EPA-450/3-73 -006-e
ENGINEERING
AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE
PETROCHEMICAL INDUSTRY
VOLUME 5: FORMALDEHYDE
MANUFACTURE
WITH THE MIXED
OXIDE CATALYST PROCESS
by
R . B . Morris , F . B . Iliggins , Jr . ,
J. A. Lee, R. Newirlh, and J. W. Pervier
Iloudry Division
Air Products and Chemicals, Inc.
P.O. Box 427
Marcus Hook, Pennsylvania 19061
Contract No. 68-02-0255
EPA Project Officer: Leslie B . Evans
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, N. C. 27711

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This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers. Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - as supplies permit - from the Air
Pollution Technical Information Center, Environmental Protection Agency,
Research Triangle Park, North Carolina 27711; or, for a fee, from the
National Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia 22161.
This report was furnished to the Environmental Protection Agency by
the Iloudry Division of Air Products and Chemicals, Inc. , in fulfillment
of Contract No. 68-02-0255. The contents of this report are reproduced
herein as received from the Houdry Division of Air Products and Chemicals,
Inc. The opinions, findings, and conclusions expressed are those
of the author and not necessarily those of the Environmental Protection
Agency. Mention of company or product names is not to be considered
as an endorsement by the Environmental Protection Agency.
Publication No. EPA-450/3-73-006-C
ii

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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
Engineerine 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, aerylonitrile,
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 formaldehyde. Had
their inputs been withheld, or valueless, the study would not have been
possible or at least not as extensive as here reported. Hence, Air Products
wishes to acknowledge this cooperation by listing the contributing companies.
Allied Chemical Corporation
Borden Chemical Company
Celanese Corporation
E. I. duPont deNemours & Company
GAF Corporation
Georgia Pacific Corporation
Gulf Oil Corporation
HercuLes, Inc.
Hooker Chemical Company
Monsanto Company
Reichhold Chemical Company
Tenneco Chemical Company
Wright Chemical Company
Additionally, Air Products wishes to acknowledge the cooperation of the
member companies of the U. S. Petrochemical Industry and the Manufacturing
Chemists Association for their participation in the pubLic review of an
early draft of this document. More specifically, the individuals who served
on the EPA's Industry Advisory Committee are to be commended for their advice
and guidance at these public meetings.

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TABLE OF CONTENTS
S ection
Summary
I.	Introduction
II.	Process Description and Typical Material Balance
III.	Manufacturing Plants and Emissions
IV.	Emission Control Devices and Systems
V.	National Emission Inventory
VI.	Ground Level Air Quality Determination
VII.	Cost Effectiveness of Controls
VIII.	Source Testing
IX.	Industry Grovth Projection
X.	Plant Inspection Procedures
XI.	Financial Impact
XII.	Cost to Industry
XIII.	Emission Control Deficiencies
XIV.	Research and Development Needs
XV.	Research and Development Programs
XVI.	Sampling, Monitoring and Analytical Methods for
Pollutants in Air Emissions
XVII.	Emergency Action Plan for Air Pollution Episodes
References
Appendix I
Appendix II
Appendix III
Page Number
i
FM-1
FM-2
FM-8
FM-16
FM-2 2
FM-2 3
FM-24
FM-2 7
FM-2 8
FM-30
FM-32
FM-37
FM-39
FM-41
FM-42
FM-45
FM-47
FM-54
I-1
II-l
III-l

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LIST OF ILLUSTRATIONS
Figure No.	Title	Page Number
Figure FM-1	Simplified Flow Diagram	FM-4
Figure FM-2	Formaldehyde Production - Capacity Projection	FM-29
LIST OF TABLES
Table No.	Title	Page Number
Table FM-1	Typical Material Balance - Lbs.	FM-5
FM-2	Typical Material Balance - Ton/Ton	FM-6
FM-3	Formaldehyde Converter Section Heat Balance	FM-7
FM-4	Tabulation of U.S. Formaldehyde Plants (2 pages) FM-9
FM-5	Survey of U.S. Formaldehyde Plants and
Atmospheric Emissions Mixed Oxide Process
(2 pages)	FM-11
FM-6	Typical Absorber Vent Gas Composition	FM-13
FM-7	Catalog of Emission Control Devices	FM-17
FM-8	Thermal Incinerator Emission Control System	FM-18
FM-9	Catalytic Incinerator Emission Control System	FM-20
FM-10	Water Scrubber Emission Control System	FM-21
FM-11	Cost Effectiveness for Alternate Emission
Control Devices	FM-25
FM-12 Formaldehyde Manufacturing Costs for a Typical
Existing 100 MM Lbs./Yr. Facility	FM-33
FM-13 Formaldehyde Manufacturing Costs for an Existing
or New 100 MM Lbs./Yr. Facility with
Incineration	FM-34
FM-14	Proforma Balance Sheet	FM-35
FM-15	Estimated 1985 Air Emissions for Alternate
Control Systems	FM-38
FM-16	Detailed Costs for R&D Project	FM-44
FM-17	Summary of Sampling and Analytical Methods
Reported for Pollutants	FM-46
FM-18 Financial Impact of Air Pollution Episodes
on Manufacturing Costs (2 pages)	FM-52

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SUMMARY
The formaldehyde 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 there are two basic processes for the production
of formaldehyde. They both utilize methanol as a raw material in an air
oxidation process. Neither appears to have any significant advantage which
would alter its relative growth rate. A third process, utilizing partial
oxidation of light hydrocarbons to produce formaldehyde appears to be
obsolete. The principal differences between the two methanol based processes
are the catalyst and the methanol/air ratio. The subject of this report is
the process utilizing a mixed metal oxide catalyst and a methanol lean feed
mixture with air. A separate study devotes itself to the other process which
uBes a silver catalyst and a methanol rich feed mixture with air. (Report
Number EPA-450/3-73-006d.)
In general terms, the air emissions from the mixed oxide catalyst process
fall into the categories of hydrocarbons (formaldehyde, dimethyl ether and
methanol) and carbon monoxide. As practiced today, virtually no oxides of
nitrogen, oxides of sulfur or particulates are emitted from the process. The
process is currently undergoing rather intensive study of techniques for
recycling the main vent stream thus reducing emissions and improving processing
efficiency. This fact makes it difficult to estimate an emission factor for
the process but it probably falls in the range between 0,02 and 0.04 lbs./lb.
of 377„ formaldehyde produced for recycle and non-recycle operation, respectively.
Of these totals, carbon monoxide account for about 0.016 lbs./lb. of 377„
formaldehyde, regardless of the recycling operation. The balance is hydrocarbon
emission, about half of which is formaldehyde and one-third dimethyl ether from
a non-recycle operation. However, from a recycle operation formaldehyde and
dimethyl ether each account for less than one-fourth of the total hydrocarbon
emission factor. Based on an approximate median between these extremes it
has been estimated that the process emitted about 25 million pounds of
hydrocarbons and about 25 million pounds of carbon monoxide into the atmosphere
in 1973. If all future mixed oxide process plants are built to incorporate
the best present day recycling techniques, it has been estimated that the
hydrocarbon emission will increase to just over 32 million pounds per year and
the carbon monoxide emissions to about 55 million pounds per year by 1985.
Formaldehyde is normally marketed as a 37-517= water solution. Therefore,
all plants have a water scrubber (absorber) on the main process stream before
it is vented to the atmosphere (or recycled). Most plants also have a mist
eliminator on this stream to minimize the entrainment of water from the
absorber. Only one of the plants surveyed has any further emission control
equipment and that is an additional water scrubber. It is quite efficient
with respect to methanol and formaldehyde but because of the low water solubility
of carbon monoxide and dimethyl ether, it does little toward reducing these
emissions. Furthermore, it is expensive to install, especially on existing
plants and merely transfers a portion of the emission problem from air to
water. Consequently, water scrubbing was not adjudged to be the "most feasible"
method of emission control although it could certainly be argued that it is the
"best demonstrated" technique. However, the available data seem to indicate
that the best recycle operations do nearly as well as water scrubbing with

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SUMMARY (continued)
respect to air emissions at a lower cost, without transferring the problem to
another medium and are thus the best demonstrated technique. The conclusion is
evidenced above by the forecast of only a little over seven million pounds
per year increase in hydrocarbon emissions by 1985 if recycling operations are
employed on all new plants. The major unanswered question is whether or not
recycling can be economically incorporated into those existing plants that
do not currently operate in this manner.
Since none of the demonstrated techniques reduce carbon monoxide emissions
and since uncertainty exists about the universal applicability of recycling
techniques, incineration techniques were also studied. It was concluded that
though not demonstrated, a thermal incinerator on every existing and new plant
would reduce the process emission factor to about 0.001 pounds per pound of
37% formaldehyde which would result in just over three million pounds per year
of atmospheric emissions by 1985. This would not cause a significant economic
burden for the industry, because at 1973 prices, these incinerators, whether
applied to either existing or new model plants of 100 MM lbs./year capacity
would cost only about $54,000 each. However, at 1973 fuel prices, this results
in nearly $40,000 per plant in total annual operating cost besides being
wasteful of fuel. The addition of a heat recovery system on thie incinerator
can not be economically justified at 1973 prices even though it would reduce
the fuel consumption by about 40 percent. In terms of total industry figures,
incinerators without heat recovery would cost about $1,000,000 for existing
plants plus an additional $1,000,000 by 1985 (all at 1973 prices) for all new
plants. However, this would result in the consumption of about 650 million
SCF of natural gas per year by 1985 to achieve an estimated reduction in
emissions of 55 million pounds per year of carbon monoxide and 30 million
pounds per year of hydrocarbon. In addition, the use of incineration techniques
will probably result in the formation of some oxides of nitrogen from the
nitrogen present in the normal vent gas.
From the foregoing, it would appear that the major research effort that
the formaldehyde industry should make is in the area of improvements in
catalysts and improvements in recycle techniques (perhaps through the injection
of oxygen to reduce nitrogen recycle). If these types of research can achieve
universal applicability of recycle operations along with a reduction in carbon
monoxide emissions, it would appear that little or no further air emission
control would be required for those producers using the mixed oxide process for
formaldehyde production.

