EPA-450/3-73-006-a
ENGINEERING AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE PETROCHEMICAL
INDUSTRY VOLUME 1:
CARBON BLACK MANUFACTURE
BY THE FURNACE PROCESS
by
W. A. Schwartz, F. B. Higgins, Jr.,
J. A. Lee, R. Newirth, and J. W. Pervier
Air Products and Chemicals, Inc.
Houdry Division
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 Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, N. C. 27711
June 1974
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This report is issued by the Environmental Protection Agency to report
technical data of interest to 3 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 from the
National Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia 22151.
This report was furnished to the Environmental Protection Agency by
Air Products and Chemicals, Inc. , in fulfillment of Contract No. 68-02-0255.
The contents of this report are reproduced herein as received from Air
Products and Chemicals, Inc. The opinions, findings, and conclusions
expressed are those of the author and not necessarily those of the Environ-
mental 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-a
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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 carbon black. 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.
Ashland Chemical Company
Cabot Corporation
Columbian Carbon Company
Continental Carbon Company
J. M. Huber Corporation
Phillips Petroleum Company
Sid Richardson Carbon 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 CB-1
II. Process Description and Typical Material Balance 2
III. Manufacturing Plants and Emissions 8
IV. Emission Control Devices and Systems 35
V. National Emission Inventory 54
VI. Ground Level Air Quality Determination 55
VII. Cost Effectiveness of Controls 56
VIII. Source Testing 62
IX. Industry Growth Projection 63
X. Plant Inspection Procedures 66
XI. Financial Impact 69
XII. Cost to Industry 69
XIII. Emission Control Deficiencies 74
XIV. Research and Development Needs 76
XV. Research and Development Programs 78
XVI. Sampling, Monitoring and Analytical Methods for
Pollutants in Air Emissions 84
XVII. Emergency Action Plan for Air Pollution Episodes 89
References 97
Appendix I 1-1
Appendix II II-l
Appendix III III-l
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LIST OF ILLUSTRATIONS
Figure Number
CB-1
2
3
4
5
6
7
Table Number
CB-1
1A
2
3A
4
5
6
7
9
10
11
12
13
13A
14
15
16
17
I-I
II-l
II-2
Title
Simplified Flow Diagram
Carbon Black Filter
Filter Bag Cleaning Process
Bag Filter Operation
Typical Vacuum Clean-up System
Carbon Black Production - Capacity Projection
Calendar Time Schedule for R & D Project
LIST OF TABLES
Title
Typical Material Balance
ii ii ii
Carbon Black Reactor System Heat Balance
Summary of U.S. Furnace Black Plants and
Atmospheric Emissions from These Facilities
(23 pages)
Typical Vent Gas Composition
CO-Boiler Emission Control System
Thermal Incinerator
CO-Boiler Plus Thermal Incinerator Emission
Control System
Thermal Incinerator Plus Waste Heat Boiler
Emission Control System
Catalytic Incinerator
Cost Effectiveness for Alternate Emission
Control Devices (3 pages)
Carbon Black Manufacturing Cost for a Typical
Existing 90 MM Lb./Yr. Facility
Carbon Black Manufacturing Cost for a Typical
Existing 90 MM Lb./Yr. Facility with
Retrofit Plume Burner
Carbon Black Manufacturing Cost for a Typical
Most Feasible New 90 MM Lb./Yr. Facility
Pro-Forma Balance Sheet
Estimated 1985 Air Emissions for Alternate
Control Systems
Detailed Costs for R & D Project
Summary of Sampling and Analytical Methods
Reported for Pollutants (3 pages)
Financial Impact of Air Pollution Episodes on
Manufacturing Costs (2 pages)
Emission Summary (3 pages)
Number of New Plants by 1980 (Illustration)
Weighted Emission Rates (Illustration)
Page No,
CB-3
-36
-37
-39
-42
-64
-84
Page No.
CB-5
-6
-7
-9
-32
-43
-46
-48
-49
-50
-57
-70
-71
-72
-73
-75
-81
-86
-94
1-3
II-2
II-4
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1
SUMMARY
The carbon black 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 the channel process for the production of carbon
black is unlikely to be incorporated into a future plant design, so does not
warrant consideration under new performance regulations. It was also concluded
that the thermal process for the production of carbon black will, at best,
achieve only a limited growth of usage so it too does not warrant consideration
at this time. Consequently, the report is devoted to the study of the furnace
process for the production of carbon black which is both the chief present
process and the one most likely to be responsible for the future growth of
the industry.
The study has revealed that the carbon black producers in the United
States have made significant progress in their efforts to reduce particulate
emissions from their operating plants. Historically, these plants were
characterized by a black plume funneling away from the site and visible for
miles. These conditions, of course, resulted in a continuous problem of
sooty deposits in the surrounding communities and country side. Through
the advent of new designs for bag filters and the development of new quality
filter cloths, the stack exhaust from furnace black plants are now typically
invisible and efficiencies of particulate removal exceed 99 percent.
However, consideration of particulates does not characterize the entire
pollution potential of the industry. Being a partial oxidation process with
a hydrocarbon feed, one of the major waste products is carbon monoxide,
typically being emitted at a rate equal to about 1.3 pounds per pound of
carbon black produced. Some United States plants have tried to eliminate
this material by installing a CO-boiler and an incinerator with supplemental
fuel but no heat recovery, or a plume burner but these practices are not
widespread. Incinerators and waste heat boilers are reported to be in use
in Europe. Furthermore, since the process feed material invariably contains
small amounts of sulfur, the process also emits hydrogen sulfide and mercaptans
if the CO is not further oxidized or oxides of sulfur if a combustion step is
included. Oxides of nitrogen are also emitted.
As a result of this study, it was concluded that the use of bag filters
is the best, demonstrated technique for control of particulate emissions from
the main process vent and should be part of all future plant designs. There
is little liklihood that any carbon black producer would build a new plant
without bag filters, even if no governmental body required such an installation,
so the inclusion of this requirement in any new source standard would not
impose any additional cost on the industry.
It was further concluded that off-gas combustion is the only demonstrated
technique for the control of emissions of reduced sulfur compounds and/or
carbon monoxide. The technique has been demonstrated in the U.S. in only
three forms, i.e., by plume burning, by means of a CO-boiler and by means of
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11
SUMMARY (continued)
a fuel fired incinerator, although various other techniques were investigated
during the course of the study and are reported to be practiced in Europe.
It should be noted that none of these control methods remove sulfur but
merely convert it to the oxide form and that no feasible technique has been
found to remove either the reduced or oxidized form of sulfur compound.
Furthermore, these control methods also produce additional oxides of nitrogen.
Therefore, assuming that oxidation of carbon monoxide and sulfur compound
are the goals of new source standards, the best demonstrated technique is
the plume burner, if minimum capital cost is the principal criterion of "best".
However, depending on the plant, it may be necessary to provide supplemental
fuel to flare the off-gas. On the other hand, the CO-boiler removes pollutants
more efficiently, and recovers a substantial quantity of energy, but typically
at a capital cost penalty because of the need for a stand-by unit to assure a
reliable supply of process steam. If a reliable off-gas combustion device
could be demonstrated (i.e., the thermal incinerator-waste heat boiler
combination as assumed in the study and reported from Europe), it would clearly
be the "best" and would probably result in a reduction in annual direct operating
costs, even though it probably would also result in a reduction in percentage
return on investment because of increased capital charges.
The actual cost to industry is difficult to estimate because of the
uncertainty of the need for stand-by units and also because of the need to
install steam driven equipment rather than the conventional electric motor
drives that are typically used today. However, it is likely that additional
capital requirements of about $1,000,000 (1973 dollars) per combustion unit per
new 90 MM pounds per year carbon black plant is the correct order of magnitude
for emission control by means of off-gas combustion with energy recovery. It
should be noted that the only feasible retrofit control technique is plume
burning or fuel fired incineration if higher efficiencies are sought, because
existing plants have no need for the potential steam that can be generated.
Several miscellaneous emission sources also exist on typical carbon black
plants. These are drier vents, product transfer systems and storage systems.
In each case, the use of bag filters was found to be the best demonstrated
technique for emission control since the only emissions of any magnitude from
these facilities are particulates. These sources of emission are almost
always controlled in this manner although the installation does not normally
pay for itself. However, the promulgation of new source standards to this
effect would not impose additional hardship on the industry because the control
is considered "standard".
It was calculated, in the course of the study, that by 1985, the carbon
black industry will emit nearly seven billion pounds of pollutants per year
(of which 6.5 billion pounds will be carbon monoxide) if plants continue to
be designed as are the "typical" existing plants. This can be reducad to
about 0.6 billion pounds per year if plume burners are installed on all
existing plants and efficient off-gas combustion devices installed on all new
plants. However, included in that total will be an increase of about 0.1
billion pounds per year of sulfur oxides and an increase of about five million
pounds per year of nitrogen oxides. Although stack analyses are not available,
the new plant emission factors can be expected to be about 0.004 pounds NOx
per piound of carbon black and 0.03 pounds of SOx per pound of carbon black with
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Ill
SUMMARY (continued)
only traces of hydrocarbon, particulates and carbon monoxide emitted if a
CO-boiler or its equivalent were installed.
The capital expenditure required by the industry to effect these
reductions will be about $23,000,000 (at 1973 prices) if stand-by combustion
devices are not required, and nearly $40,000,000 if stand-by units are
installed.
It was concluded that the most likely research area for reducing emissions
from new carbon black plants would be the development of a system using oxygen
feed to the process with partial recycle of the off-gas to control flame
temperature. The industry could not justify any sulfur removal research but
would probably benefit from any breakthrough in the petroleum industry's
efforts to desulfurize heavy oils or in the power generating industry's
efforts to desulfurize flue gas.
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CB-1
I. Introduction
Carbon black is manufactured by the burning of hydrocarbons in a limited
supply of air. This finely divided material (100 to 4000 A° diameter) is of
industrial importance primarily as a reinforcing agent for rubber. It is
also used as a colorant for printing ink, paint, paper and plastics.
Three basic processes currently exist in the United States for producing
carbon black. They are: the furnace process, accounting for about 89% of
production; the older channel process, which accounts for less than 2% of
production; and the thermal process. Atmospheric pollutants from the thermal
process are small since the principal exit gases, which are rich in hydrogen.
are used as fuel in the process. In contrast, the pollutants emitted from
the channel process are excessive and characterized by highly visible black
smoke. Emissions from the furnace process consist of water vapor, carbon
dioxide, nitrogen, carbon monoxide, hydrogen, hydrocarbons, particulate
matter, and some sulfur compounds.
A process description, industry survey of emission sources, effluent
characteristics, control practices and equipment in addition to plant economics
for the furnace process are presented in the following sections. A similar
study for the thermal and channel processes was not made because of the low
pollution and limited use of these respective processes.
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CB-2
II. Process Description and Typical Material Balance
The fundamental steps in carbon black manufacturing, by the furnace
process are:
A. Production of black from feed stock,
B. Separation of black from the gas stream, and
C4 Final conversion of the black to a marketable product.
In the furnace process, carbon black is produced by burning a feed stock.
This feed may be either light hydrocarbon gas or a mixture of gas and heavy
aromatic oil. However, because of the high cost of natural gas, a mixed
feed is used in most plants. This feed is preheated and injected into a
reactor with a limited supply of combustion air. The flue gases and
entrained carbon from the reactor (furnace) are cooled by heat exchange
against reactor feed and water quench. This stream (450 to 500° F) is then
sent to bag filters for carbon black recovery. The recovered carbon black
is transported to a finishing area by screw or pneumatic conveyors.
In the finishing area the black is passed through a pulverizer to break
up lumps. This produces a 5 to 12 Ib./cu. ft. dusty product. In order to
obtain a marketable material that can be transported, the carbon black is
converted into pellets or beads with a 20 to 35 Ibs./cu. ft. bulk density.
Normally pelleting is accomplished by a wet procedure. The resulting wet
product (30 to 40 wt. % water) is sent to driers. The drier product is
then screened, bagged and sent to storage.
Figure CB-1 presents a block flow diagram for a typical plant and indicates
the various vent streams from this unit. Particulate emissions in these vent
streams are affected by the type of collection equipment used. Total volume
and composition of the vent gas is largely determined by the overall yield
which is influenced by the type of feed (that is, liquid or gas), the ratio of
gas to oil in the feed, and the amount of combustion air.
Furnace type units with gas feed or mixed feed (high proportion of gas)
produce larger amounts of carbon oxides than units operating with predominantly
oil feed. This increased CO and C02 production means more oxygen (air) is
required and, therefore, more nitrogen has to be vented.
The main petroleum streams used as feedstock include:
A, Cracked fuel oil from thermal cracking of cycle stocks or the
vacuum flash distillate from this cracked fuel oil.
B, Thermal or catalytic cycle stocks.
C, Aromatic extract from catalytic cycle stocks.
The best raw material especially suited for the production of modern high
structure carbon blacks is highly aromatic, low sulfur, high molecular weight
resins and asphaltenes, substantially free of suspended ash, carbon and water.
Carbon black yields from oil can generally be correlated with the aromaticity
of the feed stock. The Bureau of Mines Correlation Index is an approximate
indication of suitability of feed stocks. However, this analysis alone can not
be used to determine feed stock quality. Actual yield can only be determined
by pilot plant tests.
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CB-3
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CB-4
Typical carbon black yields for the various processes are as follows:
Process
Channel
Thermal
Fine particle size
Medium " "
Furnace
Gas Feed
Small particle size
Large
Grade*
of
Carbon
Ave.
Lbs. Carbon Black
Particle per
Diam. A° 100 Ibs. of Carbon Feed
ALL
FT
MT
90-290
1800
4700
5-10
46-45
45-50
FF
HMF, SRF
Oil Feed (Typicall includes some supplemental gas)
Small particle size
Large " "
SAF, ISAF, HAF
FEF, GPF
400-500
600-800
180-280
400-550
10-15
25-40
35-55
40-65
*Industry designations, descriptive such as FT is fine thermal, SRF is
semi-reinforcing furnace, GPF is general purpose furnace. The ASTM also
has a complete system of designations which is too lengthly to include here,
Small particle size carbon black (SAF, ISAF and HAF) from the oil furnace
process represents over half the total carbon black production.
Operating conditions such as feed composition, furnace residence time,
temperature, fuel/air ratio, oil/gas ratio and quench conditions influence the
properties of the carbon black product and, therefore, can not be modified
appreciably for any given grade of product. Some producers indicate this also
applies to operating pressure.
