EPA-450/3-73-006<
NOVEMBER 1974
ENGINEERING AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE PETROCHEMICAL
INDUSTRY VOLUME 3:
ETHYLENE DICHLORIDE
MANUFACTURE
BY OXYCHLORINATION
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
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EPA-450/3-73-006-C
ENGINEERING AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE PETROCHEMICAL
INDUSTRY VOLUME 3:
ETHYLENE DICHLORIDE
MANUFACTURE
BY OXYCHLORINATION
by
W. A. Schwartz, F. G. Higgins, Jr. ,
J. A. Lee, R. Newirth, and J. W. Pervier
Houdry Division
Air Products and Chemicals, Inc.
P.O. Box 427
Marcus Hook , Pennsylvania 19061
Contract No. 68-02-0255
EPA Project Officer: Leslie B. Evans
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, N. C. 27711
November 1974
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This report is issued by the Environmental Protection Agency to report technical
data of interest to a limited number of readers. Copies are available free
of charge to Federal employees, current contractors and grantees, and nonprofit
organizations- as supplies permit-from the Air Pollution Technical information
Center, Environmental Protection Agency, Research Triangle Park, North
Carolina 27711; or, for a fee, from the National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22161.
This report was furnished to the Environmental Protection Agency by the
Houdry Division of Air Products and Chemicals, Inc. , in fulfillment of Contract
No. 68-02-0255. The contents of this report are reproduced herein as received
from the Houdry Division of Air Products and Chemicals, Inc. The opinions,
findings, and conclusions expressed are those of the author and not necessarily
those of the Environmental Protection Agency. Mention of company or product
names is not to be considered as an endorsement by the Environmental Protection
Agency.
Publication No. EPA-450/3-73-006-C
11
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PETROCHEMICAL AIR POLLUTION STUDY
INTRODUCTION TO SERIES
This document is one of a series prepared for the Environmental Protection
Agency (EPA) to assist it in determining those petrochemical processes for
which standards should be promulgated. A total of nine petrochemicals produced
by 12 distinctly different processes has been selected for this type of
in-depth study. These processes are considered to be ones which might warrant
standards as a result of their impact on air quality. Ten volumes, entitled
Engineering and Cost Study of Air Pollution Control for the Petrochemical
Industry (EPA-450/3-73-006a through j) have been prepared.
A combination of expert knowledge and an industry survey was used to
select these processes. The industry survey has been published separately
in a series of four volumes entitled Survey Reports on Atmospheric Emissions
from the Petrochemical Industry (EPA-450/3-73-005a, b, c and d).
The ten volumes of this series report on carbon black, acrylonitrile,
ethylene dichloride, phthalic anhydride (two processes in a single volume),
formaldehyde (two processes in two volumes), ethylene oxide (two processes
in a single volume) high density polyethylene, polyvinyl chloride and vinyl
chloride monomer.
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ACKNOWLEDGEMENTS
The study reported in this volume, by its nature, relied on the fullest
cooperation of the companies engaged in the production of ethylene dichloride.
Had their inputs been withheld, or valueless, the study would not have been
possible or at least not as extensive as here reported. Hence, Air Products
wishes to acknowledge this cooperation by listing the contributing companies.
Allied Chemical Corporation
American Chemical Corporation*
B. F. Goodrich Chemical Company
Conoco Chemical Company
Diamond Shamrock Chemical Company
Dow Chemical Company
Ethyl Corporation
PPG Industries
Shell Chemical Company
Vulcan Materials Company
*Subsidiary of Stauffer Chemical Company
Additionally, Air Products wishes to acknowledge the cooperation of the
member companies of the U. S. Petrochemical Industry and the Manufacturing
Chemists Association for their participation in the public review of an
early draft of this document. More specifically, the individuals who served
on the EPA's Industry Advisory Committee are to be commended for their
advice and guidance at these public meetings.
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TABLE OF CONTENTS
Section Page Number
Summary i
I. Introduction ED-1
II. Process Description and Typical Material Balance ED-2
III. Manufacturing Plants and Emissions ED-8
IV. Emission Control Devices and Systems ED-20
V. National Emission Inventory ED-36
VI. Ground Level Air Quality Determination ED-37
VII. Cost Effectiveness of Control ED-38
VIII. Source Testing ED-43
IX. Industry Growth Projection ED-44
X. Plant Inspection Procedures ED-46
XI. Financial Impact ED-48
XII. Cost to Industry ED-52
XIII. Emission Control Deficiencies ED-54
XIV. Research and Development Needs ED-57
XV. Research and Development Programs ED-59
XVI. Sampling, Monitroing and Analytical Methods for ED-64
Pollutants in Air Emissions
XVII. Emergency Action Plan for Air Pollution Episodes ED-68
References ED-75
Appendix I 1-1
Appendix II II-l
Appendix III III-l
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LIST OF ILLUSTRATIONS
Figure No.
ED-1
ED-2
ED-3
ED-4
Table No.
ED-1
ED-1A
ED-2
ED-3
ED-3A
ED-4
ED-5
ED-6
ED-7
ED-8
ED-9
ED-10
ED-11
ED-12
ED-13
ED-14
ED-15
ED-16
ED-17
I-1
II-l
II-2
Title
Simplified Flow Diagram
Process Vent Gas Contact Condenser
Flow Diagram for By-Product Disposal System
Ethylene Dichloride Production -
Capacity Projection
LIST OF TABLES
Title
Typical Material Balance
n ii M
Reactor System Heat Balance
Summary of U.S. Ethylene Dichloride Plants
Survey of U.S. Oxychlorination Plants and
Atmospheric Emissions from These Facilities
(7 pages)
Typical Vent Gas Composition
Process Vent Gas Scrubbers of Oxychlorination
Plants
Direct Fired Boiler plus Scrubber Emission
Control System for Process Vent Gas Stream
Thermal Incinerator and Scrubber System for
Process Vent Gas Stream
Thermal Incineration plus Steam Generation
and Scrubbing System
Cost Effectiveness for Alternate Emission
Control Devices (3 pages)
Ethylene Dichloride Manufacturing Cost for a
Typical Existing 700 MM Lbs./Yr. Facility
Ethylene Dichloride Manufacturing Cost for a
Typical Most Feasible 700 MM Lbs./Yr. Facility
Pro-Forma Balance Sheet
Estimated 1985 Air Emissions for Alternate
Control Systems
Detailed Costs for R & D Project A
Detailed Costs for R & D Project B
Summary of Sampling and Analytical Methods
Reported for Pollutants (3 pages)
Financial Impact of Air Pollution Episodes on
Manufacturing Costs
Emission Summary (3 pages)
Number of New Plants by 1980 (Illustration)
Weighted Emission Rates (Illustration)
Page Number
ED-3
ED-22
ED-32
ED-45
Page Number
ED-4
ED-6
ED-7
ED-9
ED-10
ED-17
ED-21
ED-24
ED-28
ED-29
ED-39
ED-49
ED-50
ED-51
ED-53
ED-60
ED-62
ED-65
ED-71
1-3
II-2
II-4
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SUMMARY
The ethylene dichloride (EDC) industry has been studied to determine
the extent of air pollution resulting from the operations of the various
plants and processes of the industry. The purpose of the work was to provide
the Environmental Protection Agency with a portion of the basic data required
in order to reach a decision on the need to promulgate air emission standards
for the industry.
It was concluded that because of raw material cost advantages, the advent
of the steam cracking process for the production of ethylene has virtually
eliminated acetylene as a raw material in the production of EDC. It was
further concluded that of the two ethylene based processes (namely oxychlorination
and direct chlorination of ethylene) the oxychlorination process is the more
significant polluter in terms of both total emissions and degree of difficulty
in reducing the emissions. However, in terms of industry growth they are about
equally significant because the chief current use for EDC is to produce vinyl
chloride monomer (VCM), with anhydrous hydrogen chloride (HC1) being produced
as a by-product. HC1 is an essential feed to the oxychlorination process and
the quantity produced in VCM manufacture is sufficient to produce 50 percent
of the EDC feed to the VCM unit. Hence, unless another source of HC1 is
available or if the EDC is going to other uses, a "balanced" plant results,
with 50 percent of its EDC capacity from each of the two ethylene based
processes. Obviously, the current national concern over the carcinogenicity
of VCM could greatly influence growth of the EDC industry. In the meantime,
however, this report is devoted to the study of the oxychlorination process,
while the less significantly polluting direct chlorination process is the
subject of one section of report number EPA-450/3-73-005b of April, 1974,
entitled "Survey Reports on Atmospheric Emissions from the Petrochemical
Industry - Volume II".
In general terms, the air emissions from the process fall into the categories
of ethylene, non-methane hydrocarbons (mostly chlorinated), carbon monoxide
and hydrogen chloride. In addition, small quantities of chlorine are sometimes
emitted. As practiced today, virtually no oxides of nitrogen have their
origin in the process and all raw materials are essentially sulfur-free thus
no oxides of sulfur are produced. The average emission factor for the process
is about 0.035 Ibs./lb. of EDC produced, over half of which is due to chlorinated
hydrocarbons with about one sixth due each to ethylene and carbon monoxide. This
amounted to about 120 million Ibs. per year of total atmospheric emissions
in 1973. If industry growth continues as forecast at that time, and if all new
plants are built as currently most typical, then, by 1985 the emissions will
be about 300 million Ibs. per year.
Most of the plants surveyed have some form of final product recovery/pollution
control device on the main process stream before it is released to the atmosphere.
Not all of the EDC producers include product fractionation in their reported
process but of those that do, only half (two plants) include vent condensers
for chlorinated hydrocarbon emission control. However, the average emissions
from this source are only about one-seventh of the estimated total. About
two percent of the emissions result from the widespread practice of using fixed
roof tanks with atmospheric vents for pure EDC storage. It has been concluded
chat there is no demonstrated technique for making significant reductions in the
air emissions from the process, although distillation vent condensers and either
floating roof storage tanks or storage vent condensers would result in reduced
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ii
SUMMARY (continued)
emissions. Installation of these devices would not lead to any significant
financial hardship because the recovered EDC would pay part, if not all, of
the cost of the emission control.
The study addressed itself to the task of finding a "feasible" though
not "demonstrated" emission control technique for the bulk of the emissions,
i.e., the main process vent. It was concluded that some form of incineration
could be practiced on this stream and if backed up with scrubbers, emissions
would be about six million pounds per year in 1985 (an emission factor of
0.0008 Ibs./lb. of EDC) with 90 percent of that total being due to existing
plants and 30 percent of the total being due to storage losses from those
same existing plants. Four forms of incineration were studied. Two of
these, namely a direct fired boiler or a thermal incineratior followed by
a waste heat boiler result in energy recovery, while the other two, namely
incineration or flaring are both wasteful of energy. Furthermore, flaring
results in an increase in hydrochloric acid and chlorine emissions while all
four result in an increase in emissions of nitrogen oxides (about one million
pounds per year or one-sixth of the total). The report concluded that the
most feasible method of emission control on existing plants is to install a
thermal incinerator and caustic scrubber on existing main process vents, and
a condenser and plume burner on existing distillation vents (this assumes that
no use can be made of the steam generating potential of these plants). The
report further concluded that the most feasible method of emission control on
future plants is to install a condenser on the distillation vent stream and then
combine it with the main process vent stream for incineration, waste heat
recovery and scrubbing. Floating roof tanks are considered £or future pure
EOC storage.
It must be emphasized that most of the above control techniques have not
been demonstrated commercially. The main problem with incineration of chlorinated
effluents is that hydrogen chloride is produced. It is corrosive to metals
at high temperatures (above about 600° F) or will form hydrochloric acid if
allowed to condense with the combustion water vapor that is present. Hence,
a difficult temperature control problem exists. A further problem with
incineration of oxychlorination off-gas is its low heating value, requiring
substantial quantities of supplemental fuel. However, incinerators for the
disposal of both gaseous and liquid chlorinated wastes have been demonstrated
in other applications and heat recovery has been deomonstrated on some of
these as described in the body of the report. Hence, it can be concluded that it
is probably feasible for oxychlorination plants
The capital investment (1973 dollars) required for the most feasible
combustion devices, as estimated in the report are about $250,000 per thermal
incinerator (two may be deemed essential for reliability) and $35,000 for a
plume burner on existing distillation vents. A waste heat boiler will add
about $375,000 (and again, two may be required) and the caustic scrubbing
system will add either $400,000 or $500,000 depending upon whether or not
waste heat recovery is employed. If not, a quench will be required, thus
increasing the volumetric throughput of the scrubber. The operating cost of
a retrofit incinerator and scrubber will exceed $500,000 per year even if a
spare unit is not installed. The addition of a heat recovery unit (either
retrofit or on a new plant) will reduce the annual cost by about $100,000.
The recommended distillation vent condensers and plume burner (retrofit) will
add about $50,000 to the plant's annual income. These estimates all apply to
the assumed 700 MM Ibs. per year capacity of a "Model Oxychlorination Plant".
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iii
SUMMARY (continued)
These are significant costs to the industry with reductions in net profit
after taxes to about 75 percent of the case without a vent gas combustion
device. This is equivalent to a reduction in return on total investment
from nearly 14 percent to nine percent, with the latter figure being based
on about 15 percent additional capital. On the other hand, a two percent
price increase would restore the net profit and most of the return on
investment.
The capital expenditure (1973 dollars) required to effect the reduction
in emissions cited above will be about $5,000,000 to retrofit the existing
plants with a single incinerator or about $6,500,000 if spares are installed.
By 1985, the industry will have invested an additional $9,000,000 in new
emission controls, as outlined above, with single incinerators and waste heat
boilers or about $14,000,000 if spares are installed. Potentially, the
industry total ranges between $14,000,000 and about $21,000,000.
The report cites two concepts for research that could lead to reduced
emissions from the oxychlorination process. The first concept involves the
use of oxygen rather than air feed to the reactor (this practice is followed
in one of the existing process plants) but employs an off-gas recycle to
minimize wastes going to the atmosphere. The second concept is also
employed in one embodiement of the industry, that is the use of chlorine
as part of the oxychlorination process feed. There is undoubtedly research
being conducted in both of these areas by today's producers of EDC. An
additional area of potentially valuable research that is more general in
nature is the design of a chlorinated hydrocarbon incinerator/waste heat
recovery system.
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ED-1
I. Introduction
Ethylene dichloride (EDC) is a colorless, oily liquid which is primarily
used to produced vinyl chloride monomer.1 It is also employed in chlorinated
solvent manufacture, ethyleneamines production and as a lead scavenger in
antiknock fluids.2
In the U.S., ethylene dichloride is almost exclusively produced by either
direct chlorination or oxychlorination of ethylene. Because of lower feedstock
costs, these processes have almost completely replaced the older acetylene plus
HCl method. Presently, about 45 percent of the total EDC production is by the
oxychlorination route.
Atmospheric pollutants from the direct chlorination process are less than
one-fifth of those emitted by the air oxidation method. Atmospheric emissions
from oxychloration consist of carbon oxides, light hydrocarbons, chlorinated
compounds, nitrogen and water vapor.
Virtually all vinyl chloride manufacturers also produce EDC. Most of
these plants employ both direct chlorination and oxychlorination facilities.
In producing vinyl chloride from ethylene dichloride, HCl is liberated. The
HCl plus ethylene is used as feed in the oxychlorination unit. Normally, EDC
production is balanced between the two chlorination processes so that no net
HCl is produced or consumed.
A process description, industry survey of emission sources, effluent
characteristics, control practices and equipment in addition to plant economics
for EDC production by oxychlorination are presented in this report. Data
for the direct chlorination process were provided in a separate report
entitled "Survey Reports on Atmospheric Emissions from the Petrochemical
Industry - Volume II" and numbered EPA-450/3-73-005-b.
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ED-2
II. Process Description and Typical Material Balance
Several U.S. companies license oxychlorination processes for producing
ethylene dichloride and several others employ their own technology.