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FM-1
I. Introduct ion
Formaldehyde was first produced in the u. S. in 1901, at that time its
chief use vas as an embalming agent and disinfectant. Today, 6ome seventy
odd years later production capacity exceedp seven and one half billion
pounds per year,
(5)
vith approximately tvo thirds of the production utilized
in the formulation of various synthetic resins.
Formaldehyde is normally marketed in aqueous solutions containing from
36 to 50 weight percent formaldehyde. The standard CUSP) solution is 37
percent, although large scale industrial users prefer a nominal 50 percent
solution. Formaldehyde solutions usually contain sufficient methanol to
prevent precipitation of polymer during storage and shipping, although
precipitation may be prevented in solutions containing relatively small
amounts of methanol by keeping the solution warm.
Formaldehyde is produced principally from methanol. Tvo processes are
dominant in the U. S. today, the mixed oxide catalyzed process and the silver
crystal (or gauze) catalyzed process.
The primary licensors of the mixed oxide process are Reichhold and Lummus,
while ICI and Borden prevail in the licensing of the silver process. The mixed
oxide catalyzed process is the subject of this report.
A third process, based on the partial oxidation of light hydrocarbons,
had been utilized by Celanese at their large Pishop, Texas plant until ouite
recently. That particular facility at Bishop has nov been shutdovn and
replaced by a silver process unit. Vith national energy source demands
escalating feedstock costs for the partial oxidation process, it is
extremely doubtful that any nev facility in the U. S. vill again employ this
proces s.
Atmospheric emissions generated by the mixed oxide catalyst process are
associated primarily vith the absorber vent gas stream. Minor ouantities of
hydrocarbons may be discharged from various other sources. Additionally,
small ouantities of vaste vater may be produced.
Today an estimated 23% of U. S. formaldehyde capacity is based on the mixed
oxide catalyst process. If this process can maintain its present share of the
total formaldehyde capacity, it will expand to 3.5 x 10^ lbs./year in 1985, from
its present 1.73 x 10^ lbs./year.

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FM-2
Process Description
A.	Chemistry
The chemistry of the formation of formaldehyde from methanol, via
the mixed (metal) oxide catalyst process may be shovn as follows:
CH3OH + \ 02 	V- CH20 4- H20 + 38 Kcal.
This differs from the classical silver-catalyzed process in that
(apparently) no hydrogen is produced, and the methanol molecule itself,
rather than the produced hydrogen, is oxidized.
Methanol is mixed with a combination of air and recycle vent gas
and then heated to between 220 and 350° F in a steam jacketed vaporizer.
The air/recycle gas mixture will normally contain about 107- (vol.) oxyge
but always less than 10.97,. The methanol will normally comprise about
9.57, (vol.) of the total converter feed, although it is limited to
about 77. for non-recycle operations. (See Figure FM-1)
The super-heated vapors from the vaporizer pass into the converter,
where the oxidation reaction takes place, in a multiplicity of tubes
filled with a mixed oxide catalystjbatween 650° F and 800° F. The heat
of reaction is removed by the circulating Dovtherm fluid surrounding
the catalyst tubes and is used to produce steam. The converter effluent
gases are cooled from approximately 500° F to about ?20° F in a heat
exchanger prior to being quenched to near 100° F in the absorber.
The absorber consists of a bubble cap column which may have two
water-cooled heat exchangers in the upper portion. The converter
effluent vapors are introduced into the bottom section of the column
and flow counter-current to the dilution/scrubbing water, which is
pumped onto the top tray and flow6 downward through the tower. The
formaldehyde vapors are absorbed by the water, forming a 37 to 537,
solution. This exits from the bottom of the tower. The non-condensible
are vented from the top of the absorber where part is recycled and part
goes directly to the atmosphere.
B.	Recycle Operation
/ 1 Q \
In 1948, du Pont discovered	that if the volume percent of oxygen
in the gas employed for the oxidation (i.e., air plus recycle gas) of
methanol is held below 10.9 vol. 7„, then no explosion will occur no
matter how much methanol is added to the mixture. This condition is
most easily effected by recycling and mixing the relatively oxygen poor
absorber vent gases with the fresh charge air prior to their admixture
with the methanol. The advantages resulting from this type of operation
are as follows:
(1)	Increased capacity.
(2)	Higher yield.
(3)	Increased safety.
(4*1 Lover emissions.
Today nearly all mixed-oxide catalyst plants utilize this mode of
operat ion.

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FM-3
C. Material Balance
Table FM-1 presents a typical material balance for mixed oxide
catalyst process formaldehyde production. Absorber vent gas composition
is based on data furnished by questionnaire respondents-at vhat are
presumed to be typical vent gas recycle rates. Yields, etc., are
based on a combination of questionnaire and published data and are
shown below:
Mole %
Total Converter Feed
Methanol	/v10
Oxygen	^.10.9
Recycle Gas
Ratio	Not Specified
Oxygen	8
Methanol Conversion	98
Formaldehyde Yield	94
Table FM-1 material balance relates to an average size plant <"100
MM lbs./year of 37% formaldehyde"). This typical unit will be used in
economic studies discussed later in this report. Table FM-2 presents
the same material balance with quantities expressed as tons per ton of
3 7% formaldehyde.
Table FM-3 presents an estimated heat balance around the converter
section.

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TABLE FM-1
TYPICAL MATERIAL BALANCE FOR
MIXED OXIDE CATALYST PROCESS FORMALDEHYDE PLANT
PRODUCING 100 MM LBS./YR. OF 377. FORMALDEHYDE
Fresh
Feed
Recycle
Absorber
Gas
Total
Feed
Absorber
'Make-Up1
Water
Absorber
Vent Gas
Absorber
Bottoms
(Product)*
Stream I. D.
Formaldehyde
Methanol
Dimethyl Ether
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Water
Total - Lbs./Hr.
B
5,121
12,994
3,944
7
22,066
TJ
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3.3
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5,156
5,156
5
21
10
12,994
1,336
22
151
429
14,968
4,534
61
7,660
12,255
Ln
*May include small amount of formic acid.
**% recycle (P.R.) - moles of recycle	 x 1Q0 (normal range - 0 to 90%)
moles of recycle + moles of vent

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TABLE FM-2
TYPICAL MATERIAL BALANCE FOR
MIXED OXIDE CATALYST PROCESS FORMALDEHYDE PLANT
UNITS - TON/TON OF 377= FORMALDEHYDE
Fresh
Feed
Recycle
Absorber
Gas
Total
Feed
Absorber
Make-Up
Water
Absorber
Vent Gas
Absorber
Bottoms
(Product)*
Stream I. D.
Formaldehyde
Methanol
Dimethyl Ether
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Water
Total
B
D
.4179
1.0603
.3218
.0006
1.8006
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*May include 6mall amount of formic acid.
**% recycle (P.R.) ¦ moles of recycle
x

c
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FM-7
TABLE FM-3
FORMALDEHYDE PRODUCTION
VIA
MIXED OXIDE CATALYST PROCESS
GROSS HEAT BALANCE - CONVERTER SECTION ONLY ('1)
Heat In	BTU/Lb. of 37% HCHO
Charge vaporizer/heater	558
Exothermic heat of reaction	878
Total 1436
Heat Out
Converter temperature control ^
After cooler (3)
Quench and residual enthalpy (4)
Total 1436
700
336
400
NOTES;
(1)	Based on Table FM"-2 Material Balance.
(2)	Converter maximum temperature (a 750° F and outlet (9 500° F.
(3)	Outlet @ 200° F.
(4)	Base temperature is 60° F.