Table CB-1 presents a material balance in pounds per hour for an oil feed
(gas and oil) furnace plant producing 30,000,000 Ibs./yr. large particle (GPF)
plus 60,000,000 Ibs./yr. small particle (HAF) carbon black. This "Typical" or
"model" unit will be used in economic studies discussed later in this report.
Table CB-1A presents the same material balance with quantities expressed as tons
per ton of product carbon black.
Table CB-2 presents an estimated heat balance around the furnace reactor
system. It should be noted that the heat balance is influenced to large
extent by the type of carbon black being produced. The presented balance is
based on Table CB-1A product distribution.
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CB-7
TABLE CB-2
CARBON BLACK REACTOR SYSTEM
HEAT BALANCE (a)
Heat Out
Quench (to 500 F)
Radiation Heat Losses (500° FAT)
Preheater Inefficiency
Incremental Effluent Heat Content (b)
Total
7,494 BTU/LB. of Carbon Black
2,436 " " " "
572 " " " "
1J85 " " " "
12,287 " " " "
Heat In
Exothermic Heat of Reaction (c)
Fuel to Feed & Air Preheaters
Total 12,287
10,381 BTU/LB. of Carbon Black
1.906 " " " "
ii ii it ii
1) Table CB-1A Material Balance.
2) 2600° F Reactor (furnace) outlet temperature.
b) Difference in heat content of effluent @ 500° F and feed @ 80° F
plus air @ 120° F.
c) Net reaction nest is exothermic. It is made up of an exothermic combustion
and an endothermic cracking reaction.
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CB-8
III. Manufacturing Plants and Emissions
Table CB-3A presents a list of U. S. plants currently producing carbon
black by the furnace process. Most of these plants are located in Texas
and Louisiana. Approximately one-third of the plants have been built in
residential areas and the remainder are within 13 miles of towns with
population ranging between 550 to 76,000.^
In addition to indicating plant sizes, Table CB-3A also shows atmospheric
emission data for these units.
A. Continuous Air Emissions
1. Main Process Vent Gas
This stream consists of the gross reactor effluent plus quench
water after recovery of carbon black product and represents the
main source of emissions from the carbon black plant. For the
"typical" or "model" plant of this study, it is equivalent to about
3.5 million scfh of which nearly half is water vapor.
In most cases, the process vent gas atmospheric emissions
presented in Table CB-3A are average values for producing various
types of carbon black in these units. Actual vent gas composition
can vary considerably from the average figures shown, depending
upon the grade of carbon black being produced. The vent gas will
normally contain six to 14 vol. ?„ (dry basis) CO. However, this
value can be as high as 20 vol. %. Total sulfur normally ranges
between 0.02 and 0.16 vol. 70 with the actual quantity depending
upon sulfur content of the hydrocarbon feed. Anywhere from 10 to
4070 of the feed sulfur is retained in the carbon black product and
the remainder is vented primarily as ^S with trace quantities of
S02, 803, thiophene, carbonyl sulfide and C$2.
The vent gas also contains 15 to 200 ppm of NOX, 5.5 to 15 vol. %
hydrogen and 0.3 to 1.5 vol. °L hydrocarbons. (See Table CB-4 for
typical breakdown of components.)
In some cases, the main process vent gas stream has a slight
H2S odor at ground level. This is reported to be the only carbon
black plant vent stream that has a noticeable odor.
No actual test data are available concerning size distribution
of particulates in this and the other vent streams. However, it
is believed that size distribution of particulates in the process
vent is similar to that of the carbon black product being produced.
This is because most if not all of the carbon black emitted is a
result of small leaks in the product recovery bag filters.
Atmospheric emissions from the various vent streams are directly
proportional to quantity of carbon black being produced. This is
primarily true because the normal carbon black plant consists of
-------
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CB-30
TABLE CB-3A FOOTNOTES Sheet 22 of 23
a) Wet gas flow rate based on carbon black average production rate unless
otherwise noted. If average production figures not shown, flow rate is based
on maximum plant capacity.
b) Average composition, actual values depend on type and quantity of
carbon black being produced.
c) Stream contains 45+2 vol. % water.
d) Reference "Atmospheric Emissions from Sulfuric Acid Manufacturing
Processes" U. S. Dept. of Health, Education and Welfare. Subsequent analysis
has not confirmed the presence of S02.
e) Total for all units at this location.
f) Particular type corresponding to emission composition shown, actual
feedstock and type of carbon black can vary.
g) Processed in unit No. 1 facility. Separate drier filter to be
installed in September, 1972.
h) In all oil furnace plants 15-25 wt. % of feed consists of natural gas
or other light hydrocarbons. In mixed feed units, percentage of feed gas is
higher.
j) Air.
k) Also have pilot plant which is not shown in this summary.
1) Approximate emissions from the various process vent stacks can be
obtained by prorating emissions shown for other units operated by same
company. Prorating factor is directly proportional to total vent gas flow
rate and inversely proportional to carbon black production rate.
m) Volume flow before combustion of gases. Composition shown is estimate
of flare effluent assuming 20% of particulate carbon black and 90% of other
combustibles are burned. Composition excludes excess oxygen and nitrogen
resulting from combustion air.
n) Total for all three units in this facility.
o) Includes drier vent from No. 4 unit.
p) Maximum flow all relief stacks venting at same time. Normally no
flow. During individual furnace warm-up, flow is vented to atmosphere.
At this time, maximum flow is equal to volume shown for one stack. During
initial part of warm-up, vent will contain no carbon black.
q) Isokinetic gas sampling used for particulate.
r) 1'otal process vent emissions from all units located at this plant.
Composition of vent stream is based on intermediate values of component
composition ranges provided by this company for producing various types of
carbon black in their plants.
s) Assumed value based on generalized data provided in survey.
-------
CB-31 Sheet 23 of 23
TABLE CB-3A FOOTNOTES (CONTINUED)
t) Total losses, including spills and leaks, estimated to be 0.001 tons
per ton of carbon black product.
u) Value estimated by carbon black manufacturer.
v) Calculated based on emission factor of 0.23 Ib. N02/1000 cu. ft. of
gas burned while reactors are on inert operation.
w) ASTM-N500 series.
x) Excludes hydrogen and methane.
y) Same as footnote (1) except prorate emissions shown for plant 50-11.
z) Same as footnote (1) except prorate emissions shown for plant 50-19.
-------
CB-32
TABLE CB-4
TYPICAL VENT GAS COMPOSITION
FOR
90 MM LB./YR. CARBON BLACK
PRODUCTION
FROM FURNACE OIL PROCESS
Component
Hydrogen
Carbon Dioxide
Carbon Monoxide
Hydrogen Sulfide
Sulfur Oxides
S02
S03
Methane
Acetylene
Nitrogen & Argon
Oxygen
Nitrogen Oxides (N02)
Carbon Black
Water
Range in Composition
Mol % (a>
5.5 - 15
3 - 6.5
6-14
0.01 - 0.2
TR - 0.03 (d)
TR
0.2 - 0.7
0.1 - 1.0
65 - 80
0 - 4.9
-------
CB-33
parallel trains of equipment with multiple reactors. These reactors
and other equipment can be put in and out of service as production
demands vary. Since product recovery bag filters and other emission
control devices remain in service during start up and shut down
operations, emissions do not increase under these circumstances.
In addition, because of multiplicity of equipment, individual
processing upsets usually will not result in significant variations
in atmospheric emissions. However, this is not always true in regard
to problems that can occur with product recovery equipment. Particulate
emissions from the process vent stream can greatly increase if
substantial leaks develop in the product bag filters.
2. Product Transport
If the carbon black plant incorporates pneumatic conveyors for
moving product to the finishing area, the carrier gas may be vented
after recovery of entrained carbon black. Some plants use a closed
loop system and eliminate this venting.
3. Drier Vent
(a) Indirect Heat Source
In most plants a large portion of the hot gas employed in the
drying operation does not come in direct contact with the carbon
black but is used as an indirect heat source and, therefore, contains
no entrained carbon black.
(b) Purge Gas
Anywhere from 35 to 70 percent of the gas is directly charged to
the drier interior for removal of water vapor. This purge gas
picks up carbon particles and is usually vented after passing through
a filter or water scrubber for particulate removal.
4. Bagging and Storage Area Vent
Carbon black content of this air stream varies depending upon
specific operations being performed in the storage area. However, since
storage and bagging areas are usually within a building, a vacuum clean-up
system which rejects filtered air is typically included.
B. Intermittent Air Emissions
1. Vacuum Clean-up
The vacuum system is normally in continuous operation. However,
carbon black is only present in the exhaust air when the facilities are
being used to clean-up carbon spills. In some plants bagging and storage
areas are tied into the vacuum system in which case carbon black emissions
would be on more of a continuous basis.
2. Emergency Relief
In some plants the furnace reactors are directly vented to the
atmosphere during reactor warm-up. This venting is very infrequent and
only occurs when a new reactor is put in service to meet increased
production requirements. Reactor warm-up is accomplished by burning
-------
CB-34
natural gas and the reactor is put on line before adding oil feed.
Therefore, no carbon black or hydrocarbons are emitted during the
direct venting operation.
C. Liquid Wastes
Liquid wastes are usually not discharged from these units. Normally,
any effluent water recovered from vent gas scrubbing operations is used
as supplemental reactor effluent quench in order to reduce the net
process water requirement and recover entrained carbon black. Water
is used in many plants to clean-up carbon black spills. This water is
normally collected in a pond where it is either allowed to completely
evaporate or is used as supplemental make-up water for reactor effluent
quench system.
D. Solid Wastes
Solid wastes consist of used filter bags (0.3 to 0.5 Ibs./ton of
carbon black) and used furnace refractory brickes (0.7 to 1.5 Ibs./ton
of carbon black) which are discarded as land fill. In addition , pond
sludge, which varies in quantity between 0 to 40 Ibs./ton of product,
is also normally used as land fill.
-------
CB-35
IV. Emission Control Devices and Systems
A. Early Methods of Product Recovery
Prior to about 1965, most units recovered product from the quenched
furnace effluent by means of electrostatic precipitators and several
stages of cyclone collectors (usually three) with or without wet gas
scrubbers. With this type of recovery system, it was possible to recover
up to about 92 percent of the contained carbon black. Based on present
high sales volume of ultra-fine products, estimated collection efficiency
for this type of recovery system would drop to 87 or 88 percent. The
remaining carbon black would be vented to the atmosphere with the combustion
gases. During this earlier time period, most drier vents were exhausted
directly to atmosphere.
B. Bag Filters on Process and Drier Vents
In order to improve product yield and reduce emissions, nearly all
present furnace type carbon black plants incorporate bag filters in the
product recovery system. The bag filter has either been added on, or
replaced the precipitator and/or the cyclones in existing plants. In
addition, bag filters on the furnace effluent and drier vent streams are
reported to obtain up to 99.95 percent carbon black recovery.
The substantial improvement in product recovery obtained by utilizing
bag filters on the main process vent stream economically justifies the
increased investment, utilities and maintenance cost for this equipment.
However, this is not usually true in regard to filters placed on drier
vent streams and filters used in the product finishing plus storage areas
in order to minimize carbon black emissions. Without this particular
equipment, approximately 1.5 percent of the carbon black production would
be lost. Recovery of this relatively small amount of material does not
economically justify the relatively high bag filter investment and
operating costs involved.
A sketch of a typical bag filter design for the main process vent
stream is shown in Figure CB-2. Carbon black-laden gases enter the hopper
below the bag cell plates. The hopper performs as a distribution duct
for the entering production stream. The process gases and carbon black
flow into the individual bags of each compartment through cell plates.
The filtered gas flows through the bags and out the bag filter stacks.
The entrained carbon black collects on the inside of these bags, and
during the cleaning or repressure cycle of each compartment, the black
is removed and dumped into the hopper (repressuring simply means that
the flow of gas through the bags is reverse, Figure CB-3). From the
hoppers, the carbon black is usually either dropped through air locks
into a pneumatic conveyor system or fed to screw conveyors for
transportation to the product finishing area.
Figure CB-2 shows a single stack for the entire bag filter. In some
cases, the filters have one stack for each compartment. This makes it
somewhat easier to locate leaking bags.
Normally, the main process vent bag filters contain 6 to 18 compartments
and each compartment contains approximately 300 to 400 bags. Each bag is
about 5% inches in diameter and 126 inches (10% ft.) long. These bags
themselves are a great cost item in the bag filter. Bag filter material
-------
CB-36
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CB-37
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CB-38
used by most major black producers consists of fiberglass which is
coated with a graphite-silicon film. Bag life would be seriously
reduced if this coating were removed, and this can easily happen if
operating temperature is allowed to exceed 450° F.
The average life expectancy of the filter bags is about 12 to 18
months. However, it is usually necessary to replace a few bags in
each compartment during this period. High sulfur content of the oil or
impurities in the quench water can shorten this life.
The bags are normally supported from hangers in the roof of the
filter compartment with metal caps. The caps are tapered on the sides
and are slightly larger in diameter than the hem around the top of the
bag. The caps are inserted into the bags edgewise. When the cap is
rotated and pulled outward, the bag is wedged around the perimeter of
the cap. The wedging action seals the cap-bag surface and provides support
for the bags. The bottom of each bag is then secured with a snap ring
onto the cell plate.
The repressuring process is controlled with an electrically operated
timer.2 Figure CB-4 illustrates the principal operations of the bag
filter. As shown, the first two compartments are filtering carbon black
from process gases as the No. 3 compartment is being cleaned. The next
event in the operation will be cleaning of compartment No. 1 while
filteration continues in the No. 2 and No. 3 compartments. This step-like
rotation is continued until all compartments have been repressured. The
cycle is then repeated.
The repressuring fan generates enough force to reverse the flow of
gases. The gases used in the cleaning cycle are taken from compartments
on the filtering cycle. In Figure CB-4, compartments No. 1 and No. 2
are supplying the repressuring gases for compartment No. 3. When com-
partment No. 1 is cleaned, the gases will be provided from compartment
No. 2. The three compartment filter illustrated is merely schematic.
On commercial bag filters, several of the compartments are used as a
source for repressuring gas.
The sequence of events which puts compartment No. 3 on-and-off the
cleaning cycle is:
1. Stack valve closes.
2. Repressuring valve opens.
3. Cleaning cycle.
4. Repressuring valve closes.
5. Stack valve opens.
6. Filter cycle.
For cleaning compartment No. 1, the sequence is slightly different
because of the repressuring intake valve. When the stack valve closes,
so does the repressuring intake valve; and when the stack valve opens,
the repressuring intake valve opens.