The basic chemical equation for the various oxychlorination processes
is as follows:
2 CH2=CH2 + 02 + 4 HC1 ^ 2 CH2C1-CH2C1 + 2 H20
Approximately stoichiometric proportions of ethylene, anhydrous hydrogen
chloride and air (except one plant which uses pure oxygen) are fed to a
catalytic reactor which operates at low pressure (20 - 75 PSIG) and 400 to
600° F. Once through flow is used since conversion of ethylene is virtually
complete. Because of the high exothermic heat of reaction (>1000 BTU/lb. of
EDC produced), efficient heat removal in the reactor is important for adequate
temperature control. For this reason, some processes utilize fluid bed
reactors 3 with internal cooling coils while at least one producer employs
fixed bed multi-tube reactors which resemble heat exchangers.4 in this design,
catalyst is contained inside the tubes and a coolant flows through the shell.
In both fluid bed and tubular reactors, most of the heat removed is recovered
as steam.
The reactor effluent is normally cooled by either direct water quench
or indirect heat exchange. After trim cooling with water and brine condensers,
the partially condensed effluent is sent to a phase separator. Non-condensible
gases consisting mainly of nitrogen are vented to the atmosphere. Before
venting, usually these gases are contacted with either water or aromatic
solvent for removal of HC1 and recovery of ebhylene dichloride. One process
incorporates chlorine addition downstream of the main oxychlorination reactor
in order to convert unreacted ethylene to EDC. In addition to reducing ethylene
loss in the vent gas, the direct chlorination step reduces the amount of air
required for oxychlorination. Therefore, the total volume of vent gas and
hydrocarbon emissions are reduced in volume. The total volume of vent gas is
even smaller for the one unit incorporating tonnage oxygen. For a detailed
description of the atmospheric emissions from the various processes, see
Section III.
The organic liquid product from the reactor effluent phase separator is
either contacted with aqueous caustic soda or sent directly to product
distillation for removal of water and chlorinated hydrocarbon impurities
which are sent to off-site disposal. In some plants final product distillation
is not provided since the crude ethylene dichloride purity (96 - 98 percent
EDC) is adequate for many applications.
An aqueous phase collected in the effluent separator is discharged to
waste. In some plants dissolved organic materials are removed and recovered
in stripping columns before the aqueous stream is rejected.
Figure ED-1 presents a flow diagram for a typical oxychlorination plant.
Table ED-1 shows a "typical" material balance for a "model plant" producing
700 MM Ibs./year of EDC. This production rate represents an estimate of average
plant capacity for future new units. Table ED-1A presents the same balance
with quantities expressed as tons per ton of EDC. These balances are based on
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ED-5
average air emission and product composition data derived from plant survey
questionnaires and do not represent actual data from any specific plant or
process. Feed requirements were determined by carbon and chlorine material
balance. It should be noted that the resulting ethylene feed requirement as
shown in Tables ED-1 and 1A is three to four more percent than reported in
the plant surveys and published articles. 155 Slight material balance
differences can be explained by the fact that most operators choose an
economical operating point which represents the lowest total cost of all
materials used. Generally, more complete conversion of HCl can be achieved
by using somewhat more than the minimum ethylene quantity. Some plants may,
therefore, prefer to optimize HCl consumption at the expense of a small
increase in ethylene feed. Beyond this optimization of raw material, feed usage
depends largely on the efficiency of the reactor control system.
Table ED-2 presents an estimated heat balance around the oxychlorination
reactor system.
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ED-7
TABLE ED-?
OXYCHLORINATION REACTOR SYSTEM
HEAT BALANCE*
Heat Out
Steam Generation
Reactor Heat Losses
Quench plus Effluent Cooling (575 - 100 °F)
Incremental Effluent Heat Content**
Total
BTU/Lb. of EDC
1,214
6
609
-284
1,545
Heat In
Exothermal Heat of Reaction
Ethylene Bichloride Formation
Effluent Neutralization
Feed Vaporization and Preheat
Total
1,383
2
160
1,545
*Basis
1) Table ED-1A material balance.
2) Feed preheated to 300 °F.
3) Reactor outlet temperature 575 °F.
**Difference in heat content of effluent (3 100 °F and ethylene feed
40 °F (liquid) plus air and anhydrous HCl @ 100 °F.
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ED-8
III. Manufacturing Plants and Emissions
Table ED-3 presents a list of U. S plants producing ethylene dichloride.
This table also shows published 2,7 capacity figures for these units. Approx-
imately 80% of the total plant capacity is located in Texas and Louisiana
with the remaining production in Kentucky and California. These EDC
plants are built within 1 to 5 miles of towns and cities with population
ranging between 2,000 and 360,000. The type of process is noted in the table.
Table ED-3A shows individual plant capacity figures and emission data
for all of the U. S. plants producing EDC by the oxychlorination process.
Emissions from these plants are as follows:
A. Continuous Air Emissions
1. Main Process Vent Gas
This stream, which generally vents from a scrubber or an
absorber, consists of the gross reactor effluent after quenching
and trim cooling for recovery of EDC. The process vent gas emis-
sions presented in Table ED-3A are average values, with the actual
composition depending on catalyst activity and reactor operating
conditions. Table ED-4 shows a typical breakdown of components
in this stream, which represents the primary air emission in the
oxychlorination process.
In addition to catalyst activity and reactor operating conditions,
the specific processing scheme employed has some influence on the
amount of vent gas emissions. For example, in one process, chlorine
is added downstream of the main oxychlorination reactor in order
to convert unreacted ethylene to EDC. By using chlorine for clean-up,
it is not essential to obtain maximum conversion in the oxychlorination
reactors. This permits a reduction in the amount of excess air
employed and also results in a significant reduction in emissions.
According to the survey data, hydrocarbon emissions in the vent gas
stream are about half as much as those indicated for plants incor-
porating several other air oxychlorination processes. In the plants
that have chlorine addition (52-7, 52-8 and 52-9), the process vent
gas is sent to a water or dilute caustic scrubber for removal of
HCl (up to 0.0004 T/T EDC) and unreacted chlorine (about 0.0002 T/T
EDC) before emitting this stream to the atmosphere,
In some of the other air oxychlorination plants (52-4, 52-5 and
52-6) 5 an absorber-stripper system is used to recover additional
chlorinated hydrocarbons from the process vent gas. In these units,
a small amount of absorption oil ("aromatic solvent) is lost in the j
atmospheric vent (0.0011 T/T EDC). Hovever, total hydrocarbon
emissions are similar to the chlorine addition plants (0.015 T'T EDC).
The main process vent gas emissions shown in Tables ED-1 and
ED-4 approximate a weighted average (based on EDC capacity) of
emissions from all surveyed air oxychlorination plants. Since about
657o of the air oxychlorination EDC is produced in plants that
incorporate absorber-stripper or chlorine clean-up systems, the
emissions shown in these tables do not truly represent actual values
obtained in any specific plant. In other words units with chlorine
addition or lean oil absorption systems would tend to have lover losses
than shown for the "typical unit". Whereas, plants with minimum
clean-up facilities would have a somewhat higher level of emissions.
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ED-16
TABLE ED-3A FOOTNOTES Page 7 of 7
(a) Based on average production rate if available, otherwise based on design
capacity.
(b) Includes HC1 and carbon tetrachloride,
(c) Air.
(d) Includes oxygen.
(e) Normal feed to scrubber contains 0.0008 tons HCl/ton EDC. However, during
reactor start-up (max. 30 min., 24 times per year), feed can contain as
much as 0.50 tons HCl/ton EDC. During emergency conditions such as
power failure, when scrubber becomes ineffective, most of this HC1 will be
vented to the atmosphere. Duration is normally 3-5 minutes required to
secure plant.
(f) Recovery unit not put in operation until after plant survey.
(g) During start-up, feed to scrubber contains 0.163 tons of nitrogen per ton
of EDC production capacity and 0.106 tons of HCl per ton of EDC. Duration
is approximately 20 minutes. During emergency venting, the vent contains
a small amount of organic material.
(h) Represents nitrogen flow during start-up.
(i) Absorber-stripper may shut down for undetermined period during which time
EDC content in vent increases to three times value shown.
(j) Sent to off-site disposal plant.
(k) Includes methane and ethane.
(1) Represents normal flow from EDC unit. Actual total vent from stack
includes streams from other units in VCM plant. Vent gas composition
shown is based on analysis of scrubber feed gas from EDC oxychlorination
unit. It has been assumed that water scrubber removes contained HCl
(0.00004 T/T EDC).
(m) Only during plant upset.
(n) Survey data does not include information regarding air emissions resulting
from EDC purification.
It should be noted that flow rates and compositions shovn for intermittent
streams represent emissions during flowing condition and not yearly
averaged values. The total plant emission figures shovn are averaged
emissions for extended periods of operation.
-------
ED-17
TABLE ED-4
TYPICAL VENT GAS COMPOSITION (a)
FOR
700 MM LB./YR. ETHYLENE BICHLORIDE PRODUCTION
BY OXYCHLORINATION PROCESS
Normal Range in Composition Average Floy Rate
Component Mol. 7, MPH Lbs./Hr.
Carbon Dioxide 0.8 - 3.5 47.9 2,110
Carbon Monoxide 0.6 - 1.3 20.8 583
Nitrogen 82 - 95 2,484.4 69,612
Oxygen 0.5 - 7.5 122.3 3,912
Methane 0 - 5.0 (c) 10.7 172
Ethylene 0.2-0.8 15.0 420
Ethane 0 - 3.8 (d) 19.1 575
Ethylene Dichloride 0.07 - 0.75 6.1 600
Ethyl Chloride 0-0.75 7.9 510
Aromatic Solvent (b) 0-0.1 0.9 94
2,735.1 78,588
(a) Downstream of vater or caustic scrubber facilities. Prior to scrubbing operations,
stream normally contains about 65 Ibs./hr. HC1 (0.0007 T/T of EDC production).
(b) Only present if aromatic solvent is used for product recovery. (Plants 52-4, 52-5 &
52-6.)
(c) Only present in plants 52-1, 52-4, and 52-5. This represents methane impurity
contained in ethylene and HCl reactor feed.
(d) Primarily represents saturate impurity in ethylene feed.
-------
ED-18
In the one U. S. oxychlorination plant using tonnage oxygen
in place of air (52-10), total vent gas emissions are greatly
reduced. However, hydrocarbon emissions for this unit are similar
to those shown in Table ED-4.
There are no odor problems associated with the main process
and other vent streams. In some instances, especially during plant
start-up, odors from HC1, Cl2 or chlorinated hydrocarbons are
detected on-site but these do not permeate beyond the plant boundary.
2. Product Fractionation Vent
This normally represents a small stream, which varies greatly
in composition, depending upon the type of fractionation system
used for product recovery and the desired product purity. In
most plants no product fractionation facilities are provided on-site.
In these units the crude EDC is either combined with products from
other plants for clean-up or impurities are rejected in downstream
vinyl chloride monomer facilities.
In some cases, this stream consists of the combined vent from
several fractionators.
3. Product Storage Losses
Because of low EDC vapor pressure at ambient temperature (3 PSI
@ 100° F) , product storage tanks are directly vented to the atmo-
sphere, usually with nitrogen padding. Some plants use conservation
type vents to reduce emissions while filling. Based upon average tank
turnaround figures, it is estimated that EDC losses from stroage
facilities equals about 0.0006 T/T EDC production.
4. Waste By-Product Disposal
Heavy chlorinated by-products removed in the product fractionation
section are normally sent to an incinerator. Light chlorinated
compounds produced in the process can be used as supplemental feed
in manufacture of perchloro-ethylene and carbon tetrachloride or
fractionated for recovery of specific fractions or compounds.
However,, in some locations where there is little or no market demarid
for this material, both by-product streams are incinerated. Plant
(52-5) burns this material plus chlorinated hydrocarbon waste products
from other processing units in an off-site incinerator. Effluent from
the incinerator is cooled and seat to absorbers for recovery of HC1.
Unrecovered HCl and any chlorine formed in the incineration are
removed in a dilute caustic scrubber before atmospheric venting of
the effluent.
B. Intermittent Air Emissions
During reactor start-ups (10 - 20 minutes duration about twice
a month) feed to the process vent gas water or dilute caustic
scrubbers contains betveen 0.10 to 0.5 tons HCl'ton EDC. Normal
feed to scrubber contains approximately 0.0005 tons HCl/ton EDC.
During emergency conditions such as power failure, when scrubber
becomes ineffective, this HCl will be vented to the atmosphere.
At least one oxychlorination process renuires a catalyst conditioning
step, which results in some ethylene emission during reactor
start-up operations.
-------
ED-19
C. Liquid Wastes
Water condensed from the reactor effluent plus spent caustic
from the neutralizer represent the primary liquid waste streams.
The combined flow of these two streams varies substantially from
plant to plant (0.2 to 1.4 T/T EDC). In one unit (52-5), waste
water strippers are provided on-site to recover contained EDC
and light chlorinated hydrocarbons (0.0016 T/T EDC). In all other
units, this water is sent off-site for treatment or used for pH
control in other processing areas.
D. Solid Wastes
Approximately 0.0002 T/T EDC of solid wastes are removed from
the reject water settling ponds in plants that use fluidized bed
reactors. These solids are catalyst particles scrubbed from the
reactor effluent. Plants with fixed bed reactors do not have solid
wastes, except intermittently when an entire catalyst charge is
replaced.
E. Fugitive Emissions
All but one plant surveyed report that fugitive emissions are
minor. The one plant that estimated losses reported that total
storage tank vents plus fugitive emissions are about 0.01 T/T EDC
production. Based upon the comments provided by the other respondents,
this loss figure appears high.
It is logical to conclude that due to the nature of the chlorinated
hydrocarbons involved, the plant operators would be careful in their
maintenance and sampling in order to minimize fugitive losses.
-------
ED-20
IV. Emission Control Devices and Systems
A. Main Process Vent Gas Stream
1. Devices Currently Employed
(a) Scrubbers
At present most U.S. plants that do not have an aromatic
solvent absorber-stripper system for product recovery employ a
water or dilute caustic scrubber on this vent stream, see
Table ED-5. The scrubber is used to remove small amounts of
HCl (approximately 0.0008 T/T EDC) and, in some cases, chlorine
(0.0002 T/T EDC) left in the non-condensed reactor effluent.
Water scrubbing is sufficient for removing HCl. However,
if chlorine is present, dilute caustic is required for efficient
operation.
In many of the units that do not have vent gas scrubbers,
HCl is removed in the gross reactor effluent water quench or
caustic scrubbing facilities.
(b) Contact Condenser
One plant (52-1) passes the vent gas through a direct contact
condenser. Whereas the above scrubbers are primarily used to
remove HCl, the contact condenser is employed to recover EDC
(0.02 T/T EDC product) and other light chlorinated hydrocarbons
(0.002 T/T EDC).
Figure ED-2 presents a simplified flow diagram for the vent
gas contact condenser system. Process vent gas is fed to the tube
side of two shell and tube heat exchangers operated in series. In
the first exchanger the gas is contacted with an unnamed absorption
fluid and indirectly cooled with processed vent gas. In the
second exchanger, refrigerant is used to further cool the mixture.
Liquid chlorinated hydrocarbons plus absorption fluid are removed
from the exchanger effluent in a vapor-liquid separator. A
decanting drum is used to separate EDC from the absorption fluid.
The recovered EDC (90 wt. percent EDC) is combined with reactor
effluent liquid for water washing and product distillation. The
circulating absorption fluid stream is sent to a stripper tower
for removal of water. Maloperation of stripper occasionally results
in water recycle and condenser freeze-up.
Based upon overall hydrocarbon emissions shown in Table
ED-3A, it would appear that the above contact condenser system is
not a very efficient air pollution control device. However, in
this case, the emission data are misleading, Plant 52-1 processes
recycled gas streams from other processing units in order to utilize
contained raw materials. This results in carbon dioxide and light
hydrocarbon impurities being charged to the oxychlorination reactors
(feed contains 82-92 wt. percent ethylene versus 99.9 vt. percent
for other plants). Most of these impurities are rejected in the
main process vent stream.
Since plant 52-1 apparently cools the vent stream to
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ED-23
a colder temperature than most other plants, it is assumed that
similar amounts of chlorinated hydrocarbons would be liquefied
and recovered in this facility as with other currently used
control devices processing the same vent gas.