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FM-8
III. Manufacturing Plants and Emissions
Table FM-4 presents a list of U. S. plants producing formaldehyde.
Production via the mixed oxide catalyst process is used by nine producers in
a total of eighteen different plants. The greatest number of plants (eight),
are located in the Southeast. Five are located in the Pacific Northwest,
three in Nev Jersey and one each in Ohio and Texas. The plants range in
capacity from 40 to 160 MM lbs./year of 37% formaldehyde.
Table FM-5 shows individual plant capacity figures and atmospheric
emission data for the various formaldehyde plants surveyed in this study.
The plants in the tabulation include both the smallest and largest plants
currently on-stream, and represent 407- of the total U. S. installed mixed
oxide catalyst process capacity. Emissions from these plants are reported to
be as follows:
A. Continuous Air Emissions
1. Absorber Vent
The emissions from this vent constitute the primary source of air
pollution associated with the production of formaldehyde. Indeed,
one respondent reports it as the sole source of his emissions.
The composition of the absorber vent gas stream is dependent
on many variables, some of which are;
(a)	Recycle ratio.
(b)	Strength of formaldehyde produced.
(c)	Catalyst formulation.
(d)	Catalyst age.
(e)	Absorber temperature.
The variable which probably has the single greatest effect on
emissions is the gas recycle ratio. The importance of this parameter
may be seen in the following comparison of absorber vent gas
composition for recycle (a) and non-recycle operations:
EmissionsLb./Lb. of 37% HCHO
Components
Recycle
Operation (b-)
Non-Recycle
Operation (
Nitrogen
1.1735

4.2918

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TABLE FM-4
SUMMARY OF U. S. FORMALDEHYDE PLANTS ' Sheet 1 of 2
NOTE; The following tabulation of formaldehyde producers indicates published
production capacity (MM lbs./year) by company, location and process. Deter-
mination of the process utilized was by combination of published information,
questionnaire responses and private communications.
Company
Allied
Location
Ironton, Ohio
Silver
Process
308
Metal Oxide
Process
Borden
Demopolis, Ala.
Diboll, Texas
Fayetteville, N. C.
Fremont, Calif.
Kent, Wash.
La Grande, Oregon
Louisville, Ky.
Missoula, Mont.
Sheboygan, Wise.
Springfield. Oregon
80
70
200
80
70
40
70
80
120
260
Celanese
Bishop, Texas
Newark, N. J.
Rock Hill, S. C.
1300
117
117
Commercial Solvents
Sterlington, La.
Seiple, Pa.
30
80
Du Pont
Belle, W. Va.
Grasselli, N. J.
Healing Spring, N.
La Porte, Texas
Toledo, Ohio
Linden, N. J.
485
150
200
200
320
150
GAF
Georgia Pacific
Calvert City, Ky.
Columbus, Ohio
Coos Bay, Oregon
Crosett, Ark.
Albany, Oregon
Taylorsvilie. Miss.
Vienna, Ga.
100
100
100
100
80
60
100
100
Gulf
Hercules
Vicksburg, Miss.
Louisiana, Mo.
Wilmington, N. C.
170
95
40
Hooker
Monsanto
N. Tonawanda, N. Y.
Alvin, Texas
Addyston, Ohio
Eugene, Oregon
Springfield, Ma9s.
135
150
110
100
280

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FM-10
Company
Reichhold
Rohm & Haas
Skelly
Tenneco
Union Carbide
Wright
TABLE FM-4 CONTINUED
SUMMARY OF U.S. FORMALDEHYDE PLANTS
Location
Hampton, S.C.
Houston, Texas
Moncure, N.C.
Tacoma, Wash.
Tuscaloosa, Ala.
Kansas City, Kansas
White City, Oregon
Malvern, Ark.
Philadelphia, Pa.
Springfield, Oregon
Winfield, La.
Fords, N.J.
Garfield, N.J.
Silver
Process
36
70
40
25
105
105
Bound Brook, N.J.
Acme, N.C.		
Total Process Capacity - MM Lbs./Year = 5,914
Number of Plants	= 35
Average Plant Size - MM Lbs./Year	= 169
Capacity of Total Industry - MM Lbs./Year	»
Percent of Total Industry Capacity	= 77.4
Sheet 2 of 2
Metal Oxide
Process
100
100
40
7,643
50
100
70
70
160
150
75
1,729*
19
91
22.6
*Most recent total reported

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TABLE KM-5
NATIONAL EMISSIONS INVENTORY
FOR
FORMALDEHYDE PRODUCTION
VIA
MIXED OXIDE CATALYST PROCESS
Page 1 of 2
Plant EPA Code No.
Capacity - Tons of 377, Formaldeliyde/Yr.
Range In Production - */. of Max.
Emissions to Atmosphere
Stream
U-l
30,000
0
Absorber Vent
Dovtherm Vent
14-16
20,000
IB.5
14-17
50,000
33.3
Absorber Vent
Tank Vent
Compressor Exhaust	Absorber Vent
Flov - Lbs./Hr.
Flov Characteristic, Continuous or Intermittent
if Intermittent - Hrs./Yr. Klov
Composition, Tons/Ton of 37Z Formaldehyde
Methanol
Formaldehyde
Dlmethylether
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Hater
Dovtherm
Catalyst Dust
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
SCFH/Stack
Emission Control Devices
Incinerator
Scrubber
Other
Ana lysis
Data or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Sumry of Air Pollutants fT/T o£ 37*i HCH0)
Hydrocarbons
Aerosols & Particulates
N°*
so*
CO
Type of Operation - Recycle CR) or Non-Recycle (N.R.)
Not Specified
Continuous
Not Specified
Yes
1
49
131
None
Never
None
Design Values
No
Cannot be determined
27,619
Continuous
|.01630
4.29180
1.07720
)
"Very Small"
)"
01S20
.12030
Yes
1
60
24
70-95
6000-8000
N.R.
Infrequent
At Stack
GLC and Design
Yea	Yea
> .01630
+
+
N.R.
Yes
1
49.5
6
<150
Unknown
None
Never
Not Specified
Intermittent?
Yes
1
20
B
210
None
Never
Hot Specified
Continuous
Yes
1
7)
30
50-55
Yes (FM-1)
Hist Ellm.
Never
No
Cannot be determined -
A

-------
Plant EPA Codt No.
Capacity - Tons of 377. FormaIdehyde/Yr.
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent - Hre./Yr. Flov
Composition, Tons/Ton of 377® Formaldehyde
Methanol
Formaldehyde
Dlnethylether
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Water
Dovtheru
Catalyst Dust
Vent Stacks
Nuofcer
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
SCFH/S tack.
Emission Control Devices
Incinerator
Scrubber
Other
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Su»ary of Air Pollutants (T/T of 37% HCHO)
Hydrocarbons
Aerosols & Particulates
SO,
CO
Type of Operation - Recycle (R) or Non-RecycLe (NR.)
TABLE FM-5
mnim emission?; inventory
FOR
FORMALDEHYDE PRODUCTION
VIA
MIXED OXIDE CATALYST PROCESS
Pa^e 2 of 2
14-19
49,500
0
14-21 and/or 14-23 ( 5
50,000 3
0
14-22
50,000
0
Absorber Vent
Tank Vent
Absorber Vent
Dovtherm Vent
Converter Cat.
Actlv. Vent
Absorber Vent
73,078
Continuous
0.07
Continuous
17.583
Continuous
Continuous
Intermittent
14,000
Continuous
.00055
.00026
.00692
)
) 6.21413
)
C. 00001
.00167
.00047
.00084
1.35081
.10*12
.00177
.01228
+
+
+
TR
.00224
.00112
.99624
.07728
.02160
.03752
Yes
1
85
24
80
16,000
Yes (FM-2)
Yes
1
8
4
100
1.7
Yes
(FM-3)
Yes
1
74
30
80
3932
None
Yes
1
40
I
80
"Nil"
None
+
Yes
1
42
14
100-700
8000
None
Yes
1
10
14
92
3199
Yes (FH-4)
10 times (1969)
At Stack
GLC
No
Never
Calc'd.
No
Newer
Calc'd.
No
Never
Never
No
Denlster
Twice
Data ex design
No
.00773
.00298
+
.00336
N.R.
.01228
R
.02160
(1) questionnaire responses from plants 14-21 and 14-23 vere Identical.
"V

-------
TABLE FM-6
typical absorber vent gas composition
FOR
100 MM LB./YR. (1) FORMALDEHYDE PLANT

MIXED
OXIDE CATALYST PROCESS


Normal
Range in Composition


Non-Recycle

Typical Flov Rate & Composition

Operation
Recycle Operation
Recycle Operation
Component
Vol. 7o (2)
Vol. % (3)
MPH LB./HR.
Formaldehyde
.01 to 1.0
.03 to .15
0.2 5
Methanol
0 to . 7
.05 to .2
0.6 21
Dimethyl Ether
.05 to 2.5
0 to .53
0.2 10
Oxygen
18.5 to 19.6
5.3 to 18.1
41.7 1336
Nitrogen
75.1 to 77.0
73.9 to 89.2 (4)
463.7 12994
Carbon Dioxide ^

.03 to .09
0.5 22
Carbon MonoxideJ
2.2 to .4
.28 to 1.9
5.4 151
Water
0.7 to 2.24 (4)
5.1
23.8 429
Totals


536.1 14968
NOTES:
(1)	Of 37% formaldehyde.
(2)	Basis - questionnaire 14-16, 14-19, 14-22.
(3)	Basis - questionnaires 14-23, 14-21.
(4)	Calculated by difference.