Similar type bag filters are used to recover carbon black from the
-------
CB-39
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CB-40
direr purge vent gas. Fiber glass bags are used in these filters
because of the normal 400° F and higher operating temperatures.
Corrosion, and its related maintenance cost, is a continuous problem in
bag filters, especially in drier vent applications. This is due to both
the sulfur and the water content of the exit gases.
C. Water Scrubbers for Particulate Removal
Water scrubbers are somevhat less efficient (90 to 9570) than bag filters
and are being phased out of product recovery service. They are still used
in drier purge gas clean-up service because of their lower costs. In some
plants, carbon black losses in drying and product finishing areas are more
than 1.5%. Under these circumstances, water scrubbing of the drier vent gas
and other product finishing vent streams for carbon black recovery can be
economically justified. However, the product trend in carbon black
specifications is toward materials that are harder to wet, thus decreasing
the effectiveness of scrubbers.
One carbon black producer (50-28) incorporates the following relatively
efficient water scrubbing system on the drier vent stream. A blower located
downstream of a tangential entry vertical cylindrical scrubber pulls vent
gas from the drier. Discharge gas from the blower is sent to a Venturi
scrubber. Essentially, this is three stages of scrubbing since water is
sprayed into the cylindrical scrubber, blower inlet and Venturi scrubber.
The Venturi scrubber discharges into a cyclone separator and out through
a stack to the atmosphere. Slurry is collected from the cylindrical
scrubber and from the cyclone separator. Some of the slurry is recycled
to the scrubber sprays and the remainder is used for quenching reactor
effluent gas. In this way, all of the black removed from the drier vent
gas stream re-enters the normal production train.
Total water usage for the scrubber system is about eight gallons per
1000 SCF of gas processed. Of this total about 33 percent is fresh water
and 67 percent is recycled slurry. Total pressure drop through the system
is about 15" H20.
D. Pneumatic Conveyor Exhaust Gas Clean-up
In plants where air pneumatic conveyors are used to transport carbon
black to the product finishing area, the transport medium is usually sent
to a bag filter for carbon black recovery before this gas is vented to
the atmosphere. Because of the low temperatures involved, wool, cotton
or orIon bags are used in these "secondary" bag filters.
E. Clean-up System for Miscellaneous Particulate Emissions
In addition to the above carbon black losses, particulate emission
can occur from the following sources;
1. Inadvertent spillages when drawing samples from production line.
2. Unplugging production line stoppages.
3. During cleaning of process equipment and hopper cars.
4. Leaks that develop in process equipment.
5. Bagging operation and loading of hopper cars.
-------
CB-41
6. Bags torn during stacking in warehouse or loading and unloading
of box cars or trucks.
Most plants minimize these emissions by improved operating methods,
preventive maintenance and employment of a vacuum clean-up system as
shown in Figure CB-5. By having multiple hose connections on a vacuum
line throughout the plant, it is possible to pick up and recover most
carbon black spills. In addition, vacuum packing of bags in a hermet-
ically sealed product packing system will prevent carbon black emissions
from this source.
Installed cost for a vacuum system similar to that shown in Figure
CB-5 for an average size carbon black plant would be $20,000 to $50,000.
Typical average overall carbon black recovery for a plant containing
bag filters on vent streams and a vacuum system for clean-up is about 99.97,.
F. Combustion Devices for Process Vent Gas
In addition to the above quipment which reduces particulate emissions,
some carbon black plants have pollution control devices on process vent
gas streams to reduce CO and t^S emissions to the atmosphere. These
devices include CO boilers, incinerators and off-gas plume burners. It
is also conceivable that catalytic oxidation could be employed. Use of
this various equipment will tend to increase carbon black manufacturing
cost.
1. Devices in Use in the U.S.A.
a. CO Boilers
Table CB-5 illustrates a CO boiler and provides the material
balance that would be expected if controlling the "typical" emission
as tabulated in Table CB-4. It should be noted that this type of
installation requires supplemental fuel and requires no heat exchange
systems other than those to preheat and vaporize the boiler feed
water and superheat the steam. It will typically produce more steam
than can be economically used in a carbon black plant, so a choice
must be made between exporting some of the steam or burning some
of the CO in a different manner.
The addition of a CO boiler is one of the more efficient methods
of controlling combustible gaseous emissions. However, by-product
steam credits can not usually off-set operating costs. It is doubtful
if the addition of a CO boiler to any existing carbon black plant
is practical since most of these units have motor driven equipment
and could not use generated steam without a large expenditure for
turbine drivers. Vent gas effluent from the CO boiler will contain
no particulates, CO and t^S. In order to insure complete combustion
of these components, it is normal practice to design for a 1600 to
1800° F operating temperature in the boiler combustion zone. In
addition, excess air is employed (2 to 4 mol % 02 in boiler effluent -
dry basis). The data in Table CB-5 are based on an 1800° F combustion
zone temperature and 4 mol 7° oxygen (dry basis) in the stack gas.
Only one existing U.S. plant utilizes CO boilers. This plant
(50-26) represents the best emission controlled U.S. carbon black
-------
01013
CB-42
FOE
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NO. 68-OZ-0155
MIT
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-------
CB-43
TABLE CE-5
CO-BOILER EMISSION nrwTRnT. SYSTEM
FOR
90 MM LB./YR. FURNACE BLACK PLANT
OVERALL MATERIAL BALANCE. LB./HR.
Component
Process
Vent Gas
Comb.
Air
Natural
Gas
Flue
Gas
C02
CO
H2S
s+so2
CH4
C2H2
C2H6
Carbon Black
H20
NO,,
TOTAL LBS./HR.
SCFM
1,229
9,978
14,071
306
TR
318
383
24
90,686
810
80,223
18
198,046
57,400
111,588
33,804
1,580
146,972
677
149
70
896
36,604
578
202,334
10,753
95,603
4£
345,914
85,000
Process Vent Gas(450°F)
Natural Gas
(Supplemental Fuel)
Comb. Air
80° F
Flue Gas
750° F
BF Water 95,230 Lb./Hr. (240° F)
Steam @ 450 PSIG and 750°F
90,700 Lb./Hr. Total
78,000 Lb./Hr. Net
Slowdown 4,530 Lb./Hr.
460° F
-------
CB-44
plant. Boilers were incorporated in the original plant design and
the decision to burn off-gases was primarilly for purposes of odor
control since this plant is located in a metropolitan area. The
choice of a CO boiler rather than an incinerator was based on energy
costs. Because of operating and maintenance difficulties, this
particular carbon black manufacturer feels that a complete new
study would be undertaken before they would again choose a CO boiler
for a new plant. The present plant went on stream about 1970.
Problems with off-gas burning in CO boilers include the following:
i Vent gas is available at low pressure.
ii Gas stream is corrosive.
iii Investment for required blowers, large diameter pipes and
valves, burning equipment, control systems and steam
utilization systems is high. This is especially true if
a spare boiler is provided for dependable steam supply.
iv Because of the low heating value (30 to 50 BUT/FT.3) of the
gas stream, up to 357= of the total heating value must be
added as supplemental fuel in order to achieve complete
combustion.
v Flame control is difficult due to low heating value and low
level of incandescence, therefore, flameouts and their
inherent safety hazzards are common.
vi An operating problem results from the need to switch to
complete fuel gas firing whenever a different type of black
is to be produced. This is necessary because oil is cut
out and complete system is purged of black before change over
can be made. Coming back on the line is then difficult.
Such changes are frequent.
In the 50-26 facility, as would most likely be true in most
carbon black plants generating steam, not all the process vent gas
is sent to the CO boilers. Steam would have to be exported if total
available heat was used to generate steam. At the 50-26 plant
electric stand-bys are provided on several key pumps, otherwise all
main equipment is steam driven except start-up units. On this basis
about 60% of the process vent gas is charged to the boilers, 107, is
used in the carbon black driers and the remainder is sent to an
incinerator.
The thermal incinerator employed at plant 50-26 is not a recommended
type since it employs supplemental fuel but does not recover heat
from either the process vent gas or the fuel. Hence, the anticipated
material balance would be as shown on Figure CB-5 but with only about
47,000 Ibs./hr. of net steam produced. The economics of this scheme
are poor and its environemntal impact is unfavorable. Therefore, it
is not considered in this report.
b. Plume Burners
Off-gas plume burners are known to be used by only one existing
carbon black manufacturer (plants 50-7 and 50-8), but is has been
reported that retro-fit burners without supplemental fuel have been
-------
CB-45
successful, both domestically and in Europe. This control device
has the following limitations:
i Efficiency for removal of contaminants is relatively poor.
Degree of combustion obtained depends on BTU content of the
vent gas. If a high yield carbon black is being produced,
a rich vent gas will result and it is estimated that 95% or
more of the CO, t^S and hydrocarbons will be burned. For
other type carbon black production, heating value of the
vent gas will be lower and only about 75-807o of these
impurities will be oxidized. It is estimated that 20-307=
of the vented carbon black is burned.
ii Small changes in vent gas composition could extinguish the
burner if supplemental fuel and adequate instrumentation
are not provided.
iii Improper firing of the burner could result in operating
temperatures which favor NOX formation.
The industry nomenclature distinguishes between plume burners and
flare stacks as devices which, respectively, do not or do require
supplemental fuel. According to the operator of the plants which
have plume burners, the minimum self supporting heating value is about
50 BTU/scf with their normal operation between 70 and 100 BTU/scf.
The "typical" vent gas of this study has a heating value of about
40 BTU/scf and thus is not adaptable to plume burning. If flared,
supplemental fuel will be required and the consensus is that
sufficient fuel to raise the heating value to 100 BTU/scf is the
minimum for a stable flame. The consensus also is that flaring
of the 100 BTU/scf gas will achieve only "about 907, combustion".
No one is willing to predict the nature of the other 107o but it is
safe to assume that is a mixture of unburned CO and hydrocarbons and
"cracked" products such as ethylene and soot. The proportions of
these are variable and unknown, hence a material balance for the
control system is not included in this report.
2. Devices Not Currently in Use in the U.S.A.
a. Thermal Incinerator
Table CB-6 presents a material balance for a thermal incinerator
that includes a section of air and vent gas preheat by heat exchange
against the products of combustion. It is based on 1800° F combustion
zone temperature and 4 mol % oxygen in the stack gas. This
technique, as illustrated on the table, results in essentially
complete combustion without any supplemental fuel (except pij.ots) and
thus is a recommended technique if no need exists for steam generation
since it results in the waste of a minimum amount of energy.
Burning of off-gas in a thermal incinerator of this type results
in off-gas burning problems and combustion efficiency similar to
that obtained with a CO boiler. Heat recovery from the burning of
the process vent gas is sufficient to obtain the desired operating
temperature. This is based on vent gas having a heating value of
40 BTU/FT.3. If heating value of the gas differs appreciably from
the typical value given in Table CB-4, heat balanced operation can
-------
CB-46
TABLE CB-6
THERMAL INCINERATOR
90 MM LB. /YR. FURNACE BLACK PLANT
OVERALL MATERIAL BALANCE. LB./HR.
Component
H2
C02
CO
H2S
S+S02
CH4
C2H2
NOX
Carbon Black
N2
°2
H20
Process
Vent Gas
1,229
9,978
14,071
306
TR
318
383
18
24
90,686
810
80,223
Air To
Incin.
98,553
29,848
1,396
34,308
578
34
189,230
10,060
93,633
TOTAL LBS./HR.
SCFM
198,046
57,400
129,797
327,843
82,500
Natural Gas
550°
Comb. Air
80° F
Process Vent Gas
(450° F)
-------
CB-47
be obtained by adjusting the amount of preheat. This system is not
presently used in the U.S. and sulfur corrosion and metalurgy
problems might occur in the preheat section.
At present only the previously mentioned 50-26 carbon black
plant is known to incorporate a thermal incinerator in the U.S.A.
At this plant more excess air is used than is normally proposed
(7 vs. 4 mol 7o 02) and there is no air preheat. For these reasons,
supplemental fuel is required.
b. Incineration Plus Steam Generation by CO-Boiler
Table CB-7 presents a material balance and sketch of a
combination CO-boiler and thermal incinerator system for a 90 MM
Ibs./yr. furnace black plant. Steam production is limited to
estimated on-site requirements (60% of process vent gas to CO-boiler)
This depicts essentially the practice followed at plant 50-26
but incorporates the more economical thermal incinerator described
above so as to minimize supplemental fuel requirements. It
requires two units, one utilizing a preheat section for burning
excess vent gas without additional fuel and the other a CO-boiler
that provides the process steam requirements without heat exchange
but with fuel to support combustion.
c. Incineration plus Steam Generation by Waste Heat Boiler
In most plants, steam utilization is limited. Hence, an
economical approach to pollution control is to burn process vent
gas in a thermal incinerator without supplemental fuel and pass
the exhaust gases through a waste heat boiler as shown in Table
CB-8. Sufficient heat is available to easily make a steam
balanced operation by preheating the air in a flue gas exchanger.
At least one European plant (19) is known to employ an air preheated
off-gas burner for steam generation without supplemental fuel.
d. Catalytic Incineration
Table CB-9 presents a material balance for a catalytic
incinerator with fresh catalyst. As the catalyst ages, combustion
efficiency will decrease. With aged catalyst, it is expected
that 10 to 15 percent of the feed combustibles will be vented to
the atmosphere together with about 50 percent of the carbon
black particulate charged to this incinerator. No existing carbon
black plants are known to employ catalytic oxidation of the process
vent gas. However, it has been reported that one attempt was
abandoned some years ago because of catalyst poisoning. With
adequate control instrumentation to prevent excessive temperatures,
it should be possible to use a catalytic incinerator in this
service. Based on general information for conventional catalytic
incinerators in other applications, it is estimated that a 900° F
inlet temperature to the catalyst bed should be sufficient to
obtain complete combustion of all H2S, hydrocarbons and carbon
monoxide with standard catalysts, provided that the sulfur does not
poison the catalyst. Maximum temperature within the bed should
be limited to 1200° F in order to prevent loss in catalyst surface
area and a resulting loss in catalyst activity. It should also be
noted that 803 may be produced by most noble metal catalysts if the
-------
CB-48
Component
H2
C02
CO
H2S
S + S02
CH4
C2H2
C2H6
Carbon Black
N2
02
H20
NOX
Total
Lbs./Hr.