(c) Refrigerated Condensers
One plant (52-2) passes the vent stream through two stages
of refrigeration, which cool the gas to -10° F for recovery of
chlorinated hydrocarbons. Specific data regarding the condenser
system and amount of material recovered are not available.
However, net hydrocarbon emissions are low (0.015 T/T EDC).
(d) Mist Eliminators
The plants that incorporate an aromatic solvent absorber-
stripper system for product recovery (52-4, 52-5 and 52-6), have
a mist eliminator in the absorber to prevent liquid carry over.
One unit (52-6) also has a downstream knock out drum for liquid
removal before stack venting of the off-gas. It is estimated
that these facilities recover approximately 0.01 tons of solvent
per ton of EDC production.
2." Combustion Devices (None currently employed)
In order to remove CO and further reduce hydrocarbon emissions in
the process vent, one of the following combustion devices could
be considered. However, at present none of these devices are used
in this service.
(a) Direct Fired Boiler and Scrubber System
A direct fired boiler is an efficient method of oxidizing
these contaminates. However, the burning of chlorinated hydrocarbons
in this, or any other combustion device, produces HCl plus some
chlorine. In order to prevent pollution of the atmosphere with
these compounds, it is desirable to water wash and or caustic
scrub the boiler effluent. The HCl content of the gas stream is
too low to make HCl recovery practical.
A large amount of steam is presently produced in the reactor
system of a conventional oxychlorination plant. Even with this
production, the overall facility (including direct chlorination and
VCM production) usually consumes a substantial quantity of steam
(about 2 Ibs./lb. of VCM production^). Therefore, in new plants,
it is conceivable that steam production resulting from pollution
control facilities could be used in the VCM complex.
Table ED-6 presents a typical material balance for a fired
boiler and scrubber system operating on the clean-up of a process
vent gas. In order to have essentially complete combustion of
pollutants, the boiler data are based on an 1800° F combustion zone
temperature and 3 mol. 70 oxygen (Dry Basis) in the effluent.
Maximum steam generation is included in order to reduce cost and
water requirements for downstream scrubbing facilities.
-------
BD-24
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ED-25
Since none of the surveyed plants use fired boilers or any
other combustion device on this vent stream, it is difficult to
predict equipment performance in this application. Based upon
applications in other areas, the following potential problems
exist:
(1) Vent gas is normally available at low pressure
(2) Investment for required blowers, burning equipment
and control systems is high.
(3) Effluent stream is corrosive at some conditions.
(4) Because of low heating value (30 to 55 BTU/Ft.3) of
the gas stream, up to 45 percent of the total heating
value must be added as supplemental fuel in order to
achieve complete combustion.
(5) Flame control is difficult and flame-outs may be
common due to low heating value and low level of
incandescence.
(6) Operating problem results from need to switch to
complete fuel gas firing whenever plant emergency
necessitates purging the reactor system with
nitrogen. This occurs about twice a year.
In similar applications of fired boilers, it has been found
that the effluent stream is especially corrosive at temperatures
either above 600° F, or below the HCl dew point. In order to
maintain steam coils within the non-corrosive temperature range,
245 PSIG saturated steam is assumed to be generated in the boiler
and effluent gases are exhausted at 550° F. Adequate instrumentation
is required to see that tube wall temperatures do not exceed 600°F
or go below 400° F while burning streams containing chlorinated
hydrocarbons. Instrumentation is also required for purging
chlorinated compounds from the system prior to furnace shutdown.
The boiler effluent is quenched and sent to either a caustic
scrubber or combination water-dilute caustic scrubbing unit. The
combination unit would be employed if dilute HCl (2-3 wt. 7, HCl)
could be used off-site for stream neutralization or sent to an
HCl recovery unit. In the dual scrubbing unit, the gas stream is
first contacted with water, which absorbs about 90 percent of the
HCl. The gas is then scrubbed with caustic before being discharged
to the atmosphere. It is estimated that the stack gases would
contain less than one PPM of HCl and 10 PPM by volume of chlorine.
The bottom portion of the scrubbing tower and inlet piping
would be lined with fiber reinforced plastics (FRP) or rubber.
Porcelain raschig rings, Berl saddles or other types of packing
can be used.
Scrubber requirements for processing boiler effluent from
the typical 700 MM Ibs./yr. oxychlorination unit are as follows:
-------
ED-26
Combination Caustic
Type of Scrubber Unit Scrubber
Tower Dimensions, Ft.
Diameter 11 11
T-T Length 35 25
Water Absorption Section
Number of Beds 2
Bed Depth, Ft. (each) 8
Reject Water Rate, GPM 30
Wash Water Recirculation Rate, GPM 170
Bed AP, in. of water 2
Caustic Scrubbing Section
Number of Beds 1 2
Bed Depth, Ft. (each) 5 8
Spent Caustic Solution*, GPM 5 5fr
Caustic Recirculation Rate, GPM 195 150
Bed AP, Inches of Water 1 2
*contains 4.5 wt. percent NaCl.
The data presented in Table ED-6 and the economics derived
therefrom are based on using straight caustic scrubbing without
HCl recovery.
(b) Thermal Incineration and Scrubber System
Table ED-7 presents a material balance for this type of
control device. Incinerator data are based on the same combustion
zone operating conditions used for the direct fired boiler.
Burning of off-gas in a thermal incinerator results in
similar burning problems and combustion efficiency anticipated
for a direct fired boiler.
Scrubbing data in Table ED-7 and subsequent economics regarding
vent gas incineration effluent scrubbing operations are based on
using a caustic scrubber similar to that proposed for the direct
fired unit.
(c) Incineration plus Steam Generation and Scrubbing System
Table ED-8 presents a material balance and sketch for a thermal
incinerator followed by a waste heat boiler and caustic scrubber.
This combination facility has an emissions control efficiency and
potential similar to that of the direct fired boiler.
There is very little commercial experience of burning
chlorinated hydrocarbons in incinerators with steam generation for
heat recovery. A Shell Chemical Co. affiliate is reported to have
had two 100 percent capacity incinerator and boiler systems
processing liquid chlorinated wastes in Europe. On stream
factor is believed to have been approximately 25 percent because
of brick work deterioration and corrosion problems. This poor
performance has resulted in the project being abandoned.
-------
ED-27
Stauffer Chemical Company has a small fired tube boiler in
Bucks, Alabama which burns gaseous chlorinated waste material.16
This unit, built by John Zink Company, was put in service in
August of 1972. After six months operation, it was shut down to
replace corroded boiler tubes and tube sheet (carbon steel).
Corrosion was attributed to a supplemental feed which contained
phosphorous. After retubing one-third of the bundle (carbon
steel tubes) and removing phosphorous containing feed, the
unit ran for two months before a shutdown was caused by an
expansion joint failure between the oxidizer and boiler. The
expansion joint had not been packed or insulated and corrosion
resulted from condensation during cold weather. Boiler inspection
during this shutdown showed no corrosion. Since returning to
operation, the unit has run several months with no apparent
corrosion problems.
John Zink Company has a pilot unit similar in size to the
Stauffer facility.
American Chemical Corporation in Long Beach, California
has a thermal oxidizer plus waste heat boiler system for disposal
of concentrated gaseous chlorinated hydrocarbons. American
Chemical is on its third boiler. The first boiler was water tube
and failed within two years. The second was fired tube and
lasted five years. The present boiler has been in service
two years.
There are reports that there is a B.F. Goodrich licensee in
Europe that employs a thermal incinerator plus a carbon steel
boiler for heat recovery. This unit has been in operation for
two years and is reported to have given satisfactory performance.
Scrubbing data and economics for this system are also based
on assumptions made for the direct fired unit.
(d) Submerged Thermal Incineration and HCl Recovery
Submerged exhaust incinerators are primarily used in disposal
of waste streams that have a high heating value. The main advan-
tage of this incinerator is that effluent gas can be cooled to
acceptable scrubber operating temperature and reject a major
portion of the HCl as dilute acid (2-5 wt. 70 HCl) at relatively
low capital expense. However, when dealing with low heating
value waste streams such as the process vent gas, a substantial
amount of supplemental fuel is required to obtain adequate
combustion zone temperature ( 1800° F). While combustion
efficiency for this furnace would be similar to other incinerator
systems, overall heat utilization is poor and operating costs
would be higher than for the above devices with steam generation.
(e) Catalytic Incinerator
A conventional catalytic incinerator could reduce pollutants
to similar levels obtained with a thermal unit. The catalytic
facility would operate at lower temperature (800-1000° F) and,
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ED-30
therefore, would probably produce somwhat less NOx. However,
the application of a catalytic incinerator is not recommended for
the following reasons:
(1) Only moderate catalyst life with possible danger of
catalyst fouling and poisoning.
(2) Limited oxidation activity.
(3) Based on thermodynamic equilibrium data (8), low
operating temperatures would favor increased chlorine
production. Chlorine is more difficult to remove
than HCl in downstream scrubbing facilities.
(f) Flare System
This control device would have the following limitations:
(1) A substantial amount of supplemental fuel is required
to burn this vent stream. Based on recommendations
from vendors, about 125 BTU/SCF is the minimum
flareable heating value. This would require about
100 MM BTU/hr. of supplemental fuel.
(2) All HCl formed during combustion (about 0.008 T/T
EDC) would be emitted to the atmosphere.
(3) Efficiency for removing contaminants is less than for
other combustion devices. Based upon qualitative data
from similar control devices in other applications, it
is estimated that approximately 90 percent of the CO and
hydrocarbon pollutants will be burned.
(4) Improper firing of the burner could result in operating
temperatures which favor NOx formation.
(5) Changes in vent gas composition could extinguish the
burner if adequate instrumentation are not provided.
3. Non-Combustion Devices
As noted in Section II and Section III, A-l, one oxychlorination
process incorporated chlorine addition in order to obtain an
economically optimum conversion of ethylene. From a conceptual
standpoint it should be possible to increase the size of the
direct chlorination reaction system in order to reduce ethylene
emissions to 10 to 100 PPM rather than the present 2000-8000 PPM
level. The process licensor believes that the increased conversion
of ethylene to EDC with this modified direct chlorination scheme
would off-set the resulting incremental operating costs.
B. Product Fractionation Vent
Four of the surveyed plants C52-1, 52-3, 52-5 and 52-6) have
product distillation facilities. The fractionation results in the
-------
ED-31
atmospheric venting of chlorinated hydrocarbons, which are primarily
emitted from the product drying column or "heads" colums. Two of
the plants '52-3 and 52-5) have pollution control devices on this
stream. In these units, emissions are reduced by cooling the tower
off-gas to 55-60° F. The cooled effluent is sent to a phase separator
where about 85 percent of the contained hydrocarbons are removed and
recycled for EDC recovery. Without a control device, the vent stream
(80-120° F) would contain about 0.01 tons of hydrocarbon per ton of
EDC production.
In addition to the drying or "heads" column vent, three of the
plants emit a small amount of hydrocarbon from one of the following
miscellaneous operations:
1. Absorber lean oil stripping (52-6).
2. Waste water stripping (52-5).
3. EDC product caustic scrubber (52-3).
Only one of these plants (52-5) has a pollution control device on
this small vent stream. The device, which is similar to that used
on the primary fractionation vent stream, removes approximately
70 percent of the contained hydrocarbons. Without vent gas cooling,
hydrocarbon emissions are about 0.002 T/T of EDC production.
Recovery of EDC from liquid condensed from the various product
fractionating vent streams off-sets the cost of providing the emission
control facilities.
If a combustion device was used in place of low temperature
cooling, hydrocarbon emissions in these vent streams could be
eliminated. However, operating costs would be higher (no EDC
recovery) and substantial amounts of HCl (0.009 T/T EDC) would be
emitted to the atmosphere. If the combustion device were to be
employed downstream of the present pollution control facilities,
the unrecovered hydrocarbon (0.0022 T/T EDC) would produce less
HCl (0.0013 T/T EDC).
C. Product Storage Vent
Normally, product storage capacity is equal to about 1.5 to 2
days production. In present plants fixed roof storage tanks are
used and these tanks are vented to the atmosphere. Changes in tank
liquid level could result in losing as much as 0.06 percent of the
EDC product to air emissions. This loss could be eliminated by
using floating roof tanks, or vent condensers.
In crude EDC storage, losses are not significant because the
product is normally stored under a water layer which effectively
reduces EDC vaporization.
D. Waste By-Product Disposal
1. Thermal Incineration
At least one plant (52-5) sends liquid chlorinated hydrocarbons
(0.0075 T/T EDC) rejected from the heads column (Table ED-1, Stream 8)
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ED-33
to an off-site incinerator for disposal. Effluent from the incinerator
is quenched and sent to a three stage absorber for recovery of HCl.
Essentially all of the contained HCl is absorbed in dilute hydro-
chloric acid. The stream is fractionated by azeotropic distillation
and dried to yield anhydrous HCl. Unrecovered HCl and the small
amount of chlorine formed during incineration are removed by dilute
caustic scrubbing before atmospheric venting of the incinerator effluent.
A system similar to that used in plant 52-5 replaces the azeotropic
distillation system with a pressure-stripping of dilute HCl (18° BE1)
followed by successive partial condensations. This represents another
method of recovering anhydrous HCl from the incinerator effluent.^
Plant 52-10 plans to install an incinerator for burning the main
process vent gas plus waste chlorinated by-products. This unit,
which will not provide HCl recovery, was expected to be placed on-stream
during the last half of 1973. (The current status is unknown.)
A submerged exhaust incinerator followed by an HCl recovery system
is another efficient by-product disposal system.8 Figure ED-3 presents
a flow diagram for a typical system that could be used to burn the
chlorinated waste and recover anhydrous HCl. In this facility, the
liquid chlorinated hydrocarbons are burned in a high performance
furnace. A limited amount of excess air (about 15 percent above
stoichometric requirement) and high combustion zone temperature are
used in order to minimize chlorine formation while obtaining complete
combustion. If the hydrocarbon waste contains more than 70 wt.
percent chlorine, supplemental fuel is required to obtain adequate
temperatures. The hot combustion gases are sparged through a down-
comer tube into liquid contained in a quench tank. By direct contact
heat exchange, the incinerator effluent is cooled to about 190° F.
Concentration of hydrogen chloride in the cooled exhaust gases is
usually less than 10 vol. percent since it is diluted with water
evaporated from the quench tank. After being quenched, the incinerator
effluent is sent to an absorber column. In this multiple bed packed
tower, most of the HCl is absorbed in water, producing dilute hydro-
chloric acid (15 wt. percent HCl). Chlorine and trace quantities of
unrecovered HCl are removed from the absorber effluent by caustic
scrubbing. The resulting stack gases are reported to contain less
than one PPM HCl and ten PPM chlorine.
Since the acid concentration produced in the absorber is less
than the azetropic composition (20.2 wt. percent HCl), it is necessary
to use extractive distillation in order to obtain anhydrous HCl.
Calcium chloride is normally used as the extraction solvent. The
azeotrope between HCl and water does not exist when the concentration
of calcium chloride reaches 30 percent.
The dilute acid from the absorber is combined with concentrated
calcium chloride solution from the incinerator quench tank and charged
to a packed bed extractive distillation column. The tower bottoms
consists of solvent and water extracted from the dilute acid. This
dilute solvent is recycled to the incinerator quench tank for water
removal. The overhead HCl vapor from the extractive distillation
column is cooled by water condensers and brine coolers to approximately
15° F. The product hydrogen chloride contains 100 PPM chlorine, 60
PPM water and 10 PPM organics.
-------
ED-34
Overall HCl recovery efficiency ia reported to be 95 percent.^
Future water pollution regulations may favor this or similar types
of high recovery systems over systems that employ extensive caustic
scrubbing.
2. Catalytic Processing
A commercially proven process is available for converting waste
chlorinated hydrocarbons into low cost perchloroethylene and tri-
chloroethylene.15 This process uses oxygen in fluidized bed reactors
to convert the wastes into usable products.
The B.F. Goodrich Chemical Company has claimed the development of
a catalytic oxidation process in which chlorinated hydrocarbons are
destroyed at relatively low temperatures producing a gaseous product
stream which can be fed into the oxychlorination reactors where the
contained HCl is converted into EDC. The remaining gases are vented
with the oxychlorination unit main process vent stream. The process,
which is called CATOXID, is reported to possess the following
characteristics:
1. Complete destruction of all types of chlorinated wastes.
2. Low capital investment.
3. Complete recovery of chlorine value as gaseous hydrogen
chloride.