-------
FM-14
2.	Dowtherm System Vent
Respondents 14-21 and 14-23 report emitting small quantities
of Dowtherm vapors to the atmosphere. The quantities are stated to
be less than one CFM (which on a lb./lb. basis is ^.0020) and
normally nil. Respondent 14-2 depicts a similar vent on his flov
sheet, but gives no further information. It is believed that most
operators maintain similar vents and that at least some of the
vent systems include vacuum ejectors. A summary of these data are
shown in Table FM-5.
3.	Storage Tank Vents
Three of the seven questionnaire respondents report the employment
of control devices on at least some of their storage tanks. The
majority of the storage tanks associated with the respondents's
formaldehyde facilities, however, vent directly to the atmosphere.
Never-the-less, emissions from this source are quite low. The
operator of plant 14-22 estimates that the emissions from his
storage tanks, which employ no vapor conservation devices, total
.04 SCFM. Calculated as methanol this amounts to approximately
.00002 lbs./lb. of 37% formaldehyde.
B.	Intermittent Air Emissions
1.	Catalyst Activation Vent
Plants 14-21 and 14-23 report a catalyst activation procedure
which results in venting relatively large quantities of N2> O2 and
CO2 to the atmosphere about once a year. (Probably for a period
of about 24 hours.) These gases may contain trace amounts of
ammonium chloride and catalyst dust. However, due to the infrequency
of the operation and the low concentration of contaminants, pollution
from this source would appear to be negligible. Presumably all
operators employ similar procedures.
2.	Compressor "Exhaust"
The operator of plant 14-17 is the only respondent reporting
atmospheric emissions from this source. The purpose of the vent
is not readily apparent nor is it quite clear whether or not there
is a continuous discharge from this point. The operator states
"normal composition is nearly 1007„ CO, air and H20. During upset
conditions, which may last for 20 - 30 minutes, contaminants may
leave this source". It would appear from the flow diagram that,
for practical purposes, this stream could be considered as part of
the absorber vent stream. Other details are summarized in Table FM-5.
C.	Continuous Liquid Wastes
The production of various waste water streams has been reported
as follows:
Plant 14-2 - "steam drum water".

-------
FM-15
Plant 14-16 - 8,000 gallons of vaste vater per day delivered to
city sever.
Plant 14-17 - 1.1 x 10& GPD cooling water circulated with discharge
(quantity unspecified) treated on-site.
Plant 14-19 - 2,000 GPH of vaste vater neutralized and solids
removed prior to discharge to county sevage
treatment plant.
Plant 14-21 and 14-23 - Both report producing and treating 14,546
gallons of waste vater per day (each).
This contains: 260 to 550 lb,/day HCHO
855 lb./day Na2 C03
285 lb./day CHOOH as sodium salt
Plant 14-22 - Reports no vaste water.
D. Intermittent Liquid Wastes
No intermittent liquid vastes were reported. It must be
assumed, therefore, that the vaste liquid stream produced during
the regeneration of the ion exchanger resins is included in the
report of total liquid vastes. This assumption is corroborated, in
part, by the indicated contained salts in plante 14-21 and 14-23
waste water (see above).
G. Solid Wastes
With the exception of one plant, all questionnaire respondents
report no solid vaste production. Plant 14-16 reports "theoretically
no solid material is produced. Actually solid paraformaldehyde, must
sometimes be cleaned from absorber sump and tank bottoms. In the last year,
an estimated 40,000 lbs. has been flushed to sludge pond on company
property vhere it has been biodegraded. Planned improvements should
drastically reduce amount of para formed".
F. Odors
Of the seven questionnaire respondents, tvo (plants 14-16 and
14-17) reported having received a community odor complaint vithin the
past year. All other plants reported detecting odors (usually
formaldehyde), at least occasionally, on-site.
G. Fugitive Emissions
Three plants offered estimates of fugitive emissions (generally
exclusive of tank vents, which were reported separately). They are;
Plant
Fugitive Emissions
Lb./Lb. of 37% HCHO
14-17
14-21
14-23
.001
.0005
.0005

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FM-16
Emission Control Devices and Systems
A.	Overview
The industry-wide acceptance and utilization of vent gas recycling
techniques has resulted in a major reduction (see Section III-A) of
typical mixed oxide plant emissions. The ensuing discussion of control
devices is based on the assumption that these devices will augment that
reduction in emissions. In practice, the devices will most probably
be more beneficial during those periods when the plant is in a non-
recycle mode or has not yet achieved optimum recycle conditions. However,
for the purpose of this report, device sizing, costing, associated material
balances, etc., will relate to emission control devices designed primarily
for normal recycle conditions.
B.	Devices Currently Employed
It would appear that - based on the information supplied in the
returned questionnaires - the majority of U.S. plants do not employ emission
control devices. Plants 14-17 and 14-22 both reported the use of mist
eliminators in the topB of their absorbers. Sufficient data to estimate
the efficiency of these devices were lacking. (See Table FM-7)
The only major emission control Bystem reported is respondent 14-19's
water scrubbing facility. Both absorber vent gases and storage tank vents
are water scrubbed prior to discharge to the atmosphere. The indicated
efficiency of the absorber scrubber is 66 to 67%, whereas the tank vent
device i6 estimated to be about 99% efficient. (The difference in efficiency
being due to the presence of the dimethyl ether in the absorber vent gas
stream, which, relative to formaldehyde and methanol, is water insoluble.)
C.	Feasible Devices - Not Currently Employed
1. Combustion Devices
With few exceptions, the devices that are most efficient in removing
carbon monoxide and contained hydrocarbons from the typical formaldehyde
vent stream shown in Table FM-6, are those utilizing combustion. For the
subject process, for these devices, investment costs are lower and
operating costs higher than for other devices evaluated. The relatively
high operating costs are attributable to the fact that supplemental fuel
must be provided to support combustion since the heat available from the
combustion of the contained pollutants is less than one MM BTU/Hr.
(a) Thermal Incinerator
Table FM-8 presents a material balance for this type of control
device. The data in the table are based on a 1500° F combustion zone
temperature and four mole % oxygen in the stack gas (exclusive of the
oxygen supplied by the absorber vent). This should assure complete
combustion of all pollutants.
Although there are no known tail gas incinerators employed in the
subject service, information available from similar installations
indicates that combustion efficiency should be quite high, 99+7o.

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TABLE FM-7
CATALOG OF EMISSION CONTROL DEVICES
FORMALDEHYDE via the mixed oxide catalyst process
ABSORBER/SCRUBBER^mxST ELIMINATOR
EPA Code No. for plant using'
Flov Diagram (Fig. I) Scream I. D,
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Coluon v/trays
Number of trays
Tray type
Other
Scrubblng/Abaorblng Liquid Rate - GPM
Design Temperature (Operating Temp.) - F°
Gas Rate, SCFM (lb./hr.)
T-T Height, rt.
Diameter, Ft.
Washed Gaaes to Stack
Stack Height - Ft.
Stack Diameter - Inches
Inptalled Cost - Mat'l. & Labor - $
Installed Cost bssed on - "year" - dollars
Installed Cost - c/lb. of 377. 11CH0 - Yr.
Operating Cost - Annual - $ - 1972
Value of Recovered Product, $/Yr.
Nat Operating Cost - Anneal - $
Net Operating Coat - c/lb. of 377. HCHO
Efficiency - X - SF.*
Efficiency - X - SERR*
14-17
E
FH-1
HCHO & CH3OH
None
lft-19
E
FM-2
HCHO
Yftter
14-19
FH-3
HCHO & CH3OH
Water
lft-22
E
FM-4
HCHO 6. CRjOH
None
Mist Elialn.
0
Not Specified
24
(80)
16,000
6.5
Seal Tank
20
(100)
1.7
"Centrlflx" Lisa Separator
0
(92)
3,199
Yes
85
2ft
52,500
1968
.0530
8.000
0
8,000
.0081
67
66
Yes
8
4
10,000
1967
.0101
200
0
200
.0002
~99
^99
Yes
10
It
4fOOO
1966 - 1971
.0040
0
0
0
0
•See Appendix III for explanation and definition of these items.

-------
TABLE FM-8
THERMAL INCINERATOR
100 MM LB./YR. FORMALDEHYDE PLANT
ABSORBER VENT STREAM
OVERALL MATERIAL BALANCE - LB./HR.C1)
Component
Formaldehyde
Methanol
Dimethyl Ether
Oxygen
Nitrogen
Carbon Dioxide
Carbon Monoxide
Water
Methane
Total
Absorber
Vent Gas
5
21
10
1,336
12,994
22
151
429
14,968
Fuel
Gas
328
328
Combustion
Air
1,356
4,493
Flue
Gas
(2)
5,849
1,252
17,487
1,215
1,191
21,145
(1)	Based on recycle operation.
(2)	Excludes any conversion of atmospheric nitrogen to NOx.
Stack Gas - 1500° F
Absorber Vent
Gas (85° F)
Combustion Air'*' 1290 SCFM
(80° F)
Fuel Gas -
130 SCFM

-------
FM-19
There are several drawbacks to thermal incinerators, as follows:
(1)	Vent gas is available only at low pressure.
(2)	Because the HC and CO concentration in the vent gas
stream is below the L.E.L., supplemental fuel must be
added to sustain combustion.
(3)	Due to the relatively small size of the stream, waste
heat recovery is not attractive.
(b)	Catalytic Incinerator
A conventional catalytic incinerator could reduce pollutants
to levels similar to those attainable with a thermal unit (see
Table FM-9 for material balance). The catalytic incinerator would
operate at lower temperatures (1000° F - 1200° F) and convert less
atmospheric nitrogen to NOx. Catalytic incinerator operating costs
are expected to be about 257» lower than those projected for a thermal
unit, with fuel savings more than off-setting catalyst costs.
(c)	Flare System
This control device is defined as one which requires supplemental
fuel, as contrasted to a plume burner which has a self supporting
flame. Its main other disadvantage is that efficiency for removal
of contaminants is less than for other combustion devices. The
efficiency will be influenced to some extent by the composition of
the vent gas. Based upon qualitative data from similar control
devices, it is estimated that 907„ of CO and hydrocarbon pollutants
will be burned.
2. Water Scrubbers
Table FM-10 presents a material balance for this type of device when
used in a recycle type of operation. It should be noted that approximately
five times more methanol and formaldehyde will be vented if non-recycle
operation is employed. The indicated performance is based on data
provided by questionnaire response. A water scrubber will require more
capital investment than any of the combustion devices. Scrubbers also
have the following performance deviciencies:
(a)	Efficiency of removing total hydrocarbons is less than for
combustion devices. Efficiency of removing dimethyl ether
is essentially zero.
(b)	Efficiency of removing carbon monoxide is near zero.
(c)	Air contaminants are transferred rather than destroyed and thus
require additional treatment or result in water pollution,
although partial recycle may be possible, or additional costs
may be minimalif the treatment is incremental to an existing
system.