SCFM
TABLE CB-7
CO-BOILER PLUS THERMAL INCINERATOR
EMISSION CONTROL SYSTEM
90 MM LB./YR. FURNACE BLACK PLANT
Vent Gas
to
CO-Boiler
737
5,987
8,442
184
TR
191
230
15
54,412
486
48,134
11
118,829
34,440
OVERALL MATERIAL BALANCE,
Natural
Air to Gas to
CO-Boiler CO-Boiler
406
89
66,942 42
20,292
948
88,182 537
LB./HR.
Flue
Gas
from
Boiler
21,962
347
121,400
6,452
57,362
25
207,548
51,000
Vent
Gas
to
Incin.
492
3,991
5,629
122
TR
127
153
9
36,274
324
32,089
7
79,217
22,960
Air to
Incin.
39,421
11,942
558
51,921
Stack
Gas
from
Incin.
13,723
231
75,696
4,024
37,450
14
131,138
33,000
Natural Gas
(Supplemental Fuel)
Flue Gas
7500 F
Comb. Air
BF Water (240 F)
57,140 Ib./hr.
80° F
Process
Vent
Gas
Steam @ 450 PSIG, 750° F !
•• 54,400 Ib./hr. Total!
46,800 Ib./hr. Net ;
550° F
Natural Gas
(Pilots)
I Stack Gas
i 1600° F
Comb. Air
80° F
Slowdown
• 2,740 Ib./hr.
460° F
1800C
60%
407c
450° F
-------
CB-49
TABLE CB-8
THERMAL INCINERATOR PLUS WASTE HEAT BOILER
EMISSION CONTROL SYSTEM
FOR
90 MM LB./YR. FURNACE BLACK PLANT
OVERALL MATERIAL BALANCE. LB./HR.
Component
H2
C02
CO
H2S
S + S02
CH.
C2H2
NOX
Carbon Black
N2
°2
H20
Process
Vent Gas
1,229
9,978
14,071
306
TR
318
383
18
24
90,686
810
80,223
Air to
Incin.
98,553
29,848
1,396
Stack
Gas
34,308
578
38
189,226
10,060
93,633
TOTAL LBS./HR.
SCFM
198,046
57,400
129,797
327,843
82,500
Slowdown, 460° F
2,740 Lb./Hr.
Natural Gas
(Pilots)
Process Vent Gas
450° F
Stack Gas
925° F
Comb. Air (80° F
B F Water (240 F)
57,140 Lb./Hr.
Steam @ 450 PSIG, 750° F
54,400 Lb./Hr. Total
46,800 Lb./Hr. Net
-------
CB-50
TABLE CB-9
CATALYTIC INCINERATOR
FOR
90 MM LB./YR. FURNACE BLACK PLANT
OVERALL MATERIAL BALANCE, LB./HR.
Component
H2
co2
CO
H2S
CH4
C2H2
NOX
Carbon Black
No
H20
Process
Vent Gas
1,229
9,978
14,071
306
TR
318
383
18
24
90,686
810
80,223
Air to
Incin.
251,062
76,234
4,472
34,303
578
24
9
341,745
56,446
96,709
TOTAL LBS./HR.
SCFM
198,046
57,400
331,768
529,814
127,200
i 900 °F
Process Vent Gas
(450° F)
Catalyst Bed
.Air (80° F)
Natural Gas (Pilots)
-------
CB-51
temperature exceeds 750° F. These temperatures can be accomplished
by permitting part of the process vent gas to by-pass the combustion
zone and employing excess air as quench between combustion zone
and the catalyst bed. During periods of high carbon black
concentration in the incinerator feed (caused by bag filter
leakage) it may be necessary to use additional quench air or to
partially by-pass the catalyst bed section of the incinerator.
Sufficient heat is available in the catalytic incinerator effluent
to generate a similar amount of steam in a waste heat boiler as was
produced with the above thermal incinerator-boiler unit.
G. Limitations of Combustion Devices
All of the above methods of contaminent removal result in 862 and
863 production and in some cases increase NOX content of the process
vent gas. Because of the relatively low concentration level of the
sulfur oxides (0.02 to 0.17 vol. % dry basis) and NOX it would be
difficult and expensive to remove these objectionable contaminants with
present technology.
It should be noted that NOx emissions shown in the material balances
for the process vent gas control devices are calculated values based on
published data ^»9 and thermodynamic considerations. Most of the other
emissions are estimated values primarily based on general data for this
type of equipment in other processing areas. This approach was necessary
since several of the proposed emission control devices (waste heat boilers
and catalytic incinerators) have not been employed in the carbon black
industry. In addition, where the other devices have been used, the
emission data are limited.
In most cases, to make practical use of the various control devices,
it is necessary to collect process vent gases from many stacks into a
collection header for combined processing. This results in the following:
1. Increased pressure drop which either increases system operating
pressure and air blower horsepower requirement or increased size
of induced draft blower.
2. Prevents a quick visual check of individual stack vent gas streams
for locating leaking bag filters. With a combined vent stream
feeding an efficient combustion device, considerable product
could be lost before a leak would be discovered unless a photo-
electric sensing device is installed up-stream of the combustion
equipment. Inefficient devices such as plume burners, probably
would not burn sufficient black to prevent leak detection.
H. Best Pollution Control System
Based upon the above observations and economics presented in Section
VII, it appears that the most feasible air pollution control system for
existing carbon black plants would include bag filters for recovery of
product from process combustion vent gas and entrained carbon black from
drier and product finishing vent gas streams. In addition, a plume burner
or flare system, depending upon the off-gas heating value, would be used
to combust burnable material in the effluent of the process vent gas
filter. If the drier vent contains combustible material this stream
should also be burned. This only occurs when a slip stream of process
-------
CB-52
vent gas is directly used for drying. If this stream is not used,
the drier filter effluent will only contain inerts, water, CC>2 with
traces of carbon black and sulfur oxides. Under these circumstances,
the drier filter could be replaced with a water scrubber assuming
source testing confirms the reported high efficiency of the scrubber
previously described.
The most feasible air pollution control system for new plants would
include the above bag filters and process vent gas thermal incinerator
plus waste heat boiler with steam driven process equipment, as in
Table CB-7. In either new or existing plants, if the resulting SOX
and/or NOX content exceeds proposed emission limits, additional
expensive removal facilities will be required.
All new and existing plants should have portable vacuum systems for
clean-up of carbon black spills.
I. Industry Research Efforts
Current industry research effort in air pollution control centers
around alternative methods of reducing the volume of vent gas which
has to be processed. Methods being explored in this area include:
1. Pilot plant operation of the furnaces at increased pressure
(several atmospheres) in order to reduce gas volume and provide
for more efficient operation of downstream air pollution
control equipment. However, as previously indicated, some
operators of carbon black plants feel that reactor pressure
is one of the operating variables that control the type and
and quality of black produced.
2. Studies of various heat exchange systems as methods of reducing
direct water quench of furnace combustion products. The vent
gas from a conventional carbon black unit with a minimum of
indirect heat exchange contains about 45 vol. percent water.
Approximately 15 percent of this water is produced in the
furnace combustion. The remainder results from water quench.
By eliminating this quench, the normal 30 to 50 BTU/FT.^ (wet
basis) vent gas heating value could be improved, and the gas
volume reduced.
3. Use of oxygen in place of air in combustion furnace. So far,
reported pilot plants tests in this regard have been unsuccessful.
The use of pure oxygen results in too high a flame temperature
for the furnace refractory.
4. Utilization of vent gas as auxiliary feed. This has also been
unsuccessful because the low heating value of the vent gas stream
results in too low a flame temperature for quality blacks.
By reducing water and nitrogen content of this stream by methods
outlined in items 2 and 3, it may be possible to recycle the
resulting vent gas. If a major portion of this gas can be
recycled to the furnace, CO and hydrocarbon emissions can be
reduced. However, a net vent stream is required to reject C02
from the system, and the quantity of sulfur in this smaller vent
stream would approximate the atmospheric sulfur rejection without
vent gas recycle. In most plants the normal feed gas is desulfurized
-------
CB-53
natural gas, hence, the change in total sulfur emission would
be negligible. However, sulfur concentration in the net
vent gas would be higher, therefore, easier and more economical
to remove.
Work has been expended on using hydrotreated feed stocks in an
effort to reduce sulfur emissions. However, hydrodesulfurized
feeds are not looked upon with favor because hydrotreating
lowers aromatic content. This reduction in aromatics results
in lower carbon black yields per given quantity of oil feed to
the reactor and also reduces the oil processing capacity of
existing reactors.
-------
CB-54
V. National Emission Inventory
Based upon the emission factors shown in Table CB-3A the total approximate
emissions from U. S. furnace carbon black plants are as follows:
Average Total
Emission (b) Emissions ^c'
Component T/T Carbon Black MM Lbs./Yr.
Hydrocarbon + H2S ^ 0.0519 155.7
Particulate 0.00?7 8.1
NOX 0.0023 6.9
SOX 0.0072 21.6
CO 1.2907 3.872.0
1.3548 4,064.3
Less than 1070 of the total U. S. carbon black production is produced in
plants that have air pollution control devices downstream of the primary
product recovery bag filters.
Assuming plume burners were used on all existing units that do not
presently have process vent gas control devices, total emissions would be
reduced to the following approximate values:
Average Total
Emissions Emissions
Component T/T Carbon Black MM Lbs./Yr. (c)
Hydrocarbon + H2S (a) 0.0052 15.6
Particulate 0.0022 6.6
NO 0.0026 7.8
SOX 0.0283 84.9
CO 0.1374 412.2
0.1757 527.1
It should be noted that carbon black production rate is rather constant
throughout the year. As a result there is no seasonal variation in emissions.
(a) Excludes methane and hydrogen.
(b) Weighted average based on individual plant emission factors and carbon
black production.
-------
CB-55
VI. Ground Level Air Quality Determination
Table CB-3A presents a summary of air emission data for the various carbon
black plants. This table includes emissions from vent of process combustion
products, drier exhaust, product finishing and storage area gas streams.
Information regarding vapor losses from oil feed storage facilities is not
included. However, emissions from this source are small since the feedstock
vapor pressure is low at storage tank operating conditions (0.2 to 1.5 PSI).
Product storage is normally in covered silos and hoppers which have no
atmospheric loss except during loading operations.
Table CB-3A provides operating conditions and physical dimensions of the
various vent stacks. The EPA will use this information together with the air
emission data to calculate ground level concentrations for later reporting.
-------
CB-56
VII. Cost Effectiveness of. Controls
Table CB-10 presents cost analysis for the alternate methods of reducing
air pollution from the various vents. Economic data presented in this table
are for a nev plant producing 90 MM Ibs./yr. of carbon black in multiple fur-
naces with three parallel trains of product recovery equipment and are based on
the following:
A. Investment
Purchase cost of boilers was obtained from 1972 vendor quotes for
packaged type units. Published data 4 were used to determine in-
cinerator costs (packaged units). Investment data provided by carbon
black manufacturers were employed to estimate installed costs for plume
burners, bag filters and water scrubbers. Flare stack estimates were
provided by vendors.
Installation costs for the various packaged units are estimated values
based on previous experience in plant construction. A major portion of
this cost represents construction labor. These costs also include
providing collection headers on multiple vent streams where required.
B. Operating Expense
1. Depreciation - 10 year straight line.
2. Interest - 67, on total capital.
3. Catalyst Replacement - Based on published data ^, cost of
catalyst for the catalytic incinerator is set at $1,800 per
thousand SCFM of gas treated, with an assumed catalyst life
of two years.
4. Maintenance - Set at three percent of investment for boilers and
two percent for incinerators. Maintenance costs for other control
devices are based on data provided by plant operators. It should
be noted that the high maintenance figures for bag filters
primarily represents replacement cost of filter bags.
5. Labor - One man per shift used for direct fired boilers and
six hrs./day for waste heat boilers. Virtually no operating
labor is required for incinerators. Labor costs for most other
units are included in the mainentance figures.
6. Utilities - Unit costs are based on typical values for the
Gulf Coast area.
Except for the plume burners, all emission control devices
listed require induced draft blowers. Power requirements for
these blowers are based on the following assumed system dif-
ferential pressures:
£> P
in. H20
CO-boiler 14
Thermal Incinerator 6
-------
CB-57
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-------
CB-58
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-------
CB-59
TABLE CB-IO
COST EFFECTIVENESS FOR ALTERNATE
EMISSION CONTROL DEVICES
(BASED ON 90 MM LBS./YEAR CARBON BLACK PRODUCTION) sheet 3 of 3
FOOTNOTES
(a) Downstream of bag filter.
(b) Expressed as (tone of particulate removed per ton of entering particulate)
x 100.
(c) 450 PSIG, 750° F steam.
(d) Afterburner systems study by Shell Development Co. for EPA (Contract
EHSD 71-3).
(e) Excludes methane and hydrogen.
(f) Based on investment and operating cost data provided by carbon black
manufacturers.
(g) Vendor quote.
(h) Emission level if cyclone is employed for recovery.
(i) Increased future fuel costs should be considered.
(j) Not feasible with "typical" vent gas of this study, but demonstrated in
certain types of operation.
(k) Based on fuel to bring "typical" vent gas to 50 BTU/SCF.
(1) Defined as:
„„ _ 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
ohRR — .. . i i ._ ._
weighted pollutants in
See Appendix for discussion and explanation.
(m) Does not consider recent inflationary trends.
-------
CB-60
A P
in. H20
Thermal Incinerator plus
Waste Heat Boiler 14
Catalytic Incinerator 9
Bag Filter 14
Water Scrubber 15
7. Production Credits - The value of steam used on-site has been
set equal to the electric power utility costs which would apply
for using motor driven equipment in the carbon black plant.
The quantity of steam required on-site is based on replacing
80 percent of total power requirement with non-condensing steam
turbines which exhaust to the atmosphere. The 75c/M Ib. credit
used for exported steam represents a typical value for steam
based on 40c/MM BTU fuel cost. Recovered carbon black is valued
at 5.5c/lb. based on figures used by several carbon black manu-
facturers. This recovered material is combined with the process
vent bag filter black and sent to the product finishing area.
In the cases involving CO-boilers for process vent emissions control,
investment costs are based on providing two boilers each of which are able to
produce the total desired steam production. Having a 100 percent spare, provides
a more dependable steam supply and eliminates need for a plant shut-down during
boiler inpsection and maintenance.
Even if excess steam production can be utilized off-site, Table CB-10
indicates that employing dual CO-boilers is not an economical method of reducing
emissions. However, if a stand-by boiler is not required and yearly boiler
inspection can be handled during normal plant turn-around, a CO-boiler can be
economically justified. This boiler also represents one of the most efficient
methods of reducing combustable emissions.