4. Low maintenance and minimum operating hazards because of
mild operating conditions.
5. Heat recovery in the form of high pressure steam, costly
feed pretreatment is not required.
The first commercial CATOXID unit was expected to come on stream
in the first quarter of 1974. Its current status is unknown.
E. Best Emission Control Systems
If it is deemed adequate to only reduce unsaturated hydrocarbon
emissions, it should be possible to accomplish this by including direct
chlorination facilities downstream of the main oxychlorination reactors.
The solution, however, porbably does not meet the requirements for a
"best" or "most feasible" emission control system.
The most feasible method of reducing total air emission from existing
oxychlorination plants would be to provide a thermal incinerator and
scrubber on the main process vent stream (Table ED-7) and a plume.
burner on the product fractionation vent. Before burning the product
distillation vent gases, these streams should be cooled to 55-60° F
in order to recover EDC and other chlorinated compounds.
Conceptually, the best pollution control system for reducing total
air emissions in new units would include a thermal incinerator, waste
heat boiler and final caustic scrubber on the main process vent stream,
see Table ED-8. After EDC recovery, the product fractionation vent
streams should also be sent to this incinerator. However, as previously
noted, there is insufficient commercial experience available to
determine if this control technique is practical.
-------
ED-35
If liquid chlorinated by-products are to be burned, the effluent
should be sent to an efficient HCl removal system or used to produce
desirable chlorinated hydrocarbons.
In future oxychlorination plants that use tonnage oxygen, all
hydrocarbon vent streams from the EDC plant could be sent to the same
incinerator and HCl recovery system.
Floating roof storage tanks in all new plants would reduce EDC
losses from product storage facilities.
F. Industry Research Efforts
Current industry effort in air pollution control centers around
development of more selective catalysts which will reduce the amount
of chlorinated by-products and increase ethylene conversion. Individual
manufacturers are involved in studies regarding the following:
1. Developing markets for chlorinated compounds rejected in
product distillation section.
2. Removal of chlorinated hydrocarbons from water reject
streams.
3. Recovery of vent material from product storage tanks.
4. Methods of reducing ethylene emissions during catalyst
conditioning.
5. Additional direct chlorination stages to reduce ethylene
emissions.
-------
ED-36
V. National Emission Inventory
Based upon the emission factors shown in Table ED-3A, the total approximate
emissions from U.S. manufacture of EDC in oxychlorination plants are as
follows:
Average Emissions (a) Total Emissions (b)
Component T/T of EDC MM Ibs./yr.
Hydrocarbons
Ethylene 0.0055 18.8
Total Other Non-Methane
Hydrocarbons (c) 0.0224 76.3
Particulates & Aerosols (d) 0.0001 0.4
CO 0.0064 21.8
0.0344 117.3
The above figures do not include any emissions resulting from off-site
processing of waste water and reject hydrocarbon streams. It should be noted
that about 55 percent of the oxychlorination EDC production is in plants that
did not show product fractionation facilities in the survey reports, see
Table ED-3A. Since all of these particular plants also produce vinyl chloride
monomer, it is assumed that any undesirable impurities in the EDC are rejected
in the downstream VCM facilities. In oxychlorination plants that purify EDC
(98.5-99 wt. percent product purity), the hydrocarbon emissions resulting
from product fractionation equal about 0.005 T/T EDC. If this typical figure
is used to project losses for plants which did not show purification facilities,
hydrocarbon emissions would be 9.4 million pounds per year higher than value shown.
Ethylene dichloride production rate is fairly constant throughout the year.
However, several plants did report slightly lower production during the first
quarter of the year. In addition, since cooling water and product storage
temperatures are higher in the summer, it is expected that emissions would be
slightly above average during the warmer months.
(a) Weighted average based on individual plant emission factors and EDC
production figures.
(b) Based on 1,705,000 tons/yr. total EDC production by the oxychlorination process.
(c) Includes 0.0006 T/T of EDC assumed to be emitted from product storage tanks.
(d) Aerosols include HCl and carbon tetrachloride.
-------
ED-37
VI. Ground Level Air Quality Determination
Table ED-3A presents a summary of air emissions data for the various
oxychlorination plants. This table includes emissions from the main process
and product fractionation vent streams. Information regarding vapor losses
from product storage have not been included but are estimated to be lov
(about 0.0006 T/T EDC) for the folloving reasons:
(a) Crude EDC is stored under a vater layer to reduce EDC vaporization.
(b) Vapor pressure of EDC is relatively lov (2-4 PSI) at normal
storage tank operating temperatures.
(c) Crude and product EDC storage tanks usually contain conservation
type vents with vacuum breakers in order to minimize losses.
Table ED-3A provides operating conditions and physical dimensions of
the various vent stacks. The EPA will use this information together vith
the air emission data to calculate ground level concentrations for latter
reporting.
-------
BD-38
VII. Cost Effectiveness of Controls
Table ED-9 presents a cost analysis for alternate methods of reducing
air pollution from the various vents. Economic data presented are for a
new plant producing 700 MM Ibs./year of EDC and are based on the following:
A. Investment
Purchased cost of boilers was obtained from current vendor quotes
for similar packaged type units. Published data 13, were used as an aid
in determining incinerator costs. Investment data provided in various
plant surveys were employed to estimate installed costs for vent gas
coolers and scrubbers. Flare system and plume burner costs for the
main process vent were obtained in a special study that was part of
the overall contract. For the distillation vent, these costs were
derived from questionnaire data for application of similar devices in
other processes.
Installation costs for the various packaged units are estimated
values based on previous experience in plant construction. A major
portion of this costs represents construction labor.
B. Operating Expense
1. Depreciation - 10 year straight line.
2. Interest - Six percent on total capital.
3. Maintenance - Set at 10 percent of investment for boilers and
five percent for incinerators. Maintenance costs for most
other control devices are based on data provided in plant
surveys.
4. Labor - One man per shift used for direct fired boilers and
six hours per day for waste heat boilers and incinerators.
Virtually no operating labor is required for other pollution
control devices.
5. Utilities - Unit costs are based on current typical values for
the Gulf Coast area. After existing contracts expire, it is
possible that fuel gas cost will rise considerably above figure
used in this economic comparison.
It is assumed that process vent gas streams are available at
sufficient pressure to meet &P requirements of the various
pollution control devices (10-20 inches of water).
In the case involving direct fired boilers, investment costs are based
on including a 100 percent spare boiler in order to provide a more dependable
steam supply. Since steam coils in the boiler are within the combustion chamber,
it is very likely that more operational problems will be experienced with this
type of unit than with a waste heat boiler system. This lower reliability may
justify providing spare equipment.
Table ED-9 indicates that employing direct fired boilers with downstream
scrubbing facilities is not economical even if a stand-by boiler system is not
required. Caustic required for effluent neutralization represents a major cost
-------
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ED-41
TABLE ED-9
COST EFFECTIVENESS FOR ALTERNATE
EMISSION CONTROL DEVICES
(BASED ON 700 MM LBS./YR.
ETHYLENE DICHLORIDE PRODUCTION BY OXYCHLORINATION) Sheet 3 of 3
FOOTNOTES:
(a) Feed excludes aromatic solvent absorption oil.
(b) Based on vendor quote for similar unit.
(c) Afterburner systems study by Shell Development Company for EPA, (Contract
EHS-D-71-3).
(d) Excludes cost for disposal of recovered liquid by-products.
(e) Downstream of condenser recovery system.
(f) It is possible that future fuel cost will be considerably higherthan
figure used in this comparison.
(g) Excludes 1,750 SCFM of supplemental fuel.
(h) _ pounds of oxygen that react with pollutants in stream to the device
~ pounds of oxygen that theoretically could react with these pollutants
weighted pollutants in - weighted pollutants out ,nn
^PPP = ; x luu
OElKK- weighted pollutants in
specific pollutant in - specific pollutant out ,nn
CT7 = . X IUU
& specific pollutant in
See Appendix for details.
(i) By definition, a flare system requires supplemental fuel to support
combustion and a plume burner has a self supporting flame.
-------
ED-42
item in this control system. If dilute acid (2-3 wt. percent HC1) can be
utilizied in other process areas, net annual cost could be reduced by 50
percent. Lime slurry, which is less expensive neutralizing agent, could also
be used. However, this material would require larger scrubbing equipment and
also results in more operating and liquid waste disposal problems then
experienced with caustic neutralization.
A thermal incinerator followed by a waste heat boiler and scrubber is
projected to be somewhat more economical to operate than using a single direct
fired unit ($390,000 vs $402,600). Vent gas emissions from this facility would
be similar to the low values predicted for the direct fired boiler. In both
cases, supplemental fuel was assumed to be used in place of feed because of
corrosion problems resulting from high metal temperatures in the preheat
exchanger.
Thermal incineration plus scurbbing of the main process vent gas
(without steam generation) has higher operating cost than the above thermal
incinerator system. However, this or the much less efficient plume burner
could be incorporated in existing plants where steam can not be exported to
other process areas.
If primary interest is to remove unsaturates from the main process vent
stream, this can probably be accomplished by using direct chlorination. The
oxychlorination process licensor that currently incorporates chlorine addition
estimates the investment cost for the proposed ethylene clean-up facility
would be approximately $200,000 and EDC produced from the recovered ethylene
would off-set operating costs. It should be noted that the process licensor
has done some research work in this area but further R & D effort is required
before this technology can be applied in a commercial unit.
It should be noted that economic data presented for the various com-
bustion facilities are based on processing a typical process vent gas having
a heating value of 38 BTU/SCF. If for a particular feedstock, air to hydro-
carbon feed ratio, and catalyst (high selectivity), the vent gas heating value
is lower, it would be necessary to increase supplemental fuel usage. For
example, if the heating value of the vent gas is 30 BTU/SCF and the same
amount of gas is processed, supplemental fuel requirements for the thermal
oxidizers would be 45 percent higher than the amount used in the "typical"
cases. (26 versus 18 MM BTU/hour ) For higher heating value gases, less
fuel would be required.
Data shown for incinerator system include costs for downstream caustic
scrubbing facilities. This neutralizer would replace water scrubbers presently
included in several of the oxychlorination processes.
Table ED-9 includes economics for condensing chlorinated hydrocarbons
from the product fractionation vent stream and flaring the unrecovered material.
In the most feasible new plant, the cooled fractionation vent stream would be
sent to the main process vent gas incinerator system. In this case, investment
costs and steam production would be similar to those values shown in Table
ED-9 for the process vent gas processing. Caustic consumption for effluent
scrubbing would increase about 15 percent.
It is estimated that cost for installing the various pollution control
equipment in existing plants would be about the same or only slightly higher
than for new plant installations shown in Table ED-9. The actual cost dif-
ferential would largely depend on space availability and location in relation
to associated process equipment.
-------
ED-43
VIII. Source Testing
It is recommended that source sampling should be performed on the
feed and effluent streams of the new incinerator being installed by plant
52-10. This represents the only unit where the main process vent stream is
burned. It should be noted that vent gas from plant 52-10 is not typical
in composition to that emitted by other existing oxych1orination units.
However, test data on this plant would be of use in evaluating emissions
from future plants which incorporate pure oxygen feed.
It may be desirable to source test around the vent gas scrubber in
plant 52-7 or 52-8. Besides determining scrubber efficiency, these tests
could be used to confirm the low emissions reported for the chlorine
addition process.
-------
ED-44
IX. Industry Growth Projection
The U. S. annual ethylene dichloride production is estimated to increase
to 20.6 billion pounds by 1985, see Figure ED-4. This represents a 12.5
billion pound per year increase over the present production level. It is
anticipated that about 40 % of this incremental production vill be by the
oxychlorination process. This increase vill reouire the construction of
approximately 8 nev plants between 1972 and 1985, based on an average oxy-
chlorination plant capacity of 700 million pounds per year of EDC.
Approximately 80% of all ethylene dichloride produced is used in the
production of vinyl chloride monomer (VCM). The previous high grovth rate
in EDC production (up to 25%/yr.) partly resulted from replacing the older
VCM manufacturing process, which used acetylene and hydrogen chloride feed,
with the newer ethylene dichloride cracking process. At present over 90%
of the U. S. vinyl chloride monomer production is from EDC. Therefore,
rather than based on plant conversion, future EDC growth vill be more
restricted to the actual growth of VCM demand, vhich is projected to be
8 - 10% per year.
Several new processes are available for VCM production. One process
offered by the Lummus Co, ^ produces VCM from ethane and chlorine. This air
oxidation process "Transcat" is reported to have a 1^/lb. lower VCM manufacturing
cost primarily because of the use of ethane in place of ethylene feedstock.
The Chloe process 10 (Produits Chimique Pechiney - Saint-Gobain, France)
produces VCM from ethylene, chlorine and recycle chloroethanes, which permits a
wide variation in the net VCM and other chlorinated compounds produced. If
either of these processes are used for a significant portion of future VCM
production, EDC demand will be reduced.
About 8% of the EDC produced in the U. S. is used as chlorinated-solvent
intermediate. While market demand for one of these solvents, trichloroethylene,
could possibly decline for ecological reasons, the overall demand in this area
is expected to increase 7 - 8% per year.
Approximately 5%, of the EDC is used to produce ethyleneamines and 3% is
employed as a lead scavenger in gasoline antiknock fluids. Whereas the growth
in amine production is expected to grow 7% per year,the gasoline additive
demand vill decrease during the next fev years as lead-free gasoline comes into
general use.
In 1971 about 57= of U. S. ethylene dichloride vas exported. However, as
more foreign plants are built, these exports are expected to decline.
-------
BD-45
10,000
1,000
tfCk,
1960
1964
1984
-------
KD-46
X. Plant Inspection Procedures
Plant inspections will be conducted by the appropriate authorities, either
on a routine basis or in response to a complaint. A quick inspection of plant
operations will often suggest whether or not a plant is exceeding allowable
emission limits. Among the items which can be easily checked are:
A. High levels of impurities in feed streams. A major portion of many
impurities may appear as air emissions if the vent gas is not
incinerated. However, most of these impurities are usually light
saturated hydrocarbons which are non-reactive.
B. Excessive vent gas flow rate.
C. Visual appearance of plumes of incinerator and other stack gas streams.
D. Discernible odor of HCl or chlorine within the plant.
If the inspector has reason to suspect that emissions are excessive, some
factors that he should consider and/or discuss with plant officials are
itemized below:
A. Process Vent Gas scrubbers
Proper operation of the water and caustic scrubbers are necessary to
limit emissions of HCl and chlorine from the process vent stream. This
vent stream should be essentially odorless and colorless. If the
scrubber is downstream of an incinerator, the effluent should have the
appearance of steam with no residual plume. Excessive vent gas emissions
could be caused by:
1. Liquid and feed gas flow rates above design values.
2. Temperature and pressure of vent gas plus process side pressure
drop across the tower being different than normal plant operating
and design values.
3. Improper waste water pH control. This can result in inefficient
removal of HCl and chlorine. Normally a pH of 7-8 is adequate
to remove HCl. A higher value may be necessary for complete
removal of chlorine.
4. Feed gas temperature exceeding design value. This could result
in excessive carryover of hydrocarbons. High temperatures could
result from inadequate cooling of the oxychlorination reactor
effluent.
B. Process Vent Gas Absorber and Contact Condensers
Proper operation of this equipment is necessary in order to limit
hydrocarbon emissions. Vent gas from plants that incorporate this
recovery equipment should be odorless and colorless. If malfunctioning
of equipment is suspected, it could be caused by:
1. Abnormal feed gas and circulating liquid flow rates.
2. Temperature and pressure of vent gas and process side pressure
drop being different than normal plant operating and design values.
-------
ED-47
3. High operating temperature resulting from (a) inadequate cooling
of the oxychlorination reactor effluent (b) excessive feed or
(c) inadequate cooling within the recovery system, would increase
hydrocarbon losses.