-------
TABLE FM-9
CATALYTIC INCINERATOR
100 MM LB./YR. FORMALDEHYDE PLANT
ABSORBER VENT STREAM
OVERALL MATERIAL BALANCE - LB./HR.C1)
Absorber	Fuel	Combustion	Flue
Component	Vent Gas	Gas	Air		Gas (2)
Formaldehyde	5
Methanol	21
Dimethyl Ether	10
Oxygen	1,336 860 1,234
Nitrogen	12,994 2,849 15,843
Carbon Dioxide	22 888
Carbon Monoxide	151
Water	429 920
Methane	208
Total	14,968	208	3,709	18,885
(1)	Based on recycle operation.
(2)	Excludes any conversion of atmospheric nitrogen to NOx.
Stack Gas - 1200° F
1000° F
Abs;orber Vent
Gas (85° F)
Fuel Gas
^ 80 SCFM
Combustion Air™ 820 SCFM
(80° F)

-------
TABLE FM-10
WATER SCRUBBER
FOR
100 MM LB./YR. FORMALDEHYDE PLANT
OVERALL MATERIAL BALANCE - LB./HR.
Component
Formaldehyde*
Methanol*
Dimethyl Ether
Nitrogen
Oxygen
Carbon Dioxide
Carbon Monoxide
Water
Absorber
Vent Gas
5
21
10
12,994
1,336
22
151
429
14,968
Scrubber
Vent Gas
0.6
1.2
10
12,994
1,336
22
151
429
14,943.8
Liquid to
Scrubber
12,500
12,500
Liquid from
Scrubber
4.4
19.8
0
12,500
12,524.2
Mist Eliminator
Recycle Gas
Scrubber
Vent Gas
V///////J
Tray No. 4
Tray No. 3
Tray No. 2
Tray No. 1
Absorber

Water to Scrubber - 25 GPI
"^¦Waste Water ex Scrubber
Mist Eliminator
*Venting rates will be about five times the levels shown if non-recycle operation
is employed.
k.

-------
FM-22
V. National Emissions Inventory
Because emissions correlate with degree of absorber vent gas recycle and
because existing plants utilize varying degrees of recycle, there are various
ways of presenting a national emissions inventory. Emissions could be based on:
(1)	Average of emissions reported by all respondents and displayed in
Table FM-5.
(2)	Average emissions based on 'average' recycle plant operation - as
shown in the tabular listing in Section III-A-1 (Page FM-8).
(3)	Emissions based on best existing recycle operation, which is thought
to be typical of future plant emissions - as presented in Table FM-1
and FM-2.
In order to typify current (1973) emissions the first listed basis will be
used. (Note that this is not the basis for emission factors, economic data, etc.
for future plants listed in other sections of this report. Since these pertain
to new or future operations, they accordingly relate to the third listed basis.)
Average Emissions (a)	Total Emissions (b)
Component	Lb./Lb. of 37% HCHO	MM Lbs./Yr.	
Hydrocarbons	0.0149
CO	0.0144
0.0293
Since formaldehyde production has generally been reported as undergoing
no seasonal variation, emissions should be fairly constant throughout the
year, unless absorber tower top section cooling capacity is marginal (or does
not exist). In that case, emissions will tend to be somewhat higher during
warm weather.
25.7
24.9
50.6
(a)	Weighted average based on individual plant emission factors and formaldehyde
production. (Includes .0005 lbs. HC/lb. of 377= HCHO as fugitive emissions.)
(b)	Based on 1729 MM lbs./year mixed oxide catalyst process capacity and assuming
production rate equals capacity.

-------
FM-23
VI. Ground Level Air Quality Determination
A Gummary of air emissions data from the various surveyed formaldehyde
plants has been presented in Table FM-5. This table includes emissions from
absorber vent streams and other reported sources. An estimate of fugitive
emissions is given in Section III-G of this report.
Table FM-5 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 concentration for use in subsequent
reports.

-------
FM-24
VII. Co6t Effectiveness of Controls
Table FM-11 presents a cost analysis of alternate methods of reducing
air pollution related to the emission of absorber vent gases. Economic data
presented in this table are for a new plant producing 100 MM lbs./year of
37% formaldehyde via the absorber vent gas recycle mode of operation. The
data are based on the following:
A.	Investment (1973 Dollars)
1.	Incinerators
Published data (14) were used to determine both thermal and
catalytic incinerator costs. It should be noted that these are
"off-the-shelf" units. Incinerators specially designed for a given
application might be considerably more expensive.
2.	Flare System
Costs for this device were based on a special flare study as
authorized by the EPA's Project Officer on this contract.
3.	Scrubbers
Investment data provided in questionnaire responses on both the
subject process and other processes were used to determine scrubber
costs.
B.	Operating Expenses
1.	Depreciation - 10 year straight line.
2.	Interest - 67o on total capital.
3.	Maintenance - If plant survey data were not provided, maintenance
was set at 2°L of investment, except for catalytic incinerators
and water scrubbers, for which the maintenance was set at 4% of
investment.
4.	Labor - Virtually no operating labor is required for any of the
devices listed in Table FM-11. A nominal eight man hours/week was
assumed for the water scrubber and catalytic incinerator and four
man hours/week labor was assigned to the other devices.
5.	Utilities - Unit costs are based on typical value for the Gulf
Coast area.
-It is judged that all of the devices listed in Table FM-11 will offer
acceptable emission control, even the water scrubber with its relatively poor
efficiency rating. The water scrubber offers considerably lower operating costs
than the other devices. Additionally, future catalyst modifications may inhibit
dimethyl ether production and, therefore, permit better scrubber efficiency. On
the debit side, the water scrubber requires the highest investment, removes
essentially no carbon monoxide and merely transfers pollutants to another media-
water, rather than destroying them. However, it may be possible to re-use a
portion of this water by recycling it to the absorber. The flare system, while
offering the lowest capital investment, results in the highest operating cost,
primarily because it also requires the highest supplemental fuel consumption.

-------
TABLE FH-11
COST EFFECTIVENESS FOR ALTERNATE
EMISSION CONTROL DEVICES
BASED ON 100 MM LBS./YR. FORMALDEHYDE PRODUCTION
Stream
Type of Emission Control. Device
Nuaber of Units
Capacity of each unit - 7.
Absorber Vent Gas
Thermal Incinerator
No Ileat Recovery	40X Heat Recovery
1
100
1
100
Catalytic Incinerator
1
100
Flare System
1
100
Water Scrubber
1
100
Feed
Total Flow, Lba./Hr.	14,968
SCFM	3,390
Composition - Lbs./Lb. of 377. HCHO
Hydrocarbons	.0029
Particulate*
NOx
SOx
Carbon Monoxide	.0123
Codiliivd Effluent
Total Flow - Lba./Hr.
SCFM
21,145
A,790
21,145
4,790
18,885
4,270
18,885
4,270
14,943
3,385
Enission Control (g)
SE - 7.
CCR - 7.
SERR - 7.
100
100
100
100
100
100
90
90
69 (H.C.)
65
Investment - $ (f)
Purchased Coat
Installation
Total Capital
Operation Cost - $/Yr,
Depreciation (10 years)
lntereat an capital (61)
Maintenance
Labor 
-------
FM-26
Thermal incineration of the absorber vent gas stream offers the most
effective means of controlling emissions. However, operating costs are
relatively high due primarily to the requirement for supplemental fuel -
since the combustibles content of the vent gas is veil belov the L.E.L.
and vill not support combustion. Unfortunately, the caloric content of even
the enriched stream is probably insufficient to warrant the addition of
significant heat recovery hardware. A thermal incinerator could be incorporated
with either existing or new plants.
The installed cost of a catalytic incinerator ("excluding catalyst
costs, which are considered as operating costs) is slightly less than
that of a comparable thermal incinerator. This results primarily from its
lower operating temperature, and the effect thereof on fabrication and
installation. Increased maintenance and catalyst charges are more than off-set
by reduced supplemental fuel requirements. Emission control capability has
been depicted as being comparable to that of thermal devices, although the
possibility for catalyst failure through poisoning, etc., always exists.
The economic data presented for the various combustion devices are
based on the absorber vent gas composition shown in the individual devices
material balance. (FM-8, FM-9)
Variations in combustible content will result in appropriate changes in
supplemental fuel costs and will increase or decrease operating costs
proportionately.
Costs for installing the various absorber vent pollution control
equipment in existing plants would, for the most part, be the same or
only slightly higher than the figures shown in Table FM-ll. The actual cost
differential would depend largely on space availability and location relative
to associated process equipment. The single exception is the absorber vent
ga6 water scrubber. The Table FM-ll cost data for this unit are based on a
"piggy-back" type close coupled facility. Installation of this type of unit
in an existing plant would be impractical. Additionally, a non "piggy-back"
type unit would require a vent gas blover to overcome the increased A p caused
by connecting piping. Thus, investment and operating costs vould be higher for
installation of this system in an existing, plant.