Assuming excess steam can not be exported, the thermal incinerator followed
by a waste heat boiler is the most economical processing scheme. Since waste
heat boilers are somewhat more dependable than direct fired units, a single
boiler should be adequate. However, if it is not desirable to shut down
the whole carbon black plant once a year for boiler inspection, two 50 percent
boiler facilities should be considered. No existing carbon black plant
incorporates this processing scheme. However, it is assumed that process vent
gas emissions from this type of unit would be similar to those predicted for
CO-boilers.
Thermal incineration of the process vent gas (without steam generation)
has a somewhat higher operating cost than the less efficient and less dependable
plume burner. Catalytic incinerators are more expensive to operate and result
in only slightly lower NOX emissions than the thermal unit.
It should be noted that economic data presented for the various combustion
devices are based on processing an average process vent gas having a heating
value of 40 BTU/SCF. If for a particular grade of carbon black production, the
vent gas heating value is lower than this average figure, it would be necessary
to increase supplemental fuel usage in the CO-boilers and increase incinerator
feed effluent heat exchange. For higher heating value gases less fuel and heat
exchange are required.
-------
CB-61
Assuming reported particulate removal efficiencies are correct, Table
CB-10 shows that water scrubbing of the drier vent gas is much more economical
than bag filtration. Even though the water scrubber is less efficient, total
particulate emissions for a plant using water scrubbers is only about 0.00025
T/T (125 Ibs./hr. based on total U.S. production) more than for bag filters in
this service.
If a plant incorporates pneumatic conveyor system for transporting carbon
black, increased product recovery can pay for bag filter operating costs.
However, this is not true for the bag filter sometimes used in product bagging
and storage areas.
Costs for installing the various pollution control equipment in existing
plants would be about the same or only slightly higher than the figures shown
in Table CB-10. The actual cost differential would largely depend on space
availability and its location relative to associated process equipment.
Obviously, with tabulations such as presented in Table CB-10, the reader
can make a variety of adjustments to satisfy his own accounting techniques or
technical standards. Thus, unit costs can be modified to be appropriate to
local situations or to account for future or recent past escalations. Similarly,
different combinations of equipment can be considered. For example, if only
a single CO-boiler were employed, the investment would drop to about $1,000,000
and the annual operating cost would become a credit of $55,000 per year,
assuming that the reliability of steam export could assure the $190,900 estimated
income.
-------
CB-62
VIII. Source Testing
It is recommended that source sampling should be performed on the
CO-boiler and incinerator feed and effluent streams at the 50-26 carbon black
plant. This is the only plant that employs these emission control devices
and available data is limited. During sampling it would also be desirable
to obtain effluent samples at reduced excess air rates (4 mol. "L 02 - dry basis)
in order to confirm the somewhat more economical design basis used in the
pollution control equipment economic comparison.
It is recommended that samples of the feed and effluent from drier
vent gas scrubbers at plant 50-28 should be analyzed in order to determine
particulate removal efficiency. If the high efficiency estimated by this
carbon black manufacturer (>947o removal) can be verified by plant tests, water
scrubbers could constitute an adequate substitute in this service for the much
more expensive bag filters.
-------
CB-63
IX. Industry Grovth Projection
The U.S. annual carbon black production (all grades) is estimated to
increase to 5.5 billion pounds by 1985, see Figure CB-6.
Approximately 95 percent of all carbon black produced is used in the
production of rubber. Demand in this area is strong because of the rubber
industry needs for new car tires. The ratio of carbon black to rubber in
tires and other rubber products continues to rise.
The projected increase in carbon black production ( three percent/year) will
require the construction of approximately 21 new units between 1972 and 1985,
based on an average capacity of 90 million pounds per year carbon black
production as used in this report. Because of the continued increase in cost
of natural gas, virtually all of the new plants will incorporate the oil or
mixed feed furnace process instead of the competing gas feed thermal and
channel processes. It is doubtful if any existing furnace carbon black plants
will be replaced during this time period. Even though the trend is toward
larger plants which are somewhat more economical to operate, the smaller
existing producers can improve their economics by adding parallel trains of
equipment as production demands increase.
In the past, most carbon black plants were located near oil and gas
feed source (i.e., Texas and Louisiana). However, recent plants have been
constructednear tire manufacturers (i.e., Toledo, Ohio plus Moundsville and
Waverly, West Virginia). It is expected that future plants will follow the
most recent trend and be located close to the major carbon black consumers.
No new channel type units will be built. At present there are only
two channel carbon black plants remaining in operation in the U.S. with a
total installed capacity of 76 MM Ibs./year. In the future these two plants,
which are located in Texas, will have to operate at reduced capacity in order
to meet state regulations on particulate emissions.
There are no known processes that can compete with the furnace process.
Besides the high polluting channel process, the only commercially operated
process for making carbon black is the thermal type unit, which presently accounts
for approximately nine percent of the U.S. carbon black production. It is
doubtful if the thermal process will increase its market share, because thermal
blacks are large particle size carbon black which have low reinforcement and
poor abrasion qualities in rubber and are, therefore, not suitable for tire
tread and many other applications. In addition, this is a gas fired process
which requires a high cost, short supply feedstock. Furthermore, even though
the process has low CO emissions, technological problems would make clean-up of
the particulates, that are emitted as puffs of smoke and flame on each furnace
switch, very expensive and difficult.
At present, approximately 10 percent of carbon black produced in this
country is exported. This percentage is dropping as additional plants are
built abroad.
As indicated in Section II, profit margin for carbon black production is
small. Therefore, any significant expenditure for air pollution control
equipment could result in a higher carbon black selling price. This in turn
might lead to a further decline in exports or might even result in importation
of carbon black from areas where air pollution controls do not exist. If
-------
CB-64
100
2) (Jhemict 1
(Jheraics 1
3). Br.ocesi
Report
(Jheraicz i Bc0rtcrnttcs"1Handbitcrk, January;
Marlieting
Profile
Reaeflr.ch, 1
on Carbon B
Reportier, February 15, 1971
nc, August 13, 1971
ack
1960
1964
1968
1972
1980
1984
-------
CB-65
substantial importation of carbon black does occur, the above growth projection
will be reduced accordingly. At the present time, only ink grade carbon
blacks are being imported because they are made chiefly by the highly polluting
channel process and most U.S. channel plants have been shut down. The industry
feels, however, that there is both a current and future possibility of
importation of other grades, because of cost considerations.
There is no known substitute for carbon black as a filler material for
tires, or as a pigment but recent improvements in cording and belting techniques
could reduce demand growth rate if they result in longer tire life.
-------
CB-66
X. Plant Inspection Procedures
Loose carbon black is light and readily disperses on handling. In the
various phases of production, every effort should be made at the plant to
contain carbon black and prevent any loss in order to avoid air pollution.
Plant inspections will be conducted by the appropriate authorities, either
on a routine basis, or in response to a complaint. Usually, the inspecting
agent will only be able to make visual observations although the distinct odor
of reduced sulfur compounds is sometimes experienced in the vicinity of carbon
black plants that do not burn their off-gases. It is unlikely that any
particulate monitoring or sampling devices will be available in the effluent
streams although some plants might have provision for gas sampling.
If the inspector has any reason to suspect that emissions are excessive,
some factors that he should consider and/or discuss with plants officials are
itemized below:
A. Emission of carbon black from the main process vent bag filter occurs
when individual filter bags fail. When a bag fails it will tint the
filter's effluent. The amount of opacity of the stack vent gas depends
on the size and number of bag failures and type of emission control
device downstream of the filter. A control agent should use the
Ringelmann Chart to make a rough estimate of the net particulate
emissions in this stream. One plant reported that during normal
operations particulate emissions do not exceed 1.5 on the Ringelmann
scale.
In addition to bag failures, visual discharges of particulates can be
caused by improperly installed bags, loose bag clamps, or improper
sealing of tube sheet joints.
If the plant is experiencing short bag life and thus frequent high
emissions, it might be due to excessive pressure drop across the
baghouse caused by high flow rates or other reasons (15).
Maintenance of the bag filter system is vital to tis efficient operation,
Therefore, many plants will keep repair and maintenance records for the
baghouse and associated ductwork, fans and conveyor system.
Since it is not practical to shut down the filter system for inspection,
it is necessary to know the maintenance schedule for the baghouses if
the plant management is agreeable to an inspection of the inside of the
filter by the control agent.
A well defined program for bag replacement based upon expected baglife
helps insure proper filter operation and minimal downtime.
B. Spillages of carbon black or losses of black to the atmosphere occur
in the following processing areas:
1. Around the pelleting equipment. When pellets cease to form in the
dry pelleting process the drum has to be emptied, reloaded with
freah black, and reseeded before pelleting can be resumed. The
emptying of the drum will result in some loss of black.
-------
CB-67
2. When cleaning the screens used to remove oversized pellets from the
product before storage.
3. Whenever samples of black are drawn from various points in the
production line, some dusting occurs.
4. Whenever a production line is plugged, the remedial measures can
involve the use of high-pressure air to dislodge the blockage.
5. Carbon black is so finely divided that whenever a leak develops
in plant equipment, black will seep out and dust into the
atmosphere. These leaks, which usually develop in the conveying
system, can be caused by external corrosion or internal erosion.
6. Black can seep from portions of the conveying equipment which may
not be completely dust-tight due to defective seals or worn
sprockets in the screw conveyor, or defective buckets in the lift
elevator.
7. Black is sometimes spilled from open or torn bags in the product
storage area.
8. Some loss of black to the atmosphere occasionally occurs in the
packing of bags or the bulk loading of hopper cars.
9. Wastage of black occurs during the cleaning of hopper cars.
10. The cleaning of equipment being repaired will release black to
the atmosphere.
A visual check of the above areas should be made to determine if
adequate effort is made to minimize these sources of particulate emission
and to ascertain if sufficient equipment such as portable vacuum devices
and water washing facilities are available to quickly clean-up any
spillage.
Emissions from water scrubbers on either main process or drier vent
gas streams, should be visually checked by observing the stack gas
opacity after dissipation of water vapor. If excessive, it could be
caused by:
1. Water pressure and flow rate to the scrubber being different than
design values.
2. Temperature and pressure of feed gas being different than plant
operating and design values.
3. Feed gas pressure drop across the scrubber being excessive.
4. Deposits of material or internal fouling of the scrubber which could
disturb flow patterns.
5. An inadequate maintenance schedule for cleaning and replacing water
nozzles.
6. Improper operation of fans and pumps.
-------
CB-68
D. Particulate emissions from drier and other stacks in product finishing
and storage areas are normally small but should be visually checked to
determine opacity. Depending upon the clean-up method employed, the
above comments are applicable.
E. If incinerators are provided on any of the vent streams, a visual check
of the stack gas should be made. When smoke appears from an incinerator,
malfunctioning of the combustion process or excessive leakage of an
upstream bag filter should be suspected. Smoke not related to the bag
filter can and should be eliminated by improving the incinerator
combustion. Smoke-free combustion requires adequate time, good
turbulence in mixing the fuel and air, and sufficient temperature
for the reaction rate to proceed to completion and produce the desired
products of oxidation. If malfunctioning of the incinerator is
suspected, it could be caused by:
1. Burner in combustion zone not operating. Process vent gas and/or
air valves not open.
2. Combustion zone temperature not in the design range.
3. The quantity of excess air may be different than design. This
might be determined by checking the air flow chart, or measuring
the temperature of stack gases. A stack gas temperature less than
design may indicate a large quantity of excess air.
4. Log data on the composition of stack gas should be reviewed, if
available. Variance in analytical results can usually be attributed
to one or more of the aformentioned factors.
The following measures are usually recommended by manufacturers to
improve performance of a smoky incinerator.
1. Usually smoke will be produced if the combustion zone temperature
is low or fuel to air ratio is not optimal. If combustion zone
temperature is low:
(a) Add supplemental fuel.
(b) Reduce the quantity of excess air if it is too high. Gaseous
fuels require at most 20 percent excess air. Air requirement
for liquid fuel varies between 10 to 75 percent excess, depending
upon the quality of the burner. Several hundred percent excess
air may be enough to chill flame and cause smoking. Caution
must be taken in reducing excess air at the burner if its
source is infiltration through a leaky furnace. Sealing leaks
or reducing negative draft is proper method when this is the
case.
(c) Process vent gas, fuel and air should be tested to detect
abnormal water content.
2. If turbulence and temperature are fixed and the furnace still smokes,
it may be necessary to increase the excess air flow. While low
excess air flames are often desirable, the availability of
additional air provides more oxygen and often results in a shorter
smokeless flame.
-------
CB-69
XI. Financial Impact
Table CB-11 presents economics for carbon black manufacture in a present
day typical 90 MM Ibs./yr. plant that incorporates bag filters on main process
and product handling vent streams, water scrubber on drier purge gas and a
vacuum recovery system for clean-up of product spills. As previously indicated,
estimated profit for carbon black manufacture is relatively small. Since
production costs of 6.54c/lb. are so close to selling price of 7.25c/lb«, any
additional expenditures for pollution control equipment may have to be reflected
in a higher carbon black selling price.
Estimated total cost for producing carbon black in this same type of
existing unit, which has been modified to burn off-gas in plume burners, would
be 6.58c/lb. (see Table CB-12). This has been defined as the most feasible
control method for existing plants, and results in a 5.6 percent reduction in
NPAT. Table CB-12 also shows the sensitivity of the calculation to capital
and operating costs for the pollution control equipment as estimated in Table
CB-10. Doubling of these cost factors results in a reduction of return on
investment (ROI) from 2.86 percent for the basic plant to 2.45 percent. However,
total NPAT could be restored by a 1.1 percent increase in selling price.
Table CB-13 shows estimated manufacturing costs for a new most feasible
type unit. This plant includes a thermal incinerator plus waste heat boiler
on the combined effluent from three parallel trains of vent gas bag filters.
The 46,800 Ibs./hr. of superheated steam generated in the boiler is used on-site
to drive process air and induce draft blowers and major pumps. Bag filters
are employed on product handling and drier purge vent gas streams and in the
product storage area. Total carbon black production cost for this unit would
be 6.63c/lb., resulting in a 13 percent reduction in NPAT. The sensitivity
analysis shows a further decrease in ROI to 1.49 percent and the need to increase
prices by 3.9 percent if total original NPAT is to be restored. It should be
noted, however, that no additional steam credit is included.