C. Product Fractionation Vents
Temperature of vent streams should not exceed design values. High
temperatures could result from insufficient cooling (refrigeration)
or excessive flow rate. High flow could be caused by maloperation of
the fractionators, poor selectivity in the oxychlorination reactors
or the plant production exceeding design EDC production capacity.
D. Incinerators
Proper operation of by-product and vent gas incinerators (if present)
is necessary to insure low emissions. Since most incinerators are
followed by scrubbing towers it is not usually possible to determine
incinerator performance by a visual inspection of the scrubbed vent
gas. Smoke meter readings on the scrubber feed are desirable in order
to see if the furnace is functioning properly. Smoke-free combustion
requires adequate time, good turbulence in mixing fuel and air plus
sufficient temperature for the reaction to proceed to completion and
produce the desired products of oxidation. The following measures
are normally recommended by manufacturers as methods to improve
performance of a smoky incinerator:
1. Usually smoke results from low combustion zone
temperature (below 1400° F) or improper fuel to air ratio. If
combustion zone temperature is low it may be desirable to
consider reducing the amount of excess air or add supplemental
fuel. Variation in overall feed composition could also result
in low operating temperatures.
2. If operating temperature appears adequate and the furnace still
smokes, it may be necessary to increase air rate to the incinerator
in order to insure complete combustion. However, large amounts of
excess air normally should be avoided since this favors chlorine
formation in the combustion of chlorinated hydrocarbons.
-------
BD-48
XI. Financial Impact
Table ED-10 presents economics for ethylene dichloride manufacture in a
typical 700 MM Ibs./year oxychlorination plant that incorporates a minimum
of air pollution control equipment (water scrubber on the main process vent
gas stream). Based on present cost/price levels, the production of EDC by
the oxychlorination process appears to be fairly profitable (ROI - 13.57o)*.
Table ED-11 provides economics for producing EDC in an existing plant
modified to reduce emissions. Modifications consist of adding an incinerator
plus caustic scrubber on the main process vent stream and condensing chlorinated
hydrocarbons from the product fractionation vent prior to burning the resulting
non-condensibles in a plume burner.
Table ED-11 also shows estimated economics for producing ethylene dichloride
in a new most feasible oxychlorination unit. This plant includes a thermal
incinerator for burning the main process vent gas and the net product
fractionation vent (after EDC recovery). Incinerator effluent is sent to a
waste heat boiler for steam generation and neutralized with caustic in a packed
tower. In addition, EDC product is assumed to be stored in floating roof tanks
($30,000 incremental investment for 350,000 gallon tank) in order to reduce
hydrocarbon losses.
The economic data indicate about a 0.05c/lb. increase in EDC production
cost for both the modified and new most feasible units. Assuming an EDC
selling price of 3.0c/lb., this corresponds to a 20 to 26 percent reduction in
profit and reduces return on investment to about 9.0 percent. Table ED-11 also
shows the effect of variations in capital charges and net operating cost of
pollution control equipment on ROI. It is conceivable that a small part
of the incremental cost for the proposed pollution system in new plants could
be off-set by deletion of scrubbing facilities currently used in some
oxychlorination processes. It is also possible that costs could be somewhat
higher if the value of EDC recovered from the fractionation system vent is
less than assumed (2.5c/lb.).
Table ED-12 presents pro forma balance sheets for the above cases. It
was assumed in developing these asset and liability positions that the ethylene
dichloride selling price would be held constant and any variation in production
costs would be taken out of profit margin in order to maintain sales volume.
Capital requirement for the most feasible new plant is about 1.1 million dollars
higher than for an existing type plant.
In addition to financial impact, it is essential to evaluate the overall
environmental impact of the most feasible method of emission control. A prime
factor for consideration in this evaluation is the effect on fuel savings.
If the vent gas streams are burned and energy recovered as steam in all
future plants, the net energy savings will be equivalent to about 1.6 billion
standard cubic feet per year of natural gas by 1985. This could be a direct
savings in natural gas or savings in energy output from coal or liquid
residual fuels which also represent sources of air pollution. However, if no
steam is produced in these units, net fuel consumption will be equivalent to
1.1 billion standard cubic feed par year of natural gas higher than for the
same units without pollution control.
*However, it should be noted that the cost of raw materials is the major
factor in determining the cost of EDC (over 80 percent of total cost). Conversion
cost is relatively low and capital related items are relatively important in this
process.
-------
ED-49
TABLE ED-10
ETHYLENE PICHLORIDE MANUFACTURING COST
FOR A TYPICAL (MODEL PLANT)
EXISTING 700 MM LB./YR. OXYCHLORINATION FACILITY
DIRECT MANUFACTURING COST
Raw Materials
99.97» Ethylene @ 3.25c/lb.
Anhydrous HCl @ 1.75c/lb.
Catalyst and Chemicals
Labor (3 men/shift @ $4.85/Hr.)
Maintenance (57= of Investment)
Utilities
INDIRECT MANUFACTURING COST
Plant Overhead (110% of Labor)
FIXED MANUFACTURING COST
Depreciation (10 Years)
Insurance & Property Taxes (2.3% of Inv.)
MANUFACTURING COST
GENERAL EXPENSES
Administration (37. of Manufacturing Cost)
Sales (17o of Manufacturing Cost)
Research (270 of Manufacturing Cost)
Finance (67. of Investment)
TOTAL COST
Selling Price
Profit Before Taxes
Profit After 527» Tax
Cash Flow
ROI (NPAT x 100/Plant Investment)
C/LB.
06
19
0.04
0.02
0.04
0.06
2.41
0.02
2.54
2.75
3.00
0.25
0.12
19,250,000
21,000,000
1,750,000
840,000
1,460,000
13.57=
-------
ED-50
TABLE ED-11
ETHYLENE BICHLORIDE MANUFACTURING COST
FOR A TYPICAL MOST FEASIBLE
700 MM LBS./YR.
Type of Unit
DIRECT MANUFACTURING COST
Raw Materials
99.97= Ethylene @ 3.25c/lb.
Anhydrous HCl @ 1.75c/lb.
Catalyst and Chemicals
Labor
Maintenance
Net Utilities
INDIRECT MANUFACTURING COST
Plant Overhead (110% ob Labor)
FIXED MANUFACTURING COST
Depreciation (10 Years)
Ins. & Prop. Taxes (2. 3% of Inv.)
MANUFACTURING COST
GENERAL EXPENSES
Administration (370 of Mfg. Cost)
Sales (17o of Mfg. Cost)
Research (27=, of Mfg. Cost)
Finance (6% of Investment)
TOTAL COST
Selling Price
Profit before Taxes
Profit after 52% Tax
Cash Flow
ROI (NPAT x 100/Plant Investment)
ROI Sensitivity
Increased Capital Charges vc)
Increased Operating Cost (d)
OXYCHLORINATION FACILITY
Modified Existing
Plant (b)
C/LB. $/YR.
1.06
1.18
0.08
0.02
0.05
0.07
2.46
0.02
0.10
0.02
0.12
2.60
0.08
0.03
0.05
0.06
0.22
2.82 19,710,000
3.00 21,000,000
0.18 1,290,000
0.09 619,000
1,322,000
8.8%
6.8%
5 . 1%
C/LB
1.06
1.18
0.08
0.02
0.05
0.04
2.43
0.03
0.10
0.02
0.12
2.58
0.08
0.03
0.05
0.06
0.22
2.80
3.00
0.20
0.10
New Plant (b)
j. $/YR.
(a)
19,600,000
21,000,000
1,400,000
672,000
1,406,000
9.2%
6.5%
5 . 9%
(a) Assumes 0.031c/lb. credit for steam produced in pollution control waste
heat boiler.
(b) Economics for pollution control equipment obtained from Table ED-9.
(c) Capital charges for pollution control equipment double values shown in Table
ED-9.
(d) Capital charges and net operating cost for pollution control equipment double
values shown in Table ED-9.
-------
ED-51
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-------
XII. Cost to Industry
In the typical plant depicted in Table ED-10, about five percent of the
plant investment is directly attributed to cost of air pollution control
equipment. This expenditure plus associated operating costs equals less than
0.5 percent of the EDO total production cost (0.01<:/lb.). If the cost of raw
materials is deducted, the air pollution control contributes about three
percent of the conversion cost.
Total capital cost for modifying all existing plants to incorporate
incineration and scrubbing facilities on the main process vent stream and
condensers plus plume burners on the fractionation vent streams would be about
$5,000,000. In the "most feasible new plant" presented in Table ED-11, air
pollution control equipment represents about 15 percent of the total plant
investment. Assuming all new oxychlorination plants built between now and
1985 incorporate this type of air emission control equipment, the total
incremental capital cost for these plants will be about $9,000,000.
The 0.05c/lb. higher EDC production cost indicated in Table ED-11 for
modified and new plants should not reduce growth in demand for ethylene
dichloride by the oxychlorination process. However, this increase plus an
increase in raw materials costs could reduce the industry growth and result
in the use of substitute materials.
The projected effect of the above expenditures on future air emissions
is shown in Table ED-13.
-------
ID-53
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ED-54
XIII. Emission Control Deficiencies
Technical deficiencies which hinder reducing the level of emissions
include the following:
A. Process Chemistry and Kinetics
In the oxychlorination process, a cupric chloride catalyst is used to
produce EDC. Based upon experimental data it is believed that the reaction
proceeds by formation of an ethylene-oxygen complex, which is subsequently
chlorinated to ethylene dichloride by either HCl or cupric chloride. The
rate determining step is the ethylene oxidation reaction.
The amount of ethylene dichloride produced is influenced by the relative
concentration of feed components, reactor residence time and other
operating conditions.
1. Reactor Feed
(a) Ethylene
Unsaturated hydrocarbon impurities in the ethylene feed can
react with HCl forming undesirable chlorinated by-products.
Therefore, in order to minimize air pollution and maximize
productivity it is desirable to use high purity ethylene. In all
but one plant, ethylene feed contains less than one percent
impurities. In the one case (52-1) where low purity feed
(82-92 percent ethylene) is utilized, chlorinated and non-chlorinated
hydrocarbon emissions are substantially higher than with the
conventional feed. In some cases economics dictate using some
excess ethylene to insure high HCl conversion. This excess
olefin is normally vented to the atmosphere, but could probably
be recovered by a direct chlorination step.
(b) Oxygen Concentration
All but one oxychlorination unit uses air as a source of
oxygen. By utilizing pure oxygen in place of air, plant 52-10
has been able to reduce the volume of vent gas. Even though
the total quantity of hydrocarbon emissions are similar to
those for the other units, most of this material consists of
unconverted ethylene. Besides containing less chlorinated
material, it should be less difficult and cheaper to control
the quantity of emissions from this source.
(c) Hydrogen Chloride
Again, depending upon economics, some excess HCl may be fed
to the reactors to insure high ethylene conversion. One published
article H indicates that excess HCl leads to the formation of
unwanted chlorinated by-products.
2. Reactor Operating Conditions
Reactor operating conditions influence ethylene conversion rate
and to a certain extent the amount of non-selective products. Since
-------
ED-55
unconverted ethylene is lost in the process vent gas stream,
operating conditions are adjusted to obtain high ethylene
conversion and maximum EDC projection.
3. Catalyst
With the catalysts presently employed, ethylene to EDC
selectivity is 90-95 mol percent. Non-selective products
contribute to CO and hydrocarbon emissions in the main process
vent gas. In addition, light and heavy chlorinated hydrocarbon
by-products are formed, which have little or no economic value.
Removal and disposal of these compunds can result in air
pollution problems.
B. Process Equipment and Operations
1. Reactors
The chemical reaction for EDC production is highly
exothermic. For this reason some oxychlorination processes
utilize fluid bed reactors with internal cooling coils. This
type of reactor results in some catalyst carry over in the
effluent stream. However, this catalyst (0.0002 I/I of EDC)
is normally completely removed in the effluent scrubbing
facilities. In fact only one plant (52-6) mentioned particulate
emissions, and in this case they were indicated to be nil.
It is conceivable, that during emergencies which cause shut
down of the scrubbers, some particulate emissions could occur.
2. Plant Operation
Several plants do not analyze the process vent gas on a
frequent basis. Plant 52-6, which normally makes these
analyses on a continuous basis, indicates that these data are
important in controlling plant operation. A continuous record
of ethylene content is desirable to maximize feedstock
utilization and limit hydrocarbon emissions.
C. Control Equipment and Operations
lo Scrubbers
Water or dilute caustic is used to remove unreacted effluent
prior to venting of non-condensibles. The resulting reject
waste water plus water condensed from the reactor effluent
contains some dissolved light chlorinated hydrocarbons.
Subsequent off-site processing of this reject water can result
in hydrocarbon air emissions. In the one oxychlorination plant
that has on-site water strippers for recovery of EDC (plant 52-5),
hydrocarbon air emissions are about 0.0005 I/I of EDC.
2o Process Vent Gas Emission Control
The proposed incineration and caustic scrubbing of the
process vent gas stream is the most feasible method of reducing
air emissions from this stream. The deficiencies in this
treatment are that is results in production of a small amount
of NOx and increases the amount of reject waste water.
-------
ED-56
3. By-Product Disposal
The proposed incineration and downstream recovery of HCl
is the best method of reducing air emissions from product
fractionation vent gas and liquid by-product disposal.
However, the same type of deficiencies exist as are indicated
for the process vent gas control system.
-------
ED-57
XIV. Research and Development Needs
If the technology deficiencies discussed under Section XIII are to be
overcome, additional R & D is desirable in the following areas:
A. Existing Plants
1. Improved Catalyst
It vould be desirable to have a more selective catalyst in
order to reduce air emissions and produce less unvanted chlorinated
by-products. Catalyst development work in this area can best be
handled by the process licensors.
B. Nev Plants
1. Recycle Vent Gas
A combination of pure oxygen feed in place of air and recycle
of vent gas to the reactors could reduce net emissions and improve
feed utilization. By using a recycle system it may be possible to
reduce the amount of excess HCl employed and improve EDC selectiv-
ity, 11 With the recycle processing scheme, it probably vould
be desirable to reduce ethylene conversion rate in order to further
improve selectivity.
2. Modified Raw Materials
In order to improve utilization of ethylene and reduce hydro-
carbon emissions, it may prove beneficial to substitute chlorine
for part of the HCl reactor feed. This proposed R & D study would
employ pure oxygen feed and a vent gas recycle system. The EDC
would be produced in a fluidized bed reactor with chlorine added
to an intermediate reaction zone.
By having the ability to add chlorine to the oxychlorination
reactor, it would be easier to maintain a "balanced" operation.
In fact, it may be possible to replace the separate direct and
oxychlorination units in a balanced plant with a single dual
purpose reactor system.
3. HCl Recovery
Reactor effluent condensation and scrubbing operations associated
with the process and emission control devices result in several
waste water reject streams. These streams could contain significant
amounts of HCl (maximum quantity equals about 0.05 T/T EDC).
Neutralization of this acid does not completely alleviate the
waste Tater disposal problem. In addition, any loss of HCl
results in an increase demand for HCl or chlorine feed to the
overall EDC facility. Therefore, from a water pollution standpoint
and in order to conserve raw materials, it is desirable to recover
this acid. Unfortunately, the oxychlorination process reauires the
use of anhydrous hydrogen chloride and there is no economical method
of obtaining anhydrous acid from the dilute acid waste water streams
(2 - 57= HCl).
It is possible to produce 20 wt. 7, acid from the reject streams
by straight distillation. In order to exceed this concentration.
-------
ED-58
which represents an azeotropic mixture, it is necessary to use
extractive distillation or pressure-stripping followed by successive
partial condensations.
In search of a more economical method of recovery, a brief
study was made of concentrating weak acid by electrodialysis.
However, above five to ten percent HCl concentration, the efficiency
of this process is said to drop off radically.^
While at the present time there appears to be no practical
process available for conentrating dilute HCl, future water
pollution regulations may create added incentive for R & D effort
in this area.
4. Heat Recovery
Since there is limited commercial data available on chlorination
waste incineration with heat recovery, it may be desirable to
study corrosion rates and other potential operating problems
associated with this type of emission control system.