-------
FM-27
VIII. Source Testing
It is recommended that source sampling be carried out at one of the
newer plants, vhich has been designed for recycle operation, and at a
plant utilizing a vater scrubbing device. Either of plants 14-21 or 14-23
would seem to be ideal candidates for the source of 'recycle operation
samples' while plant 14-19 is the only plant employing a vater scrubber.
Thus, plant 14-19 and either 14-21 or 14-23 are the recommended sites for
source sampling.
Ideally, the sampling program at plant 14-21 or 14-23 will be suf-
ficiently comprehensive to permit correlation of vent gas emissions with
recycle ratio and formaldehyde solution strength. The minimum number of sample
sets required would be six, at the following approximate combination of
conditions:

Recycle Gas
"Ratio"

07-
50/»*
1007»*
HCHO = 37 vt. %
X
X
X
HCHO - 51 wt. X
X
X
X
Sampling at plant 14-19 (currently a non-recycle operation) will
require sampling the scrubber inlet and outlet at most probably only one
set of conditions - i.e., typical full capacity operation.
*To be interpreted as 507. and 1007. of the maximum possible recycle gas ratio.

-------
FM-28
IX. Industry Growth Projection
Total annual U. S. formaldehyde production is estimated (^,5) tQ ^ncrease
to somewhere between 13 and 19 billion pounds per year of 377= solution by
1985. If the mixed oxide process maintains it6 present share of the market
it will account for the production of 3500 million pounds in 1985, see Figure
FM-2.
More than half of all formaldehyde produced is consumed by the con-
struction industry. Urea-formaldehyde resins are used as an adhesive in the
manufacture of particle board, and consume 25 percent of formaldehyde
production. phenolic resins are used as an adhesive for plywood and consume
about 25 percent of production. Melamine resins are used in decorative
laminates (kitchen counters, etc.) and consume about 8 percent of total
production. Demand in these areas is expected to remain high, if housing
starts continue to maintain record levels.
Hexamine (hexamethylene tetramine) has been accounting for about 6
percent of U. S. formaldehyde production the past few years as a result of
the use of large quantities of explosives in the Vietnam War. With the
withdrawal of u, S. Forces from that area, it is expected that hexamine
consumption will drop sharply.
Pentaerythritol (P.E.) accounts for about 7 percent of formaldehyde
production. P.E. is used in the manufacture of alkyd resin surface coatings.
Consumption is expected to remain fairly steady.
Urea-formaldehyde fertilizers consume about 5 percent of formaldehyde
production. Good growth, up to 9 percent/year, is expected for this industry.
Polyacetal resins account for about 8 percent of formaldehyde use. This
outlet is expected to maintain a growth rate of 10 percent/year.
Very little formaldehyde is either exported or imported due to the high
costs of transporting a water solution. Thus, fluctuations in the general
export/import market will not directly affect U. S. formaldehyde production.
The projected increase in formaldehyde production capacity will require
the construction of approximately 18 or 19 new 100 MM lbs./year mixed oxide
catalyst process plants between 1972 and 1985. This projection is based on
the assumption that the mixed oxide process will continue to account for 23%
of total formaldehyde capacity. It is doubtful that a resurgence of the partial
oxidation or any other third process will develop during this period.
As shown in Table FM-12, methanol coFts represent about 50 percent of
formaldehyde 'ex works' production costs. Therefore, formaldehyde selling
price is greatly influenced by methanol availability. This effect is mitigated
to some extent by the fact that the major formaldehyde producers have captive
methanol supplies. Methanol prices are currently very low as a result of
recent heavy expansions. The long-term outlook for natural gas prices should
eventually result in an upturn in methanol prices, but not until methanol
production catches up to capacity.

-------
FM'
j^RiALffiirnDE
se tcf sen mv rra ^
70.
#_.
S	
Q.
M
«c
4/
M
«TI
_c
o
X <
j"
* 1
i	
7-
A - Formaldehyde production capacity-all processes
B - Formaldehyde production-all processes.
C ¦ Formaldehyde production-mixed oxide process.
1980 C
1970
1960
1940
1950

-------
FM-30
X. Plant Inspection Procedures
Plant inspections will be conducted by the appropriate authorities, either
on a routine basis or in response to a complaint. The inspecting agent in
many cases may have only visual or olifactory observations at his disposal
although in some instances, stack monitoring equipment may be available or
it might be possible to sample the stack, through an accessible sample point.
If the inspector has any reason to suspect that emissions are excessive,
some factors that he should consider and/or discuss vith plant officials are
itemized below:
A.	Many plants require seven to ten days to achieve full recycle
operation subseauent to start-ups. Pollution control devices may
be over-loaded or by-passed during this period. A record should be
kept as to vhen and for how long this occurs. Obviously, an effort
should be made to minimize this type of operation. Also, safeguards
should be taken to prevent inadvertent opening of control device
by-pass valves.
B.	Proper operation of the absorber column is necessary to limit emissions
from the absorber vent gas in plants with no control device on this
stream. When the vent gas is discharged directly to the atmosphere
the only practical way hydrocarbon emissions can be controlled is by
manipulation of top tower temperatures. Many plants cool the top
section of the tower for this purpose. Most plants will keep a record
of some or all of the following operating variables and their design
limits.
(1)	Process and tower cooling water flow rates and temperatures.
(2)	Formaldehyde and methanol concentration in top tray (s) liquid.
(3)	Temperature and pressure of feed gas.
(4)	Temperature of the absorber vent gas, especially during warm
weather operation.
C.	A partially clogged or fouled demister can result in excessive liquid
entrainment.
D.	When absorber vent gas is burned, proper operation of the combustion
device is essential if emissions are to be minimized. Two types of
problems may be expected to be encountered, (1) flame-outs and (2)
excessive smoking. Plants are likely to periodically record some or
all of the following operating variables. Data will also be available
on design limits.
(1)	Combustion zone temperature.
(2)	Quantity of excess air (too little will cause smoking, too much
can result in flame-outs), which might be indicated by measure-
ments on one or all of the following;
a.	Device draft - inches of water.
b.	Temperature of stack gases.

-------
FM-31
c. Air flov rate.
(3)	Composition and flow rate o£ waste gas to the device.
(4)	Quantity and heating value of eupplementa1 fuel.
(5)	Composition of stack gases.
E. Periodic visual checks of flare stack opacity may be the only record
kept on the operation of this type of device. However, some plants
may record the following data for comparison with design limitations.
(1)	Feed composition, temperature and flow rate.
(2)	Occasional introduction of unusual materials into the flare
header.
(3)	Plant up-sets causing changes in loading on the flare system or
carryover of liquids to the header.
The investigating operative should be cognizant of the fact that seemingly
similar plants may have had widely differing design criteria. Thus, the flow,
temperature, pressure, composition, etc. characterizing a given stream in on
plant cannot necessarily be used as a basis for estimating like data for the
comparable stream in another plant. Nor, can data from similar streams in
separate plants be used, in themselves, to estimate comparative efficiencies
of related control equipment.

-------
FM-32
XI. Financial Impact
Table FM-12 presents economics for formaldehyde manufacture in a typical
100 MM Lbs./Year plant. This plant employs neither incineration nor scrubbing
devices, but relies solely on absorber off-gas recycling techniques and
absorber tower temperature manipulation for emission control. Two cases are
shown; the first for the current listed Gulf Coast methanol price of 12c/gal.,
and the second for the Los Angele6 area price of 17
. The
difference in production costs is based on the assumption that the required
fuel for the incinerator will be available at a price of 40^/MM BTU. Should
the cost be higher, then manufacturing costs for the new most feasible plant
will be increased proportionately.
No other case has been considered for financial impact studies because:
(1)	The cost of installing and operating an incinerator on an existing
plant will be about the same as on a new plant.
(2)	The addition of heat recovery equipment is not considered to be
economically justified.
(3)	Flare systems, while costing less to install are more expensive to
operate and wasteful of fuel.
(4)	Scrubbers, while less expensive to operate, do not achieve as effective
a clean-up of air emissions and are more expensive to install,
especially on existing plants. Furthermore, they transfer the emission
problem to the liquid effluents from the plant.
Obviously, the reader may take exception to any of these positions. In
that case, the data of Table FM-11 may be used to study the financial impact
of the alternatives.
Table FM-14 presents a proforma balance sheet for the following cases:
(1)	An existing plant - with no scrubbing, incineration or fractionator
recycle.
(2)	Most feasible new - this plant burns absorber tail gas in an incinerator.
It was assumed in developing these asset and liability positions that the
formaldehyde selling price would be held constant and the small increase in
total production costs would be taken out of the profit margin in order to
maintain sales at the same level. Capital requirement for the most feasible
new plant is estimated to be about $54,000 higher than for an existing plant
of the same capacity - 100 MM lbs./year.