Table CB-13A presents pro-forma balance sheets for the cases described
above (excluding the sensitivity analyses). It was assumed in developing these
asset and liability positions that management of the carbon black plant believes
that the possibility of an increase in foreign imports exists, if they raise
prices, and they have, therefore, chosen to accept a smaller profit margin in
order to maintain sales at a peak level. Capital requirement for the most
feasible new plant is about $910,000 higher than for existing type plant.
In addition to the financial impact, one should also evaluate the overall
environmental impact of the most feasible method of emission control described
in this report. This, of course, is a very involved type of evaluation, but
the single most important factor for consideration is the impact on the supply
of energy. If, carbon black off-gases are burned and the energy value recovered
and used to drive carbon black process equipment in all future plants, the energy
saving will be equivalent to about eight billion standard cubic feet of
natural gas per year by 1985. This would be a direct saving of natural gas
if these plants are built in the Texas/Louisiana area. If, on the other hand
they are built in the Ohio River Valley as seems to be the current trend, the
saving would probably be in energy output from a coal burning power station
thus also achieving a reduction in air pollution from that source.
-------
CB-70
TABLE CB-11
CARBON BLACK MANUFACTURING COST
FOR A TYPICAL
EXISTING 90 MM LB./YR. FACILITY
DIRECT MANUFACTURING COST
Feedstock
Natural Gas @ 40c/MM BTU
Oil @ 8.0c/Gal.
Labor (10 men/shift @ $4.85/Hr.)
Maintenance (5% of invest.)
Utilities
INDIRECT MANUFACTURING COST
Plant Overhead (110% of labor)
Laboratory
FIXED MANUFACTURING COST
Depreciation (10 years)
Insurance & property taxes (2.3% of invest.)
MANUFACTURING COST 5.49
GENERAL EXPENSES
Administration (3% of manufacturing cost)
Sales (1% of manufacturing cost)
Research (2% of manufacturing cost)
Finance (6% of investment)
Total Cost 6.54 5,886,000
Selling price 7.25* 6,525,000
Profit before taxes 639,000
Profit after 52% tax (NPAT) 306,700
Cash flow 1,377,700
ROI (NAPT x 100/Investment) 2.86%
*Based on bulk rate. If sold in bags, manufacturing cost and selling
price 0.75c/lb. higher.
-------
CB-71
TABLE CB-12
CARBON BLACK MANUFACTURING COST
FOR A TYPICAL
EXISTING 90 MM LBS./YR. FACILITY WITH
RETROFIT PLUME BURNER
DIRECT MANUFACTURING COST
Feedstock
Natural Gas @ 40c/MM BTU 0.42
Oil @ 8.0c/Gal. 1.43
Labor 0.44
Maintenance 0.60
Utilities 0.43
3.32
INDIRECT MANUFACTURING COST
Plant Overhead (110% of labor) 0.48
Laboratory 0.24
0.72
FIXED MANUFACTURING COST
Depreciation (10 years) 1.21
Insurance & property taxes (2.3% of invest.) 0.27
1.48
MANUFACTURING COST 5.52
GENERAL EXPENSES
Administration (37° of manufacturing cost) 0.17
Sales (1% of manufacturing cost) 0.06
Research (27° of manufacturing cost) 0.11
Finance (670 of investment) 0.72
1.06
Total Cost . 6.58* 5,922,000
Selling price 7.25* 6,525,000
Profit before taxes 603,000
Profit after 527= tax (NAPT) 289,400
Cash flow 1,378,400
ROI (NPAT x 100/Investment) 2.6670
*Based on bulk rate. If sold in bags, manufacturing cost and selling price
0.75c/lb. higher
Sensitivity Analysis (1007o increase in:)
Capital Charges Capital Charges plus Utility Costs
NFAT, $/Yr. 272,400 271,900
Cash Flow, $/Yr. 1,376,400 1,375,900
ROI, % 2.46 2.45
-------
CB-72
TABLE CB-13
CARBON BLACK MANUFACTURING COST
FOR A MOST FEASIBLE NEW
90 MM LBS./YR. FACILITY
WITH INCINERATOR & WASTE HEAT BOILER
DIRECT MANUFACTURING COST c/LB.
Feedstock
Natural Gas @ 40c?/MM BTU 0.42
Oil @ 8.0c/Gal. 1.43
Labor 0.45
Maintenance 0.64
Utilities 0.25
3.19
INDIRECT MANUFACTURING COST
Plant Overhead (110% of labor) 0.50
Laboratory 0.24
0.74
FIXED MANUFACTURING__COST
Depreciation (10 years) 1.29
Insurance & property taxes (2.37, of invest.) 0.30
1.59
MANUFACTURING COST 5.52
GENERAL EXPENSES
Administration (3% of manufacturing cost) 0.17
Sales (17o of manufacturing cost) 0.06
Research (27° of manufacturing cost) 0.11
Finance (67, of investment) Q.77
1.11
Total Cost 6.63* 5,967,000
Selling price ' 7.25* 6,525,000
Profit before taxes 558,000
Profit after 527, tax (NAPT) 267,000
Cash flow 1,428,000
ROI (NPAT x 100/Investment) 2.307,
*Based on bulk rate. If sold in bags, manufacturing cost and selling price
0.75c/lb. higher.
Sensitivity Analysis (1007o increase in:)
Capital Charges Capital Charges plus Utility Costs**
NPAT, $/Yr. 195,500 184,000
Cash Flow, $/Yr. 1,428,500 1,417,000
ROI, % 1.59 1.49
**Excludes additional credit for steam at escalated cost rates.
-------
CB-73
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CB-74
XII. Cost to Industry
In the typical present day plant depicted in Table CB-11 approximately
5% of the plant investment cost is directly attributed to air pollution
equipment. This expenditure plus associated operating costs equals 2% of
the carbon black total production cost (0.13 C/lb.). Included in this
expenditure are the folloving items:
A. Approximately 10% of the process vent gas bag filter investment.
The remaining cost of this facility is assumed to represent normal
process requirements for product recovery.
B. Additional concrete surfacing in plant area. This facilitates
clean-up of carbon black spills.
C. Vacuum clean-up system.
D. Net expenditures for product transport bag filter and drier vent gas
water scrubber.
As noted in Section XI, the proposed most feasible modification of
existing carbon black plants results in only a slight increase in production
cost (0.04 c/lb.). Even with the existing low profit margin, it is doubtful
if this cost increase should cause any significant economic problems to the
industry.
Assuming all existing U. S. furnace black plants without process vent
gas incineration are modified to incorporate plume burners, the total invest-
ment for this conversion would be approximately $5,000,000.
In the "most feasible new plant" presented in Table CB-13, air pollution
control equipment represents approximately 12% of total capital and 0.22 c/lb.
of the carbon black production cost. The resulting 0.09 c/lb. higher cost than
for the present day typical unit, in all likelihood, will not reduce growth in
demand for carbon black but could increase demand for foreign produced black.
Assuming all new plants built between now and 1985 incorporate this type
of air pollution control equipment, the total incremental capital cost will be
about $18,000,000.
The projected effect of the above expenditures on future air emissions
is shown in Table CB-14.
-------
CB-76
XIII. Emission Control Deficiencies
Technical deficiencies preventing reduced levels of emissions include
the following:
A. Process Chemistry and Kinetics
Production of carbon black is a non-catalytic partial oxidation
reaction. The quantity and type of carbon black produced is influenced
by feedstock quality, oxygen concentration in reactor furnace plus
reactor residence time and operating temperature.
1. Feedstock
All liquid feeds presently employed contain sulfur, most of
which is ultimately vented to the atmosphere as t^S or sulfur
oxides. Based on present technology it is not possible to
desulfurize the feed without some reduction in aromatic content
which results in lower carbon black yield.
2. Oxygen Concentration
All existing carbon black plants use air as a source of oxygen.
This results in a large volume of nitrogen being vented which dilutes
other emissions. Because of this dilution, it is more difficult
and expensive to control the quantity of these emissions.
3. Reactor Operating Conditions
Reactor operating conditions influence the quantity of non-
selective products obtained. However, since physical properties
of the carbon black are also related to the operating conditions,
temperature and other operating variables can not be arbitrarily
adjusted to limit emissions.
B. Process Equipment and Operations
1. Reactor Furnace
Each major carbon black producer has its own reactor furnace and
burner design.-' The design of this equipment does effect carbon
black selectivity to a certain extent but general magnitude of
emissions for all commercial reactors are similar.
2. Quench System
A major portion of the heat of reaction is lost in the effluent
water quench. In addition to wasting energy this quench water
increases volume of the vent stream.
C. Control Equipment and Operations
The proposed treatment scheme, involving incineration of the
exhaust from a bag filter, is the best method of reducing organics
and residual carbon to negligible quantities. The deficiency in
this treatment scheme is that it does not remove sulfur compounds or
nitrogen oxides generated in the manufacturing process. In fact,
nitrogen and sulfur oxides are generated as a result of the incineration.
-------
CB-77
If these emissions exceed future air pollution limits, additional
treatment of flue gas for removal of contaminants would be required.
Unfortunately, application of the few available treatment methods have
not been technically and economically developed on a commercial
scale. Some of these methods are:
1. Stone & Webster ^ - Ionics Process is a commercial method
to remove S0£. The process includes a sulfur dioxide
scrubber in which S02 is absorbed in a sodium hydroxide
solution.
2. A number of processes have been developed using liquid
absorption techniques for removing SC>2 but most are not
very practical 13. For instance; (a) sulphidine process
uses a mixture of xylidine and water in approximately
50-50 percent mixtures and the by-products are sodium
ulfate and SC>2, (b) the ASARCO process developed by
American Smelting & Refining Co. for the removal of SC>2
uses dimethylamiline as the absorbant, (c) SC>2 is often
absorbed by aqueous ammonia to produce ammonia sulfite, with
subsequent oxidation to sulfate.
3. Flue Gas Cleaning: Combustion Engineering's ^ Limewater -
SC"2 Scrubbing Process is a commercial flue gas cleaning
process that has been reported to remove oxides of sulfur
and nitrogen. Slaked lime or limestone aqueous suspensions,
which are capable of removing S02 or 803 as acid gases, are
capable of removing a certain amount of NOX for the same reason.
However NOx removal from stack gases is more difficult.
Other flue gas treating processes under study for S02 c°ntrol
that have shown varying abilities to remove NOX are the
Reinhuft Char Process and the Tyco Laboratories Modified Lead
Chamber Process ^. These processes are still in the research
stage.
(a) Reinluft Char Process: This process uses a slowly moving
bed of activated char to remove primarily the sulfur
oxides from flow gases. Some NOX may simultaneously be
removed.
(b) Tyco Laboratories; Modified Lead Chamber Process: This
flue gas treating process being researched by Tyco Lab-
oratories, Inc., under contract to NAPCA, utilized the
chemistry of the chamber sulfuric acid process to remove
both sulfur and nitrogen oxides.
(c) Catalytic reduction of oxides of nitrogen is also reported
to be in the development stage.
-------
CB-78
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. Feedstock Desulfurization
It would be desirable to develop a method of desulfurizing the
feed without saturating aromatics. However, it is not believed that
R & D in this area can be justified at this time. Other much larger
industries, such as the petroleum refiners and utility companies,
are spending large sums of money in desulfurization technology and
possible future developments in this effort can find application in
carbon black manufacture.
If full range crude oil is desulfurized before further processing,
the conventional high aromatic carbon black feedstocks would contain
less sulfur compounds. However, based on present technology and air
pollution laws, it is not economical or necessary to desulfurize full
range crude. Many products derived from crude oil can be produced
without desulfurization. In addition,with present technology it is
not possible to completely desulfurize the high boiling crude
fractions. Since carbon black manufacture consumes only a very small
percentage of the petroleum production,it is not possible to justify
crude oil desulfurization R & D for this particular application.
However, if a technology break-through or air quality controls make
crude oil desulfurization practical, then tests on carbon black feeds
derived from desulfurized crude should be made.
2. Oxygen Feed plus Vent Gas Recycle
A combination of pure oxygen feed in place of air and recycle
of vent gas to the reactor furnaces could possibly overcome problems
previously experienced in efforts to reduce net emissions.
B. New Plants
In addition to the above R & D areas which have application to
both new and existing plants, the following items would require new
facilities for utilization of gained technology:
1. Substitute Feeds
In the furnace carbon black process, feedstock costs represent
25-307o of the manufacturing cost. Any possible reduction in this
particular cost item could help defray the cost of future pollution
control devices. One possibility in this area could be used tires as
a substitute feedstock. Tire casings could conceivably be distilled
and the aromatic liquid used as feed in a conventional type reactor
or the casings directly charged to the carbon black furnace. For
the latter approach, the furnace design would have to include
provision for solid waste rejection. Before any R & D effort is
expended in this regard, a study of logistics is necessary in order
to determine if adequate feed would be available. By converting
tires to a liquid feed, logistics are not as critical, since the
-------
CB-79
distillation facilities would not have to be located at the carbon,
black plant site. However, in any case, since sulfur is added to
rubber during its formulation, the possibility of pollution from
this source will require consideration.
2. Modified Processing Scheme
R & D might show that the "checker" brick furnace used in the
thermal carbon black manufacturing process could have application in
a mixed feed operation. It may be possible to replace part of the
natural gas feed normally used in the thermal reactor with oil and
thereby produce carbon black at high selectivity with low average
gaseous emissions which is indicative of the thermal process.
However, even with redesign of the "checker" furnace it is very
doubtful if small particle size product can be obtained by this
modified thermal process.
-------
CB-80
XV. Research and Development Programs
Of the various R & D project areas listed in Section XIV, only one
appears to have a good chance of success for obtaining a method of reducing
emissions from future carbon black manufacture. A proposed R & D program
for scoping this project is as follows:
1. Project Title - Oxygen Feed plus Vent Gas Recycle for Reduced Emissions,
2. Object
To develop preliminary data on a modified furnace black process
which could result in vent stack gas emissions significantly lower
than the present processing scheme.
3. Project Cost (see Table CB-15 for cost breakdown)
Capital Expenditures $275,000
Operating Costs
Total Manpower 148,600
Services 12,100
Materials 7,500
Contingency 48,800
Total $492,000
4. Scope
On a laboratory scale, modify the furnace black process by
recycling stack gas so that contained combustibles can replace
part of normal fuel requirements. By employing this low heating
value fuel, it should be possible to use pure oxygen in place of
most if not all of the air presently used for combustion. In
addition to reducing the total volume of net emissions, less NOX
will be formed in the furnace reactor because of the reduction or
complete absence of nitrogen.