-------
ED-5 9
XV. Research and Development Programs
The following proposed programs are for projects within the general R & D
areas listed in Section XIV. These programs are limited to those projects
which probably have the best chance of success in reducing emissions from
future ethylene dichloride manufacture. It has been assumed that the researcher
has an existing technological base, and the capability to design EDC plants.
Project A
10 Title - Oxygen Feed plus Vent Gas Recycle for Reduced Emissions
2. Object
To study the feasibility of a modified oxychlorination process using
pure oxygen and vent gas recycle to lower gas emissions.
3. Project Cost (see Table ED-14 for cost breakdown)
Capital Expenditures $100,000
Operating Costs
Total Manpower 86,700
Services 6,100
Materials 4,000
Contingency 25,000
$221,800
4. Scope
The primary purpose of this research will be to modify the pure oxygen
oxychlorination process by recycling vent gas to the reactor system
for improved utilization of ethylene feedstock and reduced production
of chlorinated by-products. These process changes will be studied in
a small pilot plant reactor coupled to an on-line gas chromatograph.
Successful completion of the project could lead to a pilot plant
demonstration utilizing the same pilot plant equipment employed in this
study.
5. Program
(a) Construction of Test Unit
This part of the project is concerned with the design, fabrication
and start-up of a laboratory scale unit employing a small tubular reactor.
It is estimated that construction and checkout of the test unit would
require four months.
(b) Process Development
The effect of process operating conditions and recycle gas ratio on
conversion, EDC selectivity and composition of effluent gases will be
studied. A standard copper chloride catalyst will be used for all studies,
(c) Process Engineering
Data from the process development work will be used to design a
model for the oxychlorination process. This model would define
-------
ED-60
TABLE ED-14
DETAILED COSTS
FOR
R & D PROJECT A
PILOT UNIT DESIGN CONSTRUCTION & CHECKOUT
Design Manpower: Professional - 6 weeks 5,600
Technician - 12 weeks 6,200
Major Equipment, Installed 100,000
Contingency 15,OOP
126,800
PROCESS DEVELOPMENT
Operation
Manpower: Professional - 12 weeks 11,100
Technician - 2 men/shift, 3 shifts/day for 12 vks. 51,600
Services: Analytical - 150 hours 2,200
Computational 2,400
Materials 4,000
Contingency 8,OOP
79,300
ENGINEERING
Process Design and Economic Evaluation
Process Engineer - 20 weeks 12,200
Services: Computational 1,500
Contingency 2,000
15,700
-------
ED-61
optimum process parameters for maximum conversion and selectivity
at lowest emission levels.
6. Timetable
The overall time reouired for this project including pilot plant
construction, unit operations and engineering evaluation is estimated
to be 13 months (excludes eouipment delivery time).
Project B
1. Title - Reduction of Vent Gas Emissions from Modified Oxychlorination
Process by the Use of Chlorine
2. Obiect
To study the effect on vent gas emissions of substituting molecular
chlorine for a portion of the hydrogen chloride used in the modified
Oxychlorination process studied in Project A.
3. Proiect Cost (see Table ED-15 for cost breakdovn)
Capital Expenditures $ 30,000*
Operating Costs
Total Manpower 70,300
Services 6,100
Materials 3,500
Contingency 15,000
Total $124,900
"'Incremental cost for adding reactor to Project A pilot unit.
4. Scope
On a laboratory scale, modify the revised Oxychlorination processing
scheme studied in Project A by replacing part of the HCl feed vith
molecular chlorine in order to improve feedstock utilization and reduce
production of chlorinated by-products, it is assumed this study vill
be performed in the Proiect A pilot unit modified to include an
additional reactor in series vith the main Oxychlorination reactor.
5. Program
''a) Construction of Test Unit
A small tubular reactor vill be constructed and added to the
Project A pilot unit.
(b) Process Development
The effect of process operating conditions and HCl and chlorine
split on conversion, EDC selectivity and composition of effluent gases
will be studied. A standard copper chloride catalyst vill be used
for all studies.
fc) Process Engineering
Same as Projec : A
-------
SD-62
TABLE ED-15
DETAILED COSTS
FOR
R & D PROJECT B
PILOT UNIT MODIFICATION & CHECKOUT
Design Manpover: Professional - 3 weeks 2,800
Technician - 6 veeks 3,100
Major Equipment, Installed 30,000
Contingency 6,000
41,900
PROCESS DEVELOPMENT
Operation
Manpower: Professional - 10 weeks 9,200
Technician - 2 men/shift, 3 shifts/day for 10 wks. 43,000
Services: Analytical - 150 hours 2,200
Computational 2,400
Material 3,500
Contingency 7,000
67,300
ENGINEERING
Process Design and Economic Evaluation
Process Engineer - 20 weeks 12,200
Services: Computational 1,500
Contingency 2,000
15,700
-------
ED-63
6. Timetable
The overall time required for this project including pilot plant
modification, unit operations and engineering evaluation is
estimated to be 10 months.
-------
ED-64
XVI. Sampling, Monitoring and Analytical Methods for Pollutants in Air Emissions
Information available on the sampling and analysis of gaseous contaminants
is contained in Table ED-16. Sample collection methods employed in the various
plants involve the use of either bulb type samplers or continuous vacuum
withdrawal. No statements vere made in the plant surveys regarding the
prevention of condensation of vapors in sampling systems but it probably can
be assumed that heating is used where appropriate. As might be expected for
analysis of organic vapors, the gas chromatograph is the principal analytical
instrument. In most cases, inorganic gases are also analyzed on the same
equipment using silica gel or molecular sieve columns.
Only one plant C52-3) furnished sufficient detail to allov reproduction
of the sampling and analytical procedures. However, considering the nature
of the source and contaminants and assuming reasonable care in performance
of these analyses, there appears to be no reason why the methods in use are
not entirely adequate for emissions characterization. Therefore, no further
analytical development work is considered necessary for this industry.
-------
ED-65
Plant No.
52-1
TABLE ED-16
SUMMARY OF SAMPLING AND ANALYTICAL METHODS
FOR POLLUTANTS FROM
PROCESS VENT STREAMS
Page 1 of 3
Comp. ands Sampled
02, C02, Ethylene
Methane, ethane, vinyl
chloride, ethyl chloride
ethylene chloride,
dichloroethane,
dichloroethylene,
carbon tetrachloride.
chloroform
Methods
Continuous, on-stream analyzer -
type unknown. Gas flov metered
continuously.
Sample extracted using 2.5 cc syringe
4-6 times per year. Gas chroma-
tographic analysis - details
unknovn.
52-2
52-3
Carbon Monoxide
Carbon monoxide,
ethane, ethylene C02,
dichloroethane, N2,
02, argon
Ethane, ethylene,
vinyl chloride, ethyl
chloride, carbon tet-
rachloride, 1,2 - di-
chloroethane (all
streams)
Determined about 6 times per year -
method unknovn,
Stack gas flov metered by orifice.
Samples collected in a rubber
volleyball bladder (2 I.) or
glass syringe. Analysis by Varian
thermal conductivity gas chromafco-
graph. Molecular sieve column
for 02, N2, CO and argon.
Porepak S column for organics
and C02.
Sample is collected in a 300 ml.
glass bomb for analysis using a
Perkin-Elmer Model 154-D double
column gas chromatograph.
Operating parameters are:
detector block - 92° C; column
oven- 92° C; detector voltage -
8 volts D. C., - carrier gas-
helium; carrier gas flov - 60
ml./sec.; and sample size -
2 ml. Column 1 for detection
of ethane and ethylene is
V1 x 4' s.s. containing Davidson
grade 08 silica gel in 30/60 mesh
size. Column 2 for detection of
vinyl chloride, ethyl chloride,
carbon tetrachloride and 1,2- di-
chloroethane, is V * 12' s.s.
containing 30% sllicone DC 550
on 60/80 mesh fire brick. Results
are recorded on a Honeyvell
Electronik 19 Recorder and
interpreted vith the aid of a
Hevlett Packard 3370 A
Electronic Integrator. Samples
are drawn into a 2 ml. sample loop
in |ector using vacuum on the glass
bomb.
-------
ED" 66
TABLE ED-16 CONTINUED
SUMMARY OF SAMPLING AND ANALYTICAL METHODS
FOR POLLUTANTS FROM
PROCESS VENT STREAMS
Page 2 of 3
Plant No.
52-3
Compounds Sampled
02, N2, CO, C02,
ethane, ethylene
52-4
52-5
52-6
Ethylene, ethylene
dichloride, methane,
02, C02, CO, N2
Methane, ethane,
ethylene, ethylene
dichloride, solvesso,
N2, C02, CO, 02 plus
argon, H2
Ethylene, dichloro-
ethane, 02, C02, CO,
N2
Methods
Sample is collected in a 300
ml. glass bomb for analysis
using a Beckman GC-1 gas
chromatograph and Honeyvell
Electronik 19 Recorder.
Operating parameters are:
detection block - 38° C;
injection port - 38° C;
column oven - 38° C; bridge
current - 10 ma; carrier gas -
helium at 30 PSI; and
attenuation - 5X. Columns
are \" x 5' silica gel in
series vith a \" x 3' molecular
sieve. The molecular sieve is
valved for by-pass immediately
following the elution of
carbon monoxide. One microliter
samples are iniected using a
3 ul. syringe,
Sample pumped to on-stream,
triple column Bendix gas
chromatograph. Analyses at
13 minute intervals, by
procedure believed to be
similar to plant 52-6.
Flov measured using pilot tube.
Analysis by 3 column, on-stream
gas chromatograph, believed to be
similar to plant 52-6. Checked
vith laboratory chromatograph
once/veek and occasionally
against a mass spectrometer.
Sample obtained from positive
pressure stack through stainless
steel tubing and mist filer.
Analysis at 13 minute intervals
using triple column gas chroma-
tography. Column one (1,2-di-
chloroethane) consists of 3 feet
of 1/8 inch tubing packed vith
5% Octoil S on 60/80 mesh
chromosorb C,. Column tvo (C02,
ethylene) consists of 15 feet of
1/8 inch tubing containing
50/80 mesh Porepak S. Column
three ro2, N~, CO) is a 5 foot by
3/16 inch tubing packed vith 30/60
mesh, 5 Angstrom molecular sieve.
-------
ED-67
Plant No.
52-7, 8 & 9
52-10
TABLE ED-16 CONTINUED
SUMMARY OF SAMPLING AND ANALYTICAL METHODS
FOR POLLUTANTS FROM
PROCESS VENT STREAMS
Page 3 of 3
Compounds Sampled
Ethylene, ethylene
dichloride. ethyl
chloride, 02, CO,
C02
Chlorine (52-7)
Chlorine (52-8 & 9)
Hydrogen chloride
Ethylene, ethane,
ethyl chloride,
ethylene dichloride
vinyl chloride,
ethylene chloride,
vinylidene dichloride,
trans-dichloroethylene,
cis-dichloroethylene,
chloroform, dichloro-
ethane
Methods
Flov rate determined by nitrogen
balance. Occasional gas analyses
using a Peckman Model GCfc-2, triple
column gas chromatograph. Silicone
oil on a packing is used for
chlorinated hydrocarbons, a porepak
Q column for hydrocarbons and a
third column of unknown nature for
oxygen.
Continuous analysis using
ultraviolet spectroscopy.
A gas sample is bubbled through
a potassium iodide solution. Free
iodine is titrated vith sodium
thiosulfate.
HCl is collected in a vater
scrubber and the solution is
titrated vith sodium hydroxide.
Flov measured by helium injection
and dilution. Sample is vithdravn
using a vater aspirator. Hydro-
carbon samples are vithdravn using
a 10 cc syringe for analysis using
a Hevlett Packard Model 700 gas
chromatograph. A single 15 foot
by 1/8 inch column containing
Porepak Q is used for hydrocarbon
separation. Analytical methods
for other components are unknovn.
-------
ED-68
XVII. Emergency Action Plan (EAP) For Air Pollution Episodes
A. Types of Episodes
The alleviation of air pollution episodes as suggested by the U.S.
Environmental Protection Agency is based on a preplanned episode
emission reduction scheme. The criteria that set this scheme into
motion are:
1. Alert Status - The alert level is that concentration of
pollutants at which short-term health effects can be expected
to occur.
2. Warning Status - The warning level indicates that air quality is
continuing to deteriorate and that additional abatement actions
are necessary.
3. Emergency Status - The emergency level is that level at which
a substantial endangerment to human health can be expected.
These criteria are absolute in the sense that they represent
a level of pollution that must not be allowed to occur.
B. Sources of Emissions
As outlined in the foregoing in-depth study of "Ethylene Dichloride
Manufacture by the Oxychlorination Process" there are usually four
continuous streams emitted with several intermittent emissions
occasioned by reactor start-up operations, emergency conditions and,
in at least one oxychlorination process, by a catalyst conditioning
step.
1. Continuous Streams
(a) Main Process Vent Gas
This stream, which generally vents from a scrubber or an
absorber, consists of the gross reactor effluent after quenching
and trim cooling for recovery of EDC and represents the primary
source of emissions from the oxychlorination process.
The amount of vent gas emissions is dependent on a number
of factors; including reactor operating conditions, catalyst
activity, and the processing scheme employed, see Section III.
(b) Product Fractionation Vent
This normally represents a small streati which may vary in
composition to a considerable degree depending upon the type of
fractionation system used. In some cases the stream consists of
the combined vent from several fractionators and, in many
instances, no product fractionation facilities are provided
on-site.
(c) Product Storage Losses
Since the vapor pressure of EDC is low at ambient temperature,
the product storage tanks are in most cases vented directly to
the atmosphere.
-------
ED-69
(d) Waste By-Product Disposal
The chlorinated by-products are usually sent to an
incinerator. In at least one plant, effluent: from the incinerator
is cooled and sent to absorbers for recovery of HC1 with
unrecovered HC1 and chlorine formed in the incineration removed
in a dilute caustic scrubber before atmospheric venting.
2. Intermittent Air Emissions
(a) Reactor Start-Ups
Usually, during these periods (10-20 minutes duration about
twice a month) the main process vent gas to the scrubbers will
be enriched with 0.1 to 0.5 tons HCl/ton EDC. This can result
in increased HCl emissions to the atmosphere.
(b) Emergency Conditions
In an emergency such as a power failure the scrubber will
become ineffective with increased quantities of HCl being vented
to the atmosphere.
(c) Catalyst Conditioning Step
This procedure will result in some ethylene emission during
reactor start-up operations.
C. Abatement Techniques
As the various levels of the pre-planned episode reduction scheme
are declared (Alert, Warning and Emergency) a progressive reduction in
the amount of air pollutants emitted must be made. This could ultimately
lead to total curtailment of pollutant emissions if the emergency level
becomes imminent.
Basically the extent of the required cutback in emissions from ethylene
dichloride plants will depend on the relative amount of offending
constituents contributed by ethylene dichloride production to the
overall emissions which resulted in the pollution episode. Specifically,
however, each facility should be considered with respect to the degree
in which emissions are normally controlled. This should be a factor when
determining the actions required in individual plants during the various
episodes,,
Ethylene dichloride manufacturing facilities generally consist of a
single producing train of equipment with one or more reactors depending
on the capacity of the plant. A multiple reactor system provides for
added flexibility to accomplish a partial reduction in air pollutant
emissions during an air pollution alert. The prime option, however,
for a partial reduction in emissions is the capability of turning down
plant capacity. Emissions are directly proportional to plant throughput.
One hour is required to make an orderly shutdown of a single reactor and a
minimum of several hours is required for start-up. However, on those
plants that are integrated with a unit to produce vinyl chloride by
"cracking" EDC, several hours to several days may be required to shutdown
and start-up the overall complex. A turndown to 50-60 percent of EDC
-------
ED-70
capacity can normally be accomplished in two hours or less with a
similar period required to resume normal production.
In either of the foregoing options to accomplish a partial reduction
in air pollutants, consideration should be given to those plants that
do not contain on-site fractionation facilities for further processing,
thus, a significant reduction in the production of EDC would require
judicious handling of the downstream equipment.
While operating at reduced plant capacity, scrubbing facilities
and the main process vent absorber-stripper system should be maintained
at normal operating conditions with design liquid flow rates. The
reduction in emissions to this equipment should improve their efficiency
thus accomplishing a further reduction of polluting constitutents.