-------
FM-33
TABLE FM-12
FORMALDEHYDE MANUFACTURING COSTS
FOR A TYPICAL
EXISTING 100 MM LB./YR. FACILITY
C/LB. $/YR.	c/LB. $/YR.
DIRECT MANUFACTURING COST
Raw Materials
Methanol @ 17c/Gal.	1.072
Methanol @ 12c/Gal.	.757
CatalyBts & Chemicals	.111	.111
Labor (2 men/shift (3 $4.85/Hr.)	.079	.079
Maintenance (57., of Investment)	.085	.085
Utilities	. 14 6	.146
1.493	1.178
INDIRECT MANUFACTURING COST
Plant Overhead (110% of Labor)	.087	.087
FIXED MANUFACTURING COSTS
Depreciation (10 years')	.170	.170
Ins. & Prop. Taxes (2.37. of Inv.)	. 039	.039
.209	.209
MANUFACTURING COST	1.789	1.474
GENERAL EXPENSES
Administration (37, of mfr. coBt)	.054	.044
Sales (17, of mfr. cost)	.018	.015
Research (27, of mfr. cost)	.036	.029
Finance (67, of inv.)	. 102	.102
.210	.190
COST
ex Works	1.999	1.664
Delivery	.620	. 620
TOTAL DELIVERED COST	2.619	2,619,000 2.284 2,284,000
PRODUCT VALUE
377, HCHO - Uninhibited

-------
FM-34
TABLE FM-13
FORMALDEHYDE MANUFACTURINGCOSTS
FOR A TYPICAL 100 MM LB./YR. FACILITY
EXISTING OR NEW WITH THERMAL INCINERATOR (NO HEAT RECOVERY')
C/LB. $/YR.	fc/LB. $/YR.
DIRECT MANUFACTURING COST
Raw Materials
MethanoL (p 17c/Gal.	1.072
Methanol @ 1?^/Gal.	.757
Catalysts & Chemicals	.111	.111
Labor (2 men/shift Q $4.85/Hr.)	.080	.080
Maintenance (57, of Investment)	.088	.088
Utilities	. 172	.172
1.523	1.208
INDIRECT MANUFACTURING COSTS
Plant Overhead (1107= of Labor) .088	.088
FIXED MANUFACTURING COSTS
Depreciation (10 years) .175	.175
Ins. & Prop. Taxes (2.3% of Inv.) .040	.040
.215	.215
MANUFACTURING COSTS 1.826	1.511
GENERAL EXPENSE
Administration (3% of Mfr. Cost)	.055	.045
Sales (17o of Mfr. Cost)	.018	.015
Research (27, of Mfr. CoBt)	.036	.030
Finance (6%. of Inv.)	. 105	.105
.214	.195
COST
Ex Works	2.040	1.706
Delivery	. 620	.620
TOTAL DELIVERED COST	2.660 2,660,000 2.326 2,326,000
PRODUCT VALUE
37% HCH0 - Uninhibited
@ 3.5c/Lb. (DLVD)	3.500 3,500,000	3.500 3,500,000
Profit before Taxes	.840 840,000	1.174 1,174,000
Profit after 527, Tax	.403 403,000	.564 564,000
Cash Flow	578,000	739,000
RETURN ON INVESTMENT	23.0%	32.1%
ROI SENSITVITY
With Doable Capital	Charges* 21.9%	30.8%
With Double Capital	& Operating Cost* 21.17c	30.0%
*Based on Table FM-11.

-------
FM-35
TABLE FM-14
PROFORMA BALANCE SHEET
100 MM LB./YR. FORMALDEHYDE MANUFACTURING FACILITY
New or Existing with Thermal
Existing	Incinerator (No Heat Recovery)
Current Assets
Cash (A)	149,100	152,000
Accounts Receivable (B)	291,700	291,700
Inventories (C)	199,900	204,000
Fixed Assets
Plant	1,700,000	1,754,000
Building	50,000	50,000
Land	25.000	25,000
Total Assets	2,415,700	2,476,900
Current Liabilities (D)	192,300	195,000
Equity and Long Terra Debt	2,223,400	2,281,900
Total Capital	2,415,700	2,476,900
(A)	Based on one month's manufacturing cost (with methanol (? 17<:/gal.).
(B)	Based on one month's sales.
(C)	Based on 10 MM lbs. of product valued at total cost (ex works).
(D)	Based on one month's total cost (DLVD) less fixed manufacturing and
finance costs.

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FM-36
An evaluation of the overall environmental impact of the most feasible
method of emission control described in this report is as important as the
financial impact. In addition to the desirable effect of reducing atmospheric
pollution through the curtailment of hydrocarbon and carbon monoxide emissions,
one must consider the cost in terms of energy. If all new mixed oxide
catalyst process plants employ vent gas incineration, supplemental fuel in
the amount of 3.5 x 10H BTU/year will be required to properly combust the
pollutants. This is equivalent to 350 million standard cubic feet per year
of natural gas. An additional 300 million SCF/year will be required for the
employment of incinerators on all existing plants. Use of flare systems
instead of incinerators will approximately double these natural gas consumptions
while heat recovery systems on the incinerators could halve them.

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FM-37
XII. Cost to Industry
In the typical present day plant, as depicated in Table FM-12, very
little of the plant investment is directly attributable to the cost of air
pollution control.
As noted in Section XI, the proposed most feasible modification of
existing formaldehyde plants results in negligible effects on production
costs (plus .04c/lb. - Of 37% formaldehyde). Therefore, the addition of
incinerators to existing plants should not pose a significant economic
problem to the industry. The total investment required to add this device
to all existing mixed oxide catalyst process plants would be on the order of
$1,000,000.
In the "most feasible new plant" presented in Table FM-13, additional
air pollution control equipment represents about three percent of total plant
investment. The resulting total production cost will be an estimated .04c/lb.
higher than for the present day typical unit. Thus, the costs involved should
not reduce growth in demand via the requirement for higher formaldehyde prices.
Assuming all new mixed oxide catalyst process plants built between now
and 1985 incorporate this type of air pollution control equipment, the total
incremental capital cost will be on the order of $1,000,000.
The projected effect of the above expenditures on future air emissions
is shown in Table FM-15, wherein:
The first three colums depict 1985 emissions for the situation where
no pollution control devices (as defined in Section IV) are employed.
However, credit is given to new plants which can minimize emissions by
running a recycle operation. The total emission rate is estimated to be
87.6 MM lbs./year.
The other three colums show the estimated 1985 emissions with all
plants utilizing that mode termed most feasible modification to new
or existing facilities, i.e., incinerators on the absorber vent gas
stream. This has the effect of lowering the emissions by 96% to 3.34
MM lbs./year.

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Type of Emission Control
Plants Involved
Production (MM Lbs./Year)
TABLE FM-L5
ESTIMATED 1985 EMISSIONS
FOR
ALTERNATIVE CONTROL SYSTEM
None
Existing (2)
1,729
New (3)
1,791
Total
3,520
Incinerators (1)
Existing
1,729
New
1,791
Total
3,520
Emissions (Lbs./Lb.)
Hydrocarbons
Carbon Monoxide
Total
Emissions (MM Lbs./Year)
Hydrocarbons
Carbon Monoxide
Total
Weighted Emissions (4)
Hydrocarbons
Carbon Monoxide
Total
NOTES:
0.0149
0.0144
0.0293
25.7
24.9
50.6
0.0036
0.0170
0.0206
6.5
30.5
37.0
0.0092
0.0158
0.0250
32.2
55.4
87.6
2560
55
2615
0.0014
	0
0.0014
2.44
	0
2.44
0.0005
	0
0.0005
0.90
	0
0.90
0.00095
	0
0.00095
3.34
	0
3.34
267
	0
267
(1)	On absorber vent gas.
(2)	Average reported by questionnaire respondents (see Page FM-22).
(3)	Utilizing best recycle system (see Page FM-8). Note that this disagrees with data reported on page 2 and 3 0f
Table I of Appendix I because data on improved recycle operations came to light after Table I was first
published.
(4)	Weighting Factors: Hydrocarbons = 80, Carbon Monoxide = 1 (see Appendix for explanation).