5. Program
(a) Engineering
Process engineering effort is required to determine if
thermodyaamic equilibrium favor recycle of vent gas as a method
or reducing net emissions. In addition, engineering studies
will determine if it is economically desirable to cool the
recycle gas for water removal.
(b) Design, Construction and Checkout
This part of the project is concerned with the design,
fabrication and/or purchase of equipment and start-up of a
laboratory-scale pilot plant. The furnace is the heart of the
process. Since carbon black furnace design is still largely
empirical, the pilot plant reactor should be designed to allow
as much control as po**ible over temperature, turbulence and
residence time.
(c) Feasibility Demonstration
This part of the project calls for operating the unit in the
-------
CB-81
TABLE CB-15
DETAILED COSTS
FOR
R & D PROJECT
Engineering
Process Design
Process Engineer,2 Men - 16 Weeks (Each)
Contingency
Design, Construction & Checkout
Design Manpower: Professional - 16 Weeks
Major Equipment, Installed
Contingency
Feasibility Demonstration
Operation
Manpower: Professional 4.0 Weeks
Technician - 2 Men/Shift, 3 Shifts/Day for 8 Weeks
Services: Analytical - 300 Hours
Materials
Contingency
Process Development
Operation
Manpower: Professional - 8.0 Weeks
Technician - 2 Men/Shift, 3 Shifts/Day for 16 Weeks
Services: Analytical - 500 Hours
Computational
Materials
Contingency
19,500
2,500
22,000
14,800
275,000
30,200
320.000
3,700
34,400
4,400
2,500
5,000
50,000
7,400
68,800
7,200
500
5,000
11,100
100,000
-------
CB-62
conventional manner; i.e., with air and without recycle, to
demonstrate that the unit can produce carbon black. Carbon
quality would be gauged by simple analytical tests for tint
values, iodine number and oil absorption as measures of
particle size, surface area and structure, repsectively.
In addition an electron microscope would be used to examine
particle structure.
(d) Process Development
Process development work actually begins at this point in
the project. It is expected that a process variables study
might find a set of operating conditions which would yield
carbon black of commercial quality. Pure oxygen is to be mixed
with steam plus CO and C02 (composition adjusted to approximate
equilibrium operation). As a starting point, quantity of
synthetic gas and oxygen is to be adjusted to duplicate reactor
residence time and oxygen partial pressure employed in successful
feasibility run. After general scoping runs the pilot unit
would be switched to recycle operation. Again carbon quality
would be gauged by relatively simple analytical techniques.
If any extremely promising carbon black samples are obtained, they
should be sent out to be blended into rubber batches and tested
for physical properties.
6. Timetable
Total time for project is estimated to be 14 months (excludes
time required for delivery and construction of pilot plant
equipment). Figure CB-7 presents a bar graph for the proposed
work schedule.
-------
CB-13
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CB-84
XVI. Sampling. Monitoring and Analytical Methods for Pollutants in Air Emissions
A. Methods in Use for Gaseous Pollutants
In the carbon black industry, gaseous pollutants resulting from the
reducing-flame combustion of hydrocarbon fuels may be categorized as
combustion products, sulfur compounds and oxides of nitrogen. The
combustion products category includes hydrogen, carbon monoxide, carbon
dioxide, methane, acetylene and gases normally found in the atmosphere.
The sulfur compounds measured consist of a mixture of hydrogen sulfide
and sulfur dioxide, although some free sulfur may also be present in
the stack gases. The oxides of nitrogen result from combustion and
probably consist principally of nitric oxide.
Six replies were received in response to an inquery relating to
methods for sampling and analysis of combustion products. The quality
of response was quite varied, necessitating follow-up of most responses.
The information obtained is summarized in Table CB-16. It may be seen
that gas chromatography is the universal analytical tool with double
or triple columns indicated in most replies. The frequency of analysis
was related to production control requirements and ranged from daily to
semi-annually.
From the air pollution standpoint, the principal gaseous components
of interest are carbon monoxide and acetylene. The analytical method
of multi-column gas chromatography is an entirely acceptable technique
for isolation of CO and C-2^2 from a 8as mixture. Some questions, however,
might be raised concerning possible losses in the moisture removal step
or through reaction in the sample container. Although preference might
be given to inert gas dilution instead of condensation for moisture
control, the low solubility of acetylene and the short reaction time in
the case of carbon monoxide would probably minimize any errors. Assuming
that the samples are analyzed immediately following collections, it is
probable that the results obtained adequately reflect the true emissions
and further work in methods development is not warranted.
A variety of methods for the analysis of sulfur dioxide and hydrogen
sulfide were indicated by the four responses received. These are
summarized in Table CB-16. Two plants use a single train containing
peroxide impingers for S02 and cadmium sulfate impingers for H2S.16 One
plant reported the determination of total sulfur by material balance
with S02/H2S ratio measured by gas chromatography. The fourth plant
reported the determination of S02 and H2S by gas chromatography with an
S02 check using a modified West-Gaeke procedure.1? The frequency of
analysis was low in all cases (typically once per year).
The principal criticisms of the methods listed related to the possible
occurrence and behavior of free sulfur in the gases and sample train and
to the plausibility of the existance of S02 and H2S in near equal quantities,
Based upon thermodynamic equilibrium calculations, the quantity of
sulfur present as elemental sulfur and S02 would be expected to be very
small.
Any free sulfur passing the filter in the impinger trains might inflate
the S02 results or the oxidation of l^S in the peroxide impingers might
produce the same result. This effect, however, would not occur in the gas
-------
CB-85
chromatography technique unless sulfur or hydrogen sulfide is oxidized
to S02 in the sample collection bottle. The latter possibility appears
remote since the production of sulfur from SOo and HoS would be the
expected reaction.
Sufficient information is not available for a precise critique of
the methods presented, but the compatibility of results produced by
four divergent techniques would tend to indicate that the methods are
probably free of major error. Of the methods described, it appears that
the material balance combined with gae chromatography offers the greatest
potential if it could be shown that sulfur is not present in the stack
gases. It should be noted that virtually no manufacturer has been able
to close the overall plant sulfur balance.
Only one plant analyzed for total oxides of nitrogen (Table CB-16)
using a pair of small impingers containing peroxide for collection and
the phenoldisulfonic acid technique for analysis 16. Insufficient detail
was furnished for a precise evaluation of the technique, but collection
efficiency might be low and somewhat variable and there may be inter-
ferences due to the complex gas stream components. Considering the single
measurement reported, it appears that further NOX emission data should
be developed. Since the gas stream is quite complex, chemiluminescence
would be the best method of analysis.
Two plants reported particulate samples using the Alundum thimble
and stainless steel train 17. Several possible deficiencies are inherent
in this technique, including the questionable efficiency of the thimble
on the small carbon black particles and possible reaction of the gas
mixture on or with the stainless steel portions of the train. One plant
reported the reaction of HoS and S02 in a stainless sample bottle to
form free sulfur. Insufficienct information is available for a precise
critique, but it appears that the reported results are subject to
significant error. Further sampling should be undertaken using an EPA
train 18 with high efficiency glass fiber filter and glass components.
B. Recommendations for Methods Development
1. No further work is necessary for combustion gas analysis (including
carbon monoxide and acetylene).
2. A limited literature review revealed no information on the analysis
of mixtures of sulfur dioxide, elemental sulfur and hydrogen sulfide.
Development work is required to determine first whether the mixture
actually exists in the stack gases and second, to find suitable
collection techniques that will permit separation and analysis of the
components without interaction.
3. The survey revealed little information on oxides of nitrogen
emissions, but from the standpoint of methodology, it appears that
chemiluminescence should be applicable without further development.
4. The EPA sampling train and technique should be applicable to
carbon black measurement, but some consideration should be given to
the question of possible reaction of H2S and S02 in the train to
produce solid sulfur.
-------
CB-86
TABLE CB-16
SUMMARY OF
SAMPLING AND ANALYTICAL METHODS REPORTED
Component
Combustion Products
FOR POLLUTANTS
Method No.
Sheet 1 of 3
(H2, CO, C02,
CH4, C2H2,
A, 02)
N
2'
Procedure
Collect gases in glass sample
bottle after passing through
anhydrone scrubber for water
removal. Analysis by double
column gas chromatography
H2, 02, N2, CH^ on 5A molecular
sieve using argon carrier.
C02, C2H2, C2, 03, etc. on
Porepak Q using helium carrier.
Sample train consisting of metal
filter, cooling coil, knockout
pot, pump and stainless steel
pressure cylinder. Analysis of
H-
A +
CO,,, N.
CH,
and CO by double column gas
chromatography. C02 flnd C2H2 on
charcoal column witn silicate
solution. Others on 5A molecular
sieve.
5
6
Sulfur dioxide
Filter and analyze using gas
chromatography.
Pump sample into glass tube.
Analyze using gas chromatography
Analysis by gas chromatography.
Analysis by Orsat and gas
chromatography. Columns consist
of: 30% 2 ethyl hexosilicate
on 60-80 mesh chromosorb P;
5' x V stainless column
containing 45-60 mesh chromosorb
P: and 7' x %" stainless column
with 13x molecular sieve.
Collect in 3% peroxide contained
in a series of 2 ASTM D 12G6
lamp sulfur absorbers. Precipitate
with BaCl2 and filter through
Whatman # 42 filter paper. Place
filter into burned and tared
thimble. Dry and ignite paper
in thimble using Bunsen burner.
Burn thimble in muffle furnace
at 950° C for 2 hours, cool and
weigh. 16
Sintered metal filter followed by
2 impingers each containing
-------
CB-87
Component
Hydrogen Sulfide
TABLE CB-16 (continued) Sheet 2 of 3
Method No. Procedure
100 ml. of 3% H202. Measured
volume of impinger contents
and withdraw a 5 ml. aliquot.
Add 20 ml. isopropyl alcohol
and 6 drops thorin indicator.
Titrate with 0.01 N BaCl2 to
endpoint.*6
3 Determine total sulfur by
material balance. Determine
split between H2S and S02 by
gas chromatography.
4 Sulfur dioxide determined using
both a modified West-Gaeke
procedure and by gas chromatography.
The G-C column is 6" stainless
containing 1570 Yukon LB 550 x
on 60-80 mesh chromosorb P-AW-
BMCS. The column is operated
at 54° C using a helium carrier.
1 Collect in a series of 2
impingers containing a total of
200 ml. CdS04. Impingers follow
the S02 train described as me hod
1 above. The impingers are made
from 38 mm x 200 mm test tubes
with rubber stoppers and drawn
glass tubing. The impinger
contents are washed through a
tared filter crucible dryed
on a hotplate and heated for 2
hours in an oven at 550° C.
The crucible is cooled and weighed.
2 Two impingers containing a total
of 250 ml. 5% CdS04 are placed
behind the S02 impingers described
as method 2 above. Measure
volume of impinger contents and
add suitable aliquot of iodine
solution. Titrate excess iodine
with sodium thiosulfate solution
using a starch indicator.16
3 Determine total sulfur by material
balance. Determine split between
H2S and 862 by gas chromatography.
4 Hydrogen sulfide measured along
with S02 using gas chromatography.
The G-C column is 6' stainless
containing 15% Yukon LB550 x on
16
-------
CB-88
TABLE CB-16 (continued) Sheet 3 of 3
Component Method No. Procedure
60-80 mesh chromosorb P-AW-
BMCS. The column is operated
at 54° C using a helium
carrier.
Oxides of Nitrogen 1 Sample collected in a series of
2 impingers fabricated from 4 oz.
bottles with rubber stoppers and
drawn glass tubing. Each
impinger contains 50 ml. 3%
perox e solution. Collect a
suitable sample at 0.075 cfm.
Let stand overnight and analyze
using the phenoldisulfonic acid
technique described in "Atmospheric
Emissions from Sulfuric Acid
Manufacturing Processes".16
Particulates 1 Equipment and technique described
in Bulletin WP-50 17, Alundum
thimble filtration and isokinetic
sampling based on calculated
sampling rate.
2 Isokinetic sampling based on an
Alundum thimble and stainless
steel train. Western Precipitation
equipment implied. 17
-------
CB-89
XVII. Emergency Action Plan (EAP) For Air Pollution Episodes
A. Types of Episodes
Alleviation of Air Pollution Episodes as suggested by the U.S.
Environmental Protection Agency is based on a pre-planned 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 Emission
As outlined in the foregoing in-depth study of "Carbon Black Manufac-
ture by the Furnace Process" there are four continuous and two intermittent
vent streams to the atmosphere.
1. Continuous Streams
(a) Main Process Vent Gas - This consists of the gross
reactor effluent plus quench water after recovery of
carbon black product and represents the primary source
of emissions from the plant.
(b) Product Transport Vent - Some plants incorporate
pneumatic conveyors for moving product to the finishing
area. The carrier gas for this operation is vented to
the atmosphere after recovery of entrained carbon black.
(c) Drier Vent(s) - In most plants a major portion of the
hot gas employed in the product drying operation does
not come in contact with carbon black but is used as
an indirect heat source and, therefore, contains no
entrained carbon black. The only consequence of this
stream, with respect to atmosphered contaminates, is
due to the products of combustion from natural gas.
The remaining portion of the hot gas used in drying
and representing 35 to 70% of the total is charged
directly to the drier interior for removal of water
vapor. This latter stream will contain carbon
particles and is vented after passing through a filter
or water scrubber for particulate removal.
-------
CB-90
(d) Bagging and Storage Area Vent - Carbon black content
of this air stream varies depending upon specific
operations being performed in the storage area. The
emissions from this source could be significantly
reduced temporarily without a loss in production by
curtailing the bagging operation if adequate bulk
storage is available.
2. Intermittent Air Emissions
(a) Vacuum Clean-Up - The vacuum clean-up system is
usually in a standby condition with carbon black
only present in the exhaust stream when the system is
being used to clean-up carbon spills. However, in
some plants bagging and storage areas are an adjunct
of the clean-up system. In this case, some emissions
would always be present if the plant was in operation.
(b) Emergency Relief - It is assumed that this consists
of vent gas from pressure safety valves or expansion
discs and would occur very infrequently.
C. Abatement Techniques
As the various levels of the pre-planned episode reduction scheme
are declared (Alert, Warning and Emergency) a progressive reduction in
emissions of air pollutants must be made. This could ultimately lead
to total curtailment of pollutant emissions if the emergency level
becomes imminent. The extent of required cutback in emissions from
carbon black plants will depend on the relative amount of offending
constituents contributed by carbon black production to the overall
emissions which resulted in the pollution episode. This plus other
factors will be used by control authorities in determining the amount
of emissions to be tolerated during various episodes.