During any air pollution episode, intermittent air emissions
should be curtailed to the greatest possible extent. Since reactor
start-ups will contribute to increased emissions, resumption of reactor
operation should not be undertaken until an "all clear" is announced
for the episode. Additionally, since mal-operation of the scrubber
and/or absorber-stripper will result in a significant increase in
pollutant emissions, increased vigilance in the operation of this equipment
should be in force.
1. Declaration of Alert Condition
When an alert condition is declared, the episode emission
reduction plan is immediately set into motion. Under this plan
in addition to notifying the manufacturer of the alert condition
it may be deemed necessary to reduce emissions from ethylene
dichloride manufacture somewhat to conform in the overall reduction
plan set forth by the Environmental Protection Authorities. This
may be accomplished by employing one"of the foregoing options.
The time required to affect the reduction will depend on the route
selected and the amount of reduction in plant capacity required.
As previously stated, effort should be made to curtail any emissions
that would result from intermittent sources. Usually the alert
condition can be expected to continue for 12 hours or more.
2. Declaration of Warning Condition
When the air pollution warning episode is announced, a substantial
reduction of air contaminants is desirable even to the point of
assuming reasonable economic hardship in the cutback of production
and allied operations. This could involve a 50-60 percent decrease
in EDC production which would reduce the principal source of emission,
represented by the main process vent gas, to a value equivalent to
the reduction made in plant capacity. The other sources of emissions
represented by the product fractionation vent and product storage
losses may decrease to some degree by virtue of the reduction made
in the producing equipment.
The reduction in operation of the producing units could temporarily
result in some increase in emissions during the "Line out period" at
the reduced operation.
-------
ED-71
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ED-7 2
3. Emergency Condition
When it appears that an air pollution emergency episode is
imminent, all air contaminants except those resulting from storage
facilities may have to be eliminated immediately. This may be
accomplished by ceasing production and allied operations exclusive
of emission control equipment to the extent possible without
causing injury to persons or damage to equipment. Complete
shutdown of the unit will require approximately three to four
hours, if done in an orderly fashion. Otherwise there may be
excessive emissions for a short (one hour) period of time.
Normally, complete cessation of production should not result in
increased emissions since the polluting constituents in the stream
to the pollution control equipment will rapidly decrease as the
plant ceases operation.
D. Economic Considerations
The economic impact on ethylene dichloride manufacturers of
curtailing operations during any of the air pollution episodes depends
on the duration and number of episodes in a given period. It is
indicated that the duration of air pollution episodes is usually one
to seven days with meteorology episode potentials as high as 80 per
year.17 The frequency of air pollution episodes in some areas is
indicated as being one to four per year. These data do not differentiate
between the episode levels. Normally, since the alert level does not
require a cutback in production, it will not influence plant economics.
Therefore, in discussing economic considerations resulting from the air
pollution abatement plan, it is only necessary to estimate the frequency
and number of warning and emergency episodes. For the economic study,
it has been assumed that three warning and no emergency episodes occur
per year. Each warning episode is assumed to require a 50 percent
reduction in air contaminants for a period of five and one half days.
This then equates to a complete loss in plant production of about eight
and one-half days per year.
The financial impact resulting from this loss in production is shown
in Table ED-17. This table contains comparative manufacturing costs for
a typical existing 700 MM Ibs./year oxychlorination facility without
extensive pollution control (Table ED-10), a modified existing plant
(Table ED-11) and a most feasible new plant (Table ED-11), all of the
same capacity. Economics are shown for each of these plants with and
without the financial impact accredited to the air pollution episodes.
It should be noted that whereas the assumed cutback in ethylene
dichloride production for emission control appears small (2.5 percent
on a yearly basis), it reduces net profit from 6.5 to 8.5 percent for
the three cases shown.
In most cases, a plant producing ethylene dichloride by oxychlorination
is part of an integrated chemical complex and the economic effect of
curtailing EDC prdocution can not be completely evaluated without considering
the effect on other related operations, such as ethylene and chlorine
production. In addition, the pollution contributions from these other
plants will also be affected as a result of curtailed production.
-------
ED-7 3
E. Summary of Estimated Emissions
In the foregoing, a reduction in air pollutant emissions
was suggested for the various air pollution levels that may be
encountered. This was predicated on an existing plant that
incorporates a minimum of air pollution control equipment. Special
consideration should be made in the EAP for Air Pollution Episode
Avoidance for plants that incorporate control facilities similar
to those proposed for the "most feasible modified existing plant" and
"most feasible new plant".
The following presents estimated air emissions for a typical
present day system with and without extensive pollution control.
Pollutant
Hydrocarbons
Ethylene
Other Non-Methane
Hydrocarbons
Paritculates & Aerosols
NOx
CO
Typical
Existing
Plant
Average
Emissions,
T/T (A)
0.0055
0.0224 (D)
0.0001
0.0064
0.0344
Most
Feasible
Modified
Plants
Average
Emissions
T/T (B)
Most
Feasible New
Plants
Average
Emissions,
T/T (C)
0.0007 (D)
0.0009
0.0001 0.0001
0.0017
0.0001
(A) Minimum air pollution control (water scrubber on main process gas
stream).
(B) Incorporates thermal incinerator and scrubber on process vent
stream plus distillation vent condensers and plume burners.
(C) Incorporates thermal incineration with waste heat boiler, caustic
scrubber on process and fractionation vent streans and floating
roof product storage tanks.
(D) Includes 0.0006 T/T of EDC lost from product storage tanks.
As noted in the above, total emissions for the most feasible modified
plant and the most feasible new plant have been reduced to 5.0 percent
and 0.3 percent respectively of that estimated for the existing plant
with minimum pollution control. However, it should be noted that some
NOx emissions result from the inclusion of the incinerating devices.
The particular type and concentration of pollutants in the atmosphere
at the time of the episode would dictate the degree to which reductions
would be made on the most feasible modified plant and the most feasible
new plant. If NOx is the offending material, then it is conceivalbe
that some reduction in production in these plants may be required under
"Declaration of Warning Condition". If the offending pollutants are in
the form of hydrocarbons or particulates, the degree of cutback on the
-------
ED-74
most feasible modified plants could be proportionally less severe
than on the existing plant with minimum air pollution control. In
this instance no cutback would be required on the most feasible new
plant.
In addition to the above items, variations in the process and
processing scheme in the plants should be considered in setting the
production cutback requirement during air pollution episodes. For
example oxygen based plants have the potential for low emissions.
If normal end ssione are low, production cutback may not be necessary.
-------
ED-7 5
References
1. "Chemical Economics Handbook", Stanford Research Institute, January, 1972.
2. "Ethylene Dichloride Chemical Profile", Chemical Marketing Reporter,
October 1, 1968, September 20, 1971.
3. "Vinyl Chloride", Hydrocarbon Processing, page 220, November, 1971.
4. De Forester, E. M. and Penners, S. E., "Fixed-Bed Oxychlorination Yields
1,2 - Dichloroethane", Chemical Engineering, page 54, August 7, 1972.
5. Spitz, P. H. , "Vinyl Chloride Economics - Effects of Plant Size and Changing
Technology", Chemical Engineering Progress, page 19, March, 1968.
6. "Background Information for Establishment of Standards of Air Pollution
Control in the Petrochemical Industry Ethylene and Derivatives", Processes
Research, Inc. for Environmental Protection Agency (Task Order No. 15),
August 13, 1971.
7. "1971 Directory of Chemical Producers - USA", Chemical Information Services,
Stanford Research Institute,
8. Santoleri, J. J., "Chlorinated Hydrocarbon Waste Disposal and Recovery
Systems", Chemical Engineering Progress, page 68, January, 1973.
9. "New VCM Process Uses Ethane Feedstock", Hydrocarbon Processing, page 11,
March, 1971.
10. Rosenzweig, M. D., "VCM Process Has Wide Range of By-Products", Chemical
Engineering, page 105, October 18, 1971.
11. Carrubba, R. V. and Spencer, J. L., "Kinetics of the Oxychlorination of
Ethylene", Industrial Engineering Chemistry Process Des. Develop.,
page 414-419, Vol. 9, No. 3, 1970.
12. Private communications with Ionics Incorporated, Watertown, Massachusetts.
13. Rolke, R. W., et al, "Afterburner Systems Study", by Shell Development
Company for Environmental Protection Agency (Contract EHS-D-71-3).
14. Russell, R. R. and Mraz, J. A., of Union Carbide Corporation, "Hydrochloric
Acid Recovery From Chlorinated Organic Waste" paper presented at AICHE
Workshop in Midland, Michigan, November, 1972.
15. Knoop, J. F. and Neikirk, G. R., "Oxychlorinate for PER/TRI" Hydrocarbon
Processing, page 109, November, 1972.
16. Herrington, L. E., "Ethyl Chloride Gas Stream Consumed by Thermal Oxidation",
Chemic a1 Processing, page 20, September, 1973.
17. "Guide for Air Pollution Episode Avoidance", Environmental Protection Agency,
Office of Air Programs, Publication No. AP-73, June, 1971.
-------
APPENDIX I
BASIS OF THE STUDY
I. Industry Survey
The study which led to this document was undertaken to obtain information
about selected production processes that are practiced in the Petrochemical
Industry. The objective of the study was to provide data for the EPA to use
in the fulfillment of their obligations under the Clean Air Amendments of 1970.
The information obtained during the study includes industry descriptions,
air emission control problems, sources of air emissions, statistics on quantities
and types of emissions and descriptions of emission control devices currently
in use. The principal source for these data was an Industry Questionnaire
but it was supplemented by plant visits, literature searches, in-house back-
ground knowledge and direct support from the Manufacturing Chemists Association.
More than 200 petrochemicals are currently produced in the United States,
and many of these by two or more different processes. It was obvious that
the most immediate need was to study the largest tonnage, fastest growth
processes that produce the most pollution. Consequently, the following 32
chemicals (as produced by a total of 41 different processes) were selected
for study:
Acetaldehyde (two processes)
Acetic Acid (three processes)
Acetic Anhydride
Acrylonitrile
Adipic Acid
Adiponitrile (two processes)
Carbon Black
Carbon Bisulfide
Cyclohexanone
Ethylene
Ethylene Dichloride (two processes)
Ethylene Oxide (two processes)
Formaldehyde (two processes)
Glycerol
Hydrogen Cyanide
Maleic Anhydride
Nylon 6
Nylon 6,6
"Oxo" Alcohols and Aldehydes
Phenol
Phthalic Anhydride (two processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Terephthalic Acid (1)
Toluene Di-isocyanate (2)
Vinyl Acetate (two processes)
Vinyl Chloride
(1) Includes dimethyl terephthalate.
(2) Includes methylenediphenyl and polymethylene polyphenyl isocyanates.
The Industry Questionnaire, which was used as the main source of information,
was the result of cooperative efforts between the EPA, Air Products and the
EPA's Industry Advisory Committee. After receiving approval from the Office of
Management and Budget, the questionnaire was sent to selected producers of
most of the chemicals listed above. The data obtained from the returned
questionnaires formed the basis for what have been named "Survey Reports".
These have been separately published in four volumes, numbered EPA-450/3-73-005a,
b, c, and d and entitled "Survey Reports on Atmospheric Emissions from the
Petrochemical Industry - Volumes I, II, III, and IV.
-------
1-2
The purpose of the survey reports was to screen the various petrochemical
processes into the "more" and "less - significantly polluting processes".
Obviously, significance of pollution is a term whi':h is difficult if not
impossible to define because value judgements ara involved. Recognizing this
difficulty, a quantitative method for Significant Emission Index (SEI) was
developed. This procedure is discussed and illustrated in Appendix II of
this report. Each survey report includes the calculation of an SEI for the
petrochemical that is the subject of the report. These SEI's have been
incorporated into the Emission Summary Table that constitutes part of this
Appendix (Table I). This table can be used as an aid when establishing
priorities in the work required to set standards for emission controls on
new stationary sources of air pollution in accordance with the terms of the
Clean Air Amendments of 1970.
The completed survey reports constitute a preliminary data bank on each
of the processes studied. In addition to the SEI calculation, each report
includes a general introductory discussion of the process, a process description
(including chemical reactions), a simplified process flow diagram, as well as
heat and material balances. More pertinent to the air pollution study, each
report lists and discusses the sources of air emissions (including odors and
fugitive emissions) and the types of air pollution control equipment employed.
In tabular form, each reports summarizes the emission data (amount, composition,
temperature, and frequency); the sampling and analytical techniques; stack
numbers and dimensions; and emission control device data (types, sizes, capital
and operating costs, and efficiencies).
Calculation of efficiency on a pollution control device is not necessarily
a simple and straight-forward procedure. Consequently, two rating techniques
were developed for each type of device, as follows:
1. For flares, incinerators, and boilers a Completeness of Combustion Rating
(CCR) and Significance of Emission Reduction Rating (SERR) were used.
2. For scrubbers and dust removal equipment, a Specific Pollutant
Efficiency (SE) and a SERR were used.
The bases for these ratings and example calculations are included in
Appendix III of this report.
II. In-Depth Studies
The original performance concept was to select: a number of petrochemical
processes as "significant polluters", on the basis of data contained in
completed questionnaires. These processes were then to be studied "in-depth".
However, the overall time schedule was such that the EPA requested an initial
selection of three processes on the basis that they would probably turn out
to be "significant polluters". The processes selected in this manner were:
1. The Furnace Process for producing Carbon Black.
2o The Sohio Process for producing Acrylonitrile.
3. The Oxychlorination Process for producing 1,2 Dichloroethane
(Ethylene Bichloride) from Ethylene.
-------
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1-6
In order to obtain data on these processes, the operators and/or
licensors of each were approached directly by Air Products' personnel.
This, of course, was a slow and tedious method of data collection because
mass mailing techniques could not be used, nor could the request for data
be identified as an "Official EPA Requirement". Yet, by the time that OMB
approval was given for use of the Industry Questionnaire, a substantial
volume of data pertaining to each process had already been received. The
value of this procedure is indicated by the fact that first drafts of these
three reports had already been submitted to the EPA, and reviewed by the
Industry Advisory Committee, prior to the completion of many of the survey
reports.
In addition, because of timing requirements, the EPA decided that three
additional chemicals be "nominated" for in-depth study. These were phthalic
anhydride, formaldehyde and ethylene oxide. Consequently, four additional
in-depth studies were undertaken, as follows:
1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.
2. Air Oxidation of Methanol in a Methanol Rich Process to produce
Formaldehyde over a Silver Catalyst. (Also, the subject of a
survey report.)
3. Air Oxidation of Methanol in a Methanol-Lean Process to
produce Formaldehyde over an Iron Oxide Catalyst.
4. Direct Oxidation of Ethylene to produce Ethylene Oxide.
The primary data source for these was the Industry Questionnaire,
although SEI rankings had not been completed by the time the choices were
made.
The Survey Reports, having now been completed are available, for use in
the selection of additional processes for in-depth study.
-------
INTRODUCTION TO APPENDIX II AND III_
The following discussions describe techniques that were developed for
the single purpose of providing a portion of the guidance required in the
selection of processes for in-depth study. It is believed that the underlying
concepts of these techniques are sound. However, use of them without sub-
stantial further refinement is discouraged because the data base for their
specifics is not sufficiently accurate for wide application. The subjects
covered in the Appendix II discussion are:
1. Prediction of numbers of new plants.
2. Prediction of emissions from the new plants on a weighted
(significance) basis.
The subject covered in the Appendix III discussion is:
Calculation of pollution control device efficiency on a variety of
bases, including a weighted (significance) basis.
It should be noted that the weighting factors used are arbitrary.
Hence, if any reader of this report wishes to determine the effect of
different weighing factors, the calculation technique permits changes in
these, at the reader's discretion.
-------
APPENDIX El
Number of New Plants*
Attached Table 1 illustrates the format for this calculation.
Briefly, the procedure is as follows:
1. For each petrochemical that is to be evaluated, estimate what
amount of today's production capacity is likely to be on-stream
in 1980. This will be done by subtracting plants having marginal
economics due either to their size or to the employment of an
out-of-date process.
