is a refinery-
associated site and Class 4B is not a refinery-associated site.
3 The following codes are used to indicate products produced at the site
AN alky!naphthalenes N naphthalene
B benzene NP normal paraffins
BT Ci» olefins & diolefins OC ortho-cresol
C mixed cresols OX ortho-xylene
CA cresylic acids P propylene
E ethylene PC para-cresol
EB ethyl benzene PX para-xylene
H heptene T toluene
MX meta-xylene X mixed xylenes
145
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-SOO/2-77-0236
12.
NTB No. PB 266224/AS
3. RECIPIENT'S ACCESSION- NO.
4. TITLE AND SUBTITLE
Industrial Process Profiles for Environmental Use:
Chapter 5. Basic Petrochemicals Industry
5. REPORT DATE
January 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
T. B. Parsons, C. M. Thompson, and G. E. Wilkins
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Radian Corporation
P. O. Box 9948
Austin, Texas 78766
1AB015; ROAP 21AFH-025
11. CONTRACT/GRANT NO.
68-02-1319, Task 34
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Initial: 8/75-11/76
14. SPONSORING AGENCY CODE
EPA/600/13
is.SUPPLEMENTARY NOTES JERL-RTP project officer I. A. Jefcoat is no longer with EPA:
contact G. Tucker (IERL-RTP), Mail Drop 63, 919/541-2745.
16. ABSTRACT
The catalog was developed to aid in defining the environmental impacts of
U.S. industrial activity. Entries for each industry are in consistent format and form
separate chapters of the catalog. The basic petrochemicals industry includes com-
panies that treat hydrocarbon streams from the petroleum refining industry, as well as
natural gas liquids from the oil and gas production industry. From these raw mate-
rials, feedstocks are produced for the organic chemicals industry. The products are
pure or mixed chemicals for use as solvents or chemical intermediates. This industry
is described by six operations composed of related processes. Four chemical trees,
six process flow sheets, and 28 process descriptions characterize the industry. For
each process description, available data is presented on input materials, operating
parameters, utility requirements, and waste streams. Related information, provided
as appendices, includes company, raw material, and product data.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Industrial Processes
Chemical Engineering
Petrochemistry
Hydrocarbons
Natural Gas Liquids
Solvents
Process Assessment
Environmental Impact
Basic Petrochemical
Industry
Chemical Intermediates
13B
13H
07A
08G
07C
2 ID
UK
8. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
154
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
146
------- |