Carbon black manufacturing facilities generally consist of several
units with each unit being composed of two or more reactors attached to
a single collection system. This provides for a certain degree of flexi-
bility for a partial reduction in air pollutant emissions during an air
pollution alert. Several options are available to accomplish this reduction:
Option 1 - Ceasing production on one or more reactors of a given
unit and then placing these reactors on heating load by maintaining
air flow and using natural gas for temperature control.
Option 2 - Ceasing production on one or more entire units and
maintaining them on heating load.
Option 5 - A carbon black manufacturing plant has a certain
inherent inflexibility with respect to operating conditions,
with a delicate balance between operating variables and product
quality. However, a turndown of feed rate is possible in some
-------
CB-91
cases for a partial reduction in emissions. It has been reported
that atmospheric emissions from the various vent streams are
directly proportional to quantity of carbon black being produced.
Option 4 - If the contaminant producting the air pollution episode is
sulfur, the utilization of a lower sulfur content feedstock could
produce the desired reduction of pollutant.
In the case of Option 1, the curtailment of operation of one or
more reactors of a given unit must be considered with respect to
downstream emission. For example, in plants that employ thermal
incinerators of plume burners, removal of feed stock from one or
more reactors of a unit while maintaining these reactors on heating
load would decrease the amount of combustibles flowing to the
combustion device. Unless adequate supplemental fuel is available
to replace these combustibles, lower incineration temperature or
burner flame out could occur resulting in a net increase in emissions
from the operating units. An alternate to Option 1 would be to
either directly vent standby reactors to the atmosphere or to forego
the maintenance of these reactors on heating load. This latter
approach would result in an economic hardship since shutdown time
would be as much as three hours with several days required to heat
up and return these reactors to productive operation. Whereas to
place an operating reactor on hot standby operation requires about
one hour and to resume productive operation requires another two to
three hours.
In the case of Option 2, the same general comments outlined above
are applicable with respect to those plants containing combustion
devices as a control of emissions. The alternate in Option 2 would
be to forego the maintenance of the standby condition and accept the
resulting economic hardship.
The overall quantity of emissions produced depend on the type of
carbon black being manufactured. Soft black reactors produce approximately
one-half the emissions of a hard black producing reactor. Since most
plants produce both types of carbon black, the manufacturer has some
flexibility in determining which reactors or units are to be shutdown or
placed in standby in order to reduce emissions to prescribed levels.
Product recovery bag filters will remain in service during shut-
down and startup. Consequently, particulate emissions in the bag
filter effluent will not increase under these circumstances. Therefore,
the choice in operations outlined in Options 1 and 2 to effect a
partial reduction in atmospheric pollutants depends primarily on the
facilities that control the pollutants contained in the filter bag
effluent. In plants that send the bag filter effluent to an incinerator,
the alternates in Option 1 and 2 would be in force. This results in
reduced flow to the incinerator and, due to longer residence time,
will permit a reduction in furnace operating temperature. This in turn
should offset the tendency to form more NOx caused by the increased
residence time. However, it the incinerators include steam generation
facilities, it may be necessary to continue operation of this pollution
control system at normal levels during the alert utilizing additional
supplemental fuel.
-------
CB-92
Plants employing water scrubbers on the main process vent and/or
drier vent streams will continue to run this item at design water rates
during an alert. This should improve scrubbing efficiency over that
obtained at normal carbon black production levels.
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
by the Environmental Protection Authorities to reduce emissions
from carbon black manufacture by a small amount in order to deter
further increases in pollution level which could result in
warning or emergency episodes. This may be accomplished
by employing one of the foregoing options. The specific option
to be used for the reduction is at the discretion of the manufacturer.
The time required to affect the reduction will depend on the route
selected and will be approximately as stated in the preceding
discussion. This will reduce the principal source of emissions,
represented by the main process vent, to a value equivalent to the
reduction made in the producing units. The other sources of
emission, represented by the product transport vent (if pneumatic
conveyor), drier vents, bagging and storage vents and the vacuum
clean-up vent will be reduced to some degree by virtue of the
reduction made in the producing equipment. Usually the alert
condition can be expected to continue for 12 hours or more.
2. Declaration of Warning Condition - When the air pollution emergency
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 to 60 percent decrease in carbon black production.
3. Emergency Condition - When it appears that an air pollution
emergency episode is imminent, all air contaminants may have to
be eliminated immediately be ceasing production and allied
operations to the extent possible without causing injury to persons
or damage to equipment.
The cessation of operation of the producing units whether wholly
or in part will not result in increased emissions. This is also
true for startup operations since the principal pollution control
devices are in service during both operations.
D. Economic Considerations
The economic impact on carbon black manufacturers of curtailing
operations during any of the air pollution episodes is based on the
duration and number of episodes in a given period. It is indicated
that the normal duration of air pollution episodes is usually one to
seven days with meteorology episode potentials as high as 80 per year.19
The frequency of air pollution episodes in any given area 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 energency episodes. For the economic study, it has been
-------
CB-93
assumed that three warning and no emergency episodes occur during a
typical year. Each warning episode is assumed to require a 50 percent
reduction in air contaminants for a period of four days with an
additional day allocated to returning the plant to full capacity.
This then equates to a complete loss in plant production for about eight
and one-half days per year.
The financial impact resulting from this loss in production is shown
in Table CB-17. This table contains comparative manufacturing costs for
an existing 90 MM Ibs./year facility without extensive pollution control
(Table CB-11) and for a most feasible new facility of the same capacity
(Table CB-13). 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 proposed cutback in carbon black
production for emission control appears small (2.5 percent on a yearly
basis), it has a substantial influence on net profit (17.5 percent and
21.0 percent reduction respectively).
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
primarily predicated on existing plants which generally utilize bag filters
but do not have the more sophisticated pollution control equipment.
Special consideration should be made in the EAP for Air Pollution
Episode Avoidance for new and existing plants that employ incineration
control equipment on the bag filter effluent. The following presents
estimated 1985 air emissions for a typical present day system without
incineration and the most feasible new plant with this type of control.
Typical Present System Most Feasible New Plant
Average Emissions, Average Emissions,
Pollutant Tons/Ton Tons/Ton
Hydrocarbons + H2S 0.0513
Particulate 0.0027
NOX 0.0023 0.0042
SOX 0.0085 0.0307
CO 1.2907 —
Total Emissions 1.3555 0.0349
As noted in the above, total emissions for the most feasible new
plant has been reduced to one-fortieth of that estimated for the typical
present system without incineration. However, emissions of NOx and SOx
are substantially higher for the plant employing an incinerator.
-------
CB-94
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CB-96
The particular type and concentration of pollutants in the atmosphere
at the time of the episode would dictate the degree to which a reduction
would be made on the most feasible new plant. If NOx and/or SOx are the
offending material, then a reduction in plant production should be made as
outlined uncer "Abatement Techniques". In this case, SOx emissions would
be reduced in direct proportion to the reduction of carbon black production.
The NOx emissions would probably be reduced by a greater percentage
because of reduced furnace operating temperature.
If the offending pollutants are in the form of hydrocarbons,
paniculate or CO, less severe cutbacks in production need to be taken
on the declaration of warning condition.
-------
CB-97
References
1. Drogin, I. "Carbon Black," Journal of the Air Pollution Control
Association, vol. 18, 216-228, (April, 1968).
2. Adair, J. G. and Boots, H. L., "Control System for Bag Filters,"
U. S. Patent 3,630,004, December 28, 1971.
3. The Babcock & Welcox Company, "Steam, Its Generation and Use,"
George McKibbin & Sons, New York, 1937, pages 4-10.
4. Rolke, R. W. et al. "Afterburner Systems Study" by Shell Development
Company for Environmental Protection Agency (Contract EHSD 71*3).
5. Kirk - Othmer; "Encyclopedia of Chemical Technology", 2nd Edition,
Vol. 4 (1964) and supplement vol. (1971).
6. "Chemical Economics Handbook", Stanford Research Institute,
January, 1970.
7. "Background Information for Establishment of Standards of Air Pollution
Control in the Petrochemical Industry Benzene and Xylene Products
and Carbon Black," Processes Research Inc. for Environmental
Protection Agency (Task Order No. 14), August 13, 1971.
8. "Carbon Black Chemical Profile" Chemical Marketing Reporter,
February 15, 1971.
9. "Control Techniques for Nitrogen Oxide Emissions from Stationary
Sources", National Air Pollution Control Administration,Publication
No. AP-67, page 7-30.
10. Crynes, B. L. and Maddox, R. N., "Status of NO Control from Combustion
Sources", Chem Tech, pages 502-509, August, 1971.
11. Ross, R. D., Air Pollution and Industry, Van Nostrand Reinhold
Environmental Engineering Series, pages 319-337.
12. Sulfur Dioxide Scrubbers - Stone & Webster - Ionic Process, Bulletin
189377.
13. Ross, R. D., Air Pollution and Industry, Van Nostrand Reinhold
Environmental Engineering Series, pages 432-433.
14. NAPCA Publication AP-52,"control Techniques for Sulfur Oxide Air
Pollutants," January, 1969.
15. "Field Operations and Enforcement Manual for Air Pollution Control
Vol. II," Pacific Environmental Services, Inc. for Environmental
Protection Agency, Publication No. APTD-1101, August, 1972.
16. "Atmospheric Emissions from Sulfuric Acid Manufacturing Processes",
Public Health Service Publication No. 999-AP-13, 1965.
-------
CB-98
References
17. "Methods for Determination of Velocity, Volume Dust and Mist Content
of Gases", Bulletin WP-50, Western Precipitation Group, Joy Manu-
facturing Company.
18. "Standards of Performance for New Stationary Sources", Federal Register,
Vol. 36, No. 247, 24876-24895, December 23, 1971.
19. "Burning Low Colorific Gases", Hurley, E. G., Paper No. 15, Incineration
Conference, U. K. Institute of Fuel.
20. "Guide for Air Pollution Episode Avoidance", Environmental Protection
Agency, Office of Air Programs, Publication No. AP-76, 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 Disulfide
Cyclohexanone
Ethylene
Ethylene Bichloride (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 which is difficult if not
impossible to define because value judgements are 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.
2. The Sohio Process for producing Acrylonitrile.
3. The Oxychlorination Process for producing 1,2 Dichloroethane
(Ethylene Bichloride) from Ethylene.
-------
1-3
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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 m 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 II
Number of New Plants*
Attached Table 1 illustrates the format for this calculation.
Briefly, the procedure is as follovs:
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
periodo Their rankings, on an effect factor basis with carbon monoxide
arbitrarily used as a reference are as follows:
Babcock
Walther
Hydrocarbons
Particulates
NOX
SOX
CO
2.1
107
7709
28.1
1
Pr imary
125
21.5
22.4
15.3
1
Secondary
125
37.3
22.4
21.5
1
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
-------
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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-
20 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.
-------
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 nitrogen 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:
lo 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 was 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 > 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 of Emission Reduction Rating (SERR) (continued)
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Total
SERR = 8000 -
Weighting
Factor
80
60
40
20
1
958.5
Pounds in
Actual Weighted
100 8000
0
0
0
0
8000
Pounds out
Actual Weighted
0
14.2 852
1 40
0
66.5 66.5
958.5
8000 x 1UU ~ 00/°
Example 2 - The same as Example 1, except the hydrocarbons are
burned to completion. Then,
CCR = 342
342
x 100 = 100%
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 CHjCl + 3 02
2 C02 + 2 H20 + 2 HC1
This is complete combustion, by definition, therefore, the CCR is
10070. However, (assuming no oxides of nitrogen are formed), the SERR
is less than 100% because 72.5 Ibs. of HC1 are formed. Hence,
considering HC1 as an aerosol or particulate;
SERR = 100 x 80 - 72.5 x 60
100 x 80
x 100 = 45.5%
The conclusion from this final example, of course, is that it is
an excellent combustion device but a very poor pollution control device,
unless it is followed by an efficient scrubber for HC1 removal.
Example 4 - The stacks of two hydrogen cyanide incinerators, each
burning 100 pounds per unit time of HCN are sampled. Neither has any
carbon monoxide or particulate in the effluent. However, the first is
producing one pound of NOX and the second is producing ten pounds of
NOX in the same unit time. The assumed reactions are:
-------
III-4
Efficiency of Pollution Control Devices
2. Significance of Emission Reduction Rating (SERB.) (continued)
4 HCN + 5 02 ' ' fr 2 H20 + 4 C02 + 2 N2
N2 (atmospheric) + X02 V 2 NOX
Thus, CCRi = 1007o and CCR2 = 100% both by definition.
However, SERRi = 100 x 80 - 1 x 40 mn - QQ •;<•/
100 x 80 X I0° ~ 99'5/°
and SERR9 = 100 x 80 - 10 x 40
2 100 x 80 x 10° = 95/°
Obviously, if either of these were "smoky" then both the CCR and
the SERR would be lower, as in Example 1.
Cither 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
997, 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 + 7» 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 , .-.
—c ~. TT^ :—c 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.
-------
IU-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 Ibs0 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,
and SERR = (100 x 60 + 10 x 20 + 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 S02 per unit time. All
but one pound of the S02 is removed but two pounds of
the hydrocarbon evaporate into the vented stream. Then
SE
and SERR = (50 x 20) - (1 x 20 + 2 x 80)
(50 x 20)
x 10°
= 1000 - 180
1000
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 , REPORT NO.
EPA-450/3-73-006-a
3. RECIPIENT'S ACCESSION NO.
4, TITLE AND SUBTITLE
Engineering and Cost Study of Air Pollution Control
for the Petrochemical Industry, Volume 1: Carbon Blacke
Manufacture by the Furnace Process
5. REPORT DATE
June 1974
>. 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.O. Box 427
Marcus Hook, Pennsylvania 19061
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-0255
12 SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
EPA, Office of Air Quality Planning & Standards
Industrial Studies Branch
Research Triangle Park, N.C. 27711
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-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).
This volume covers the manufacture of carbon black by the furnace process.
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 Black
Carbon Monoxide
Hydrocarbons
Hydrogen sulfide
b.IDENTIFIERS/OPEN ENDED TERMS
Petrochemical Industry
Particulates
c. COSATI Held/Group
7A
7B
7C
11G
13B
13H
13 DISTR BUTION STATEMENT
19. SECURITY CLASS (This Report)
Unclassified
21 NO OF PAGES
127
20 SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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17. KEY WORDS AND DOCUMENT ANALYSIS
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