-------
FM-39
XIII. Emission Control Deficiencies
The control of formaldehyde plant emissions is effected by the
folloving technical considerations:
A. Process Chemistry and Kinetics
Production of formaldehyde by the mixed oxide catalyst process is
based on the air oxidation of methanol. The amount of formaldehyde
produced (per unit of methanol) is influenced by a variety of
parameters; among which are converter residence time, converter
temperature and methanol/oxygen ratio.
1. Converter Feed
(a) Methanol
Methanol feed must be pure. Impurities in the feed will
generally end up as impurities in the product. Formic acid,
one of the more common formaldehyde contaminants, can be
produced through the use of impure methanol. Ion exchange
resins are normally used to remove acidic contaminants from
the product. Regeneration of these resins may lead to acid
waste stream disposal problems.
(b) Air
Air is the source of oxygen required for the primary
reaction. Unlike the silver catalyst process, the metal oxide
catalyst is not adversely affected by SO2 and thus the air
requires no special treatment prior to its admixture vith methanol.
Air is also the source of nitrogen, which constitutes about
75% '"for recycle plants) of the absorber vent stream. Because
the major portion of the hydrocarbon emissions relating to the
subject process are those transported to the atmosphere by
venting non-reactants and reaction by-products, then reducing
the amount of nitrogen vented should reduce the amount of
hydrocarbons emitted. One way this can be done fvhen using
air as the source of oxygen) is to reduce the amount of air
charged to the process. This has been accomplished by proceeding
from non-recycle type operation to recycle operation. Thus,
emission reduction by this technique is probably as far
advanced - in modern 'recycle plants' - as practicable.
2.	Converter Operating Conditions
Converter operating conditions influence methanol conversion
rate and to some extent, the amount of non-selective products
formed. One of the non-selective products, (carbon monoxide) is
a major component of the absorber vent gas stream. Converter
operating conditions are normally selected to obtain the optimum
balance between conversion and selectivity.
3.	Catalyst
Since there is more than one licensor for the subject
process, it seems reasonable to surmise that there are various

-------
FM-40
catalyst formulations employed by the industry. Unfortunately,
detailed comparisons of the available catalysts are not
available. As discussed elsewhere in this report, a catalyst
that produced no dimethyl ether would be highly desirable from
an emission control standpoint.
Catalyst life is stated (^) , by one licensee, to be in the
range of 18-24 months. It is expected, however, that the
increased severity of recycle type operations will result in
somewhat shorter life.
B.	Process Equipment
1. Absorber
The absorber tail gas contains both gases and uncondensed vapors,
The uncondensed hydrocarbon vapors (methanol and formaldehyde),
because of their high 'weighted' value constitute the single most
significant source of emitted pollutants in the formaldehyde plant.
More complete condensation of the hydrocarbons is possible if the
absorber pressure is increased or the top temperature is decreased.
Unfortunately, neither action is practical. Increasing pressure to
a level sufficiently high to significantly affect vapor-liquid
equilibria would result in prohibitively high equipment and utility
costs. Decreasing the tower top temperature appreciably is impractical
because the freezing point of the liquid on the top tray is close
to 32° F, which, after allowing for a normal margin of safety, is not
significantly lower than the temperature at which many producers
actually operate their absorbers.
C.	Control Equipment and Operations
The current practice of recycling absorber vent gases provides
reasonably good control of hydrocarbon emissions. The emissions can
be further reduced by either water scrubbing or incineration. Each
method has its own deficiency. Water scrubbing requires relatively
high capital investment and is only moderately efficient. Additionally,
secondary water treatment is required, although this might only be
incremental to the overall plant water treatment costs and thus
relatively inexpensive. Incineration, due to high supplemental fuel
requirements, is burdened with high operating costs, but is quite
efficient.

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FM-41
XIV. Research and Development Goals
If the technological deficiencies discussed in Section XIII are to be
overcome, additional R & D is indicated in the following areas:
A.	Existing Plants - Improved Catalyst
It would be desirable to have a more selective catalyst in order
to produce fewer by-products; particularly by-product hydrocarbons,
which are especially objectionable when emitted to the atmosphere.
Private communications with the industry indicate that such changes
in catalyst performance are feasible and perhaps imminent. Thus,
R & D in this area may possibly be already under way. Intensification
of existing R&D programs (if any) should be considered.
B.	New Plants - Utilization of Pure Oxygen
In addition to the above mentioned R&D area, which has application
to both new and existing plants, technology involving the substitution
of oxygen for air would require modification of existing facilities or
moet probably would be applicable only to new plants. The use of oxygen
is presumably only feasible in plants utilizing gas recycle. In those
plants the oxygen could be diluted to below 10.9 vol. % by mixture with
the recycle gas. The effect of high carbon monoxide content recycle gas
on conversion, yield, temperature control, etc., will require definition
via appropriate R&D programs.

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FM-42
XV. Research and Development Programs
The following proposed projects relate to those areas of R & D which
seem to offer the best chance of obtaining a method of reducing emissions
from formaldehyde plants.
A. Project A
1.	Title - Catalyst Modification Program
2.	Objective - To investigate variations in the composition of
existing commercial mixed oxide catalysts from the standpoint
of the effect of these variations on activity, selectivity,
aging characteristics and reduction of by-product formation,
especially dimethyl ether,
3.	Estimated Project Costs (see Table FM-16 for cost breakdown)
Capital Expenditures	$ 22,100
Operating Costs
Unit Operations	57,300
Services	22,400
Miscellaneous	4,000
Contingency	52,900
$158,700
4.	Scope - This project would seek to reduce formaldehyde plant
emissions by catalyst modification.
5.	Program - A catalyst screening unit will be constructed with
facilities for the evaluation of the effluent by chromatographic
procedures, with emphasis on the quantitative analysis of by-
products. The normal operating characteristics of the
screening unit will be determined by employing a commercial
mixed oxide catalyst (Reichhold, Lummus, etc.). Experimental
catalysts containing metal oxides (chromium, manganese, copper
etc.) as additives to the normal iron-moly oxide catalyst will
be screened to determine if by-product formation can be reduced
without adversely altering the main catalytic function.
Adjustment of physical properties of the catalysts (e.g., pore
volume distribution, surface PH, total surface area, etc.) will
also be studied.
6.	Timetable - It is estimated that the above program will require
a total of 12 months to complete.
B. Project B
1.	Title - Process Modification Program
2.	Objective - To investigate variations or modifications to the
existing formaldehyde manufacturing process that would reduce
vent gas emissions. Emphasis will be given to the substitution
of oxygen for air in the feed.

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FM-43
3. Estimated Project Costs (see Table FM-16 for cost breakdown)
Capital Expenditures
Operating Costs
$ 67,100
Services
Process Engineering
Miscellaneous
Contingency
Unit Operations
62,500
11,400
9,100
5,800
78,000
Total
$233,900
4.	Scope - This program would seek to reduce formaldehyde plant
emissions by process modifications.
5.	Program
(a)	Construction of Pilot Unit
The first phase in this program would be the construction
of a small pilot unit. This unit would include converters,
quench system, absorber and vent gas recycle facilities and
would fully simulate commercial operations. Effluent gases
from the converter and absorber will be connected to an on-line
gas chromatograph. (If project A and project B are run sequentially,
some portions of the project A screening unit might be utilized
in the construction of the subject pilot unit.)
(b)	A number of process modifications will be explored to
determine their effect on methanol conversion, selectivity to
formaldehyde and vent gas emissions. The primary thrust of
the program, however, will be directed toward evaluating the
effect of substituting oxygen for (make-up) air in the feed.
In the beginning a standard commercial (or project A variation)
mixed oxide catalyst will be used. However, the program will
recognize the possibility that catalyst modifications may be
necessary to accomodate these changes.
(c)	Process Engineering
Date from the process research will be used to develop a
model for methanol conversion to formaldehyde. This model will
define optimum conversions and selectivities as a function of
vent gas emissions.
6.	Timetable - It is estimated that the above program will require
17 months to complete.

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FM-44
TABLE FM-16
DETAILED COSTS
FOR
R&D PROJECTS
Project "A"
Project "B"
A.	Capital Expenditures
Test Unit Construction
Unit Checkout
Professional
Operator
B.	Operating Expenses
Unit Operation
Professional
Operator
Services
Analytical
Cat. Prep. & Testing
Computer Operator
Unit Maint.
C.	Process Engineering
Professional
D.	Miscellaneous
Computer time
Materials
Report Writing
$15,000
A,500 (5 weeks)
2,600 (5 weeks)
36,500 (AO veeks)
20,800 (AO weeks)
1,300 (2 weeks)
17,500 (35 weeks)
3,600 (8 weeks)
2,700
1,300
$60,000
A,500 (5 veeks)
2,600 (5 weeks)
36,500 (AO weeks)
26,000 (50 weeks)
3,200 (5 veeks)
500 (1 week)
3,200 (6 weeks)
A,500 (10 weeks)
9,100 (10 weeks)
2,000
2,000
1,800
Totals of A to D
105,800
155,900
Contingency
Total Cost
52.900
$158,700
78,000
$233,900

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FM-45
XVI. Summary of Analytical Methods for Formaldehyde Plant Emissions
Of the seven plants responding to the mixed oxide catalyst formaldehyde
process questionnaire, three had measured emissions from the absorber vent
stack at some time in the past. The information received as to sampling
and analytical techniques was very sketchy, but is summarized below.
One plant has determined formaldehyde and dimethyl ether in the stack
gases using a grab sampling technique in conjunction with gas chromatographic
analysis. Samples have also been analyzed using the sodium sulfite (1) method.
No details regarding gas flow measurements, sampling equipment or chromatograph
operation are available. A second plant used a train consisting of absorber
vacuum pump and wet test meter followed by analysis of the absorber contents by
the sodium sulfite method (1). Gas flow was not measured.
The third plant has sanpled for formaldehyde, methanol, dimethyl ether
and carbon monoxide. Formaldehyde and dimethyl ether samples were collected in
a train consisting of a knockout flask, two Greenberg-Smith impingers containing
250 ml. water each, a rotameter and a vacuum pump. A Fuchsin-sulfurous acid
test solution was used for the colorimetric analysis of formaldehyde, while
methanol was measured by injection into an F and M Model 720 chromatograph
using a 20 foot column packed with ethofat. Dimethyl ether and carbon monoxide
samples were collected in a 500 ml. glass bulb preceded by a knockout flask.
A vacuum pump was connected to the glass bulb to insure adequate purging