2. Estimate the 1980 demand for the chemical and assume a 1980
installed capacity that will be required in order to satisfy
this demand.
3. Estimate the portion of the excess of the 1980 required capacity
over today's remaining capacity that will be made up by
installation of each process that is being evaluated.
4. Estimate an economic plant or unit size on the basis of today's
technology.
5. Divide the total required new capacity for each process by the
economic plant size to obtain the number of new units.
In order to illustrate the procedure, data have been incorporated
into Table I, for the three processes for producing carbon black, namely
the furnace process, the relatively non-polluting thermal process, and
the non-growth channel process.
*The format is based on 1980, but any future year may be selected.
-------
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II-3
Increased Emissions (Weighted) by 1980
Attached Table 2 illustrates the format for this calculation.
However, more important than format is a proposal for a weighting basis.
There is a wide divergence of opinion on which pollutants are more noxious
and even when agreement can be reached on an order of noxiousness, dis-
agreements remain as to relative magnitudes for tolerance factors. In
general pollutants from the petrochemical industry can be broken down into
categories of hydrogen sulfide, hydrocarbons, particulates, carbon monoxide,
and oxides of sulfur and nitrogen. Of course, two of these can be further
broken down; hydrocarbons into paraffins, olefins, chlorinated hydrocarbons,
nitrogen or sulfur bearing hydrocarbons, etc. and particulates into ash,
catalyst, finely divided end products, etc. It was felt that no useful
end is served by creating a large number of sub-groupings because it would
merely compound the problem of assigning a weighting factor,, Therefore,
it was proposed to classify all pollutants into one of five of the six
categories with hydrogen sulfide included with hydrocarbons,,
There appears to be general agreement among the experts that carbon
monoxide is the least noxious of the five and that NOX is somewhat more
noxious than SOX. However, there are widely divergent opinions concerning
hydrocarbons and particulates - probably due to the fact that these are
both widely divergent categories. In recent years, at least two authors
have attempted to assign tolerance factors to these five categories.
Babcock (1), based his on the proposed 1969 California standards for
one hour ambient air conditions with his own standard used for hydrocarbons.
On the other hand, Walther (2), based his ranking on both primary
and secondary standards for a 24-hour period. Both authors found it
necessary to extrapolate some of the basic standards to the chosen time
period. Their rankings, on an effect factor basis with carbon monoxide
arbitrarily used as a reference are as follows:
Babcock
Walther
Hydrocarbons
Particulates
NOX
so.
CO
x
2.1
107
77.9
28.1
1
Primary
125
21.5
22.4
15.3
1
Secondary
125
37.3
22.4
21.5
Recognizing that it is completely unscientific and potentially subject
to substantial criticism it was proposed to take arithmetic averages of the
above values and round them to the nearest multiple of ten to establish a
rating basis as follows:
Hydrocarbons
Particulates
NOX
sox
CO
Average
84.0
55.3
40.9
21.6
1
Rounded
80
60
40
20
1
-------
II-4
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II-5
Increased Emissions (Weighted) by 1980 (continued)
This ranking can be defended qualitatively, if not quantitatively for
the following reasons:
1. The level of noxiousness follows the same sequence as is obtained
using national air quality standards.
2. Approximately two orders of magnitude exist between top and bottom
rankings.
3. Hydrocarbons should probably have a lower value than in the
Walther analysis because such relatively non-noxious compounds
as ethane and propane are included.
4. Hydrocarbons should probably have a higher value than in the
Babcock analysis because such noxious (or posionous) substances
as aromatics, chlorinated hydrocarbons, phenol, formaldehyde, and
cyanides are included.
5. Particulates should probably have a higher value than in the
Walther analysis because national air standards are based mostly
on fly ash while emissions from the petrochemical industry are
more noxious being such things as carbon black, phthalic anhydride,
PVC dust, active catalysts, etc.
6. NOX should probably have a higher value than in the Walther
analysis because its role in oxidant synthesis has been neglected.
This is demonstrated in Babcock's analysis.
Briefly, the procedure, using the recommended factors and Table 2, is
as follows:
1. Determine the emission rate for each major pollutant category in
terms of pounds of pollutant per pound of final product. (This
determination was made, on the basis of data reported on returned
questionnaires>in the Survey Reports^.
2. Multiply these emission rates by the estimate of increased production
capacity to be installed by 1980 (as calculated while determining
the number of new plants), to determine the estimated pounds of
new emissions of each pollutant.
3. Multiply the pounds of new emissions of each pollutant by its
weighting factor to determine a weighted pounds of new emissions
for each pollutant.
4. Total the weighted pounds of new emissions for all pollutants to
obtain an estimate of the significance of emission from the process
being evaluated. It was proposed that this total be named
"Significant Emission Index" and abbreviated "SEI".
It should be pointed out that the concepts outlined above are not
completely original and considerable credit should be given to Mr. L. B. Evans
of the EPA for setting up the formats of these evaluating procedures.
-------
II-6
Increased Emissions (Weighted) by 1980 (continued)
(1) Babcock, L. F., "A Combined Pollution Index for Measurement of Total
Air Pollution," JAPCA, October, 1970; Vol. 20, No. 10; pp 653-659
(2) Walther, E. G., "A Rating of the Major Air Pollutants and Their Sources
by Effect", JAPCA, May, 1972; Vol. 22, No. 5; pp 352-355
-------
Appendix III
Efficiency of Pollution Control Devices
Incinerators and Flares
The burning process is unique among the various techniques for
reducing air pollution in that it does not remove the noxious substance
but changes it to a different and hopefully Less noxious form. It can be,
and usually is, a very efficient process when applied to hydrocarbons,
because when burned completely the only products of combustion are carbon
dioxide and water. However, if the combustion is incomplete a wide range
of additional products such as cracked hydrocarbons, soot and carbon
monoxide might be formed. The problem is further complicated if the
hydrocarbon that is being burned is halogenated, contains sulfur or is
mixed with hydrogen sulfide, because hydrogen chloride and/or sulfur oxides
then become products of combustion. In addition, if nitrogen is present,
either as air or nitrogenated hydrocarbons, oxides of nitrog;en might be
formed, depending upon flame temperature and residence time.
Consequently, the definition of efficiency of a burner, as a pollution
control device, is difficult. The usual definition of percentage removal of
the noxious substance in the feed to the device is inappropriate, because
with this definition, a "smoky" flare would achieve the same nearly 100
percent rating, as a "smokeless" one because most of the feed hydrocarbon
will have either cracked or burned in the flame. On the other hand, any
system that rates efficiency by considering only the total quantity of
pollutant in both the feed to and the effluent from the device would be
meaningless. For example, the complete combustion of one pound of hydrogen
sulfide results in the production of nearly two pounds of sulfur dioxide, or
the incomplete combustion of one pound of ethane could result in the
production of nearly two pounds of carbon monoxide.
For these reasons, it was proposed that two separate efficiency rating
be applied to incineration devices. The first of these is a "Completeness
of Combustion Rating" and the other is a "Significance of Emission Reduction
Rating", as follows:
1. Completeness of Combustion Rating (CCR)
This rating is based on oxygen rather than on pollutants and is
the pounds of oxygen that react with the pollutants in the feed to
the device, divided by the theoretical maximum number of pounds that
would react: Thus a smokeless flare would receive a 100 percent
rating while a smoky one would be rated somewhat less, depending upon
how incomplete the combustion.
In utilizing this rating, it is clear that carbon dioxide and water
are the products of complete combustion of hydrocarbons. However, some
question could occur as to the theoretical completion of combustion
when burning materials other than hydrocarbons. It was recommended
that the formation of HX be considered complete combustion of halogenated
hydrocarbons since the oxidation most typically does not change the
valence of the halogen. On the other hand, since some incinerators will
be catalytic in nature it was recommended that sulfur trioxide be
considered as complete oxidation of sulfur bearing compounds.
-------
III-2
Efficiency of Pollution Control Devices
1. Completeness of Combustion Rating (OCR) (continued)
Nitrogen is more complex, because of the equilibria that exist
between oxygen, nitrogen, nitric oxide, nitrogen dioxide and the
various nitrogen radicals such as nitrile. In fact, many scientists
continue to dispute the role of fuel nitrogen versus ambient nitrogen
in the production of NOX. In order to make the CCR a meaningful
rating for the incineration of nitrogenous wastes it vas recommended
that complete combustion be defined as the production of N2, thus
assuming that all NOX formed comes from the air rather than the fuel,
and that no oxygen is consumed by the nitrogen in the waste material.
Hence, the CCR becomes a measure of how completely the hydrocarbon
content is burned, while any NOX produced (regardless of its source)
will be rated by the SERR as described below.
2„ Significance of Emission Reduction Rating (SERR)
This rating is based primarily on the weighting factors that
were proposed above. All air pollutants in the feed to the device
and all in the effluents from the device are multiplied by the
appropriate factor. The total weighted pollutants in and out are
then used in the conventional manner of calculating efficiency
of pollutant removal, that is pollutants in minus pollutants out,
divided by pollutants in, gives the efficiency of removal on a
significance of emission basis.
Several examples will serve to illustrate these rating factors.
as follows:
Example 1 - One hundred pounds of ethylene per unit time is burned
in a flare, in accordance with the following reaction;
3C2H4 + 7 02 "" fr C + 2 CO + 3 C02 + 6 H20
Thus, 14.2 Ibs. of particulate carbon and 66.5 Ibs. of carbon
monoxide are emitted, and 265 Ibs. of oxygen are consumed.
Theoretical complete combustion would consume 342 Ibs. of oxygen
in accordance with the following reaction:
C2H4 + 3 02 > 2 C02 +2 H20
Thus, this device would have a CCR of 265/342 or 77.5%
Assuming that one pound of nitric oxide is formed in the reaction
as a result of the air used for combustion (this is about equivalent to
100 ppm), a SERR can also be calculated. It should be noted that the
formation of this NO is not considered in calculating a CCR because it
came from nitrogen in the air rather than nitrogen in the pollutant
being incinerated. The calculation follows:
-------
III-3
Efficiency of Pollution Control Devices
2. Significance
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Total
of Emission
Weighting
Factor
80
60
40
20
1
Reduction Rating (SERR)
Pounds in
(continued)
Pounds out
Actual Weighted Actual Weighted
100 8000 0
0 14
0 1
0 0
0 66
8000
.2 852
40
.5 66.5
958.5
SERR = 8000 - 958.5
8000 x i(JU ~ °0/°
Example 2 - The same as Example 1, except the hydrocarbons are
burned to completion. Then,
342 '
and
SERR = 8000 - 40
8000
= 99.5%
Example 3 - One hundred pounds per unit time of methyl chloride is
incinerated, in accordance with the following reaction.
2 CH3C1 + 3 02 > 2 C02 +2 H20 + 2 HC1
This is complete combustion, by definition, therefore, the CCR is
100%. However, (assuming no oxides of nitrogen are formed), the SERR
is less than 100% because 72.5 Ibs. of HC1 are formed. Hence,
considering HCl as an aerosol or particulate;
SERR = 100 x 80 - 72.5 x 60 1nn _ ,, c
-------
III-4
Efficiency of Pollution Control Devices
Significance of Emission Reduction Rating (SERR) (continued)
4 HCN + 5 02 ' ' fr 2 H20 + 4 C02 + 2 N2
N2 (atmospheric) + X02 •• ---^ 2 N0x
Thus, CCR^ = 1007o and CCR2 = 100% both by definition.
However, SERRj^ = 100 x 80 - 1 x 40
100 x 80
and SERR9 = 100 x 80 - 10 x 40
2 - 100 x 80 - * 10° = 957°
Obviously, if either of these were "smoky" then both the CGR and
the SERR would be lower, as in Example 1.
Other Pollution Control Devices
Most pollution control devices, such as bag filters, electrostatic
precipitators and scrubbers are designed to physically remove one or more
noxious substances from the stream being vented. Typically, the efficiency
of these devices is rated relative only to the substance which they are
designed to remove and for this reason could be misleading. For example:
1. The electrostatic precipitator on a power house stack might be
99% efficient relative to particulates , but will remove little
or none of the SOX and NOX which are usually present.
2, A bag filter on a carbon black plant will remove 99 + °L of the
particulate but will remove none of the CO and only relatively
small amounts of the compounds of sulfur that are present.
3. A water scrubber on a vinyl chloride monomer plant will remove
all of the hydrogen chloride but only relatively small amounts
of the chlorinated hydrocarbons present.
4o An organic liquid scrubber on an ethylene dichloride plant will
remove nearly all of the EDC but will introduce another pollutant
into the air due to its own vapor pressure.
For these reasons, it was suggested again that two efficiency ratings be
applied. However, in this case, the first is merely a specific efficiency as
is typically reported, i.e., "specific to the pollutant (or pollutants) for
which it was designed", thus:
SE = specific pollutant in - specific- pollutant out - „_.
- - TT. - \ ., / - : — - x 100
specific pollutant in
The second rating proposed is an SERR, defined exactly as in the case
of incinerators.
Two examples will illustrate these ratings.
-------
IH-5
Efficiency of Pollution Control Devices
Other Pollution Control Devices (continued)
Example 1 - Assume that a catalytic cracker regenerator effluent
contains 100 pounds of catalyst dust, 200 Ibs. of
carbon monoxide and 10 pounds of sulfur oxides per unit
time. It is passed through a cyclone separator where
95 pounds of catalyst are removed. Therefore,
SE = 100 - 5
x 100 = 95%
and SERR = (100 x 60 + 10 x 20 -f 200 x 1) - (5 x 60 + 10 x 20 + 200 x 1) x 100
(100 x 60 + 10 x 20 + 200 x 1)
= 6400 - 700 x 100 = 89%
6400
Example 2 - Assume that an organic liquid scrubber is used to wash a
stream containing 50 pounds of 862 per unit time. All
but one pound of the S(>2 is removed but two pounds of
the hydrocarbon evaporate into the vented stream. Then
= 987°
and SERR = (50 x 20) - (1 x 20 + 2 x 80)
- (50 x 20) - x 10°
- 180 x 100 = 82%
1000
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-45Q/3-73-006-C
2.
3. RECIPIENT'S ACCESSION NO.
4 TITLE AND SUBTITLE
Engineering and Cost Study of Air Pollution Control
for the Petrochemical Industry, Volume 3: Ethylene
Pi chloride Manufacture by Oxychlorination
5. REPORT DATE
November 1974
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
W. A. Schwartz, F. B. Higgins, Jr., J. A. Lee,
R. Newirth, J. W. Pervier
8. PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Houdry Division/Air Products and Chemicals, Inc
P. 0. Box 427
Marcus Hook, Pennsylvania 19061
10. PROGRAM ELEMENT NO.
11 CONTRACT/GRANT NO.
68-02-0255
12 SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Air Quality Planning & Standards
Industrial Studies Branch
Research Triangle Park, N. C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This document is one of a series prepared for the Environmental Protection
Agency (EPA) to assist it in determining those petrochemical processes for which
standards should be promulgated. A total of nine petrochemicals produced by
twelve distinctly different processes has been selected for this type of in-depth
study. Ten volumes, entitled Engineering and Cost Study of Air Pollution Control
for the Petrochemical Industry (EPA-45Q/3-73-QQ6a through j) have been prepared.
A combination of expert knowledge and an industry survey was used to select
these processes. The industry survey has been published separately in a series of
four volumes entitled Survey Reports on Atmospheric Emissions from the Petrochemical
Industry (EPA-450/3-73-005a, b, c, and d).
This volume covers the manufacture of ethylene dichloride by oxychlorination.
Included is a process and industry description, an engineering description of
available emission control systems, the cost of these systems, and the financial
impact of emission control on the industry. Also presented are suggested air
episode procedures and plant inspection procedures.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Air Pollution
Carbon Monoxide
Chlorohydrocarbons
Hydrocarbons
b.IDENTIFIERS/OPEN ENDED TERMS
Petrochemical Industry
Ethylene Dichloride
c. COSATI I ield/Group
7A
7B
7C
11G
13B
13H
13 DISTRIBUTION STATEMENT
19. SECURITY CLASS (This Report)
Unclassified
21
NO. OF PAGES
104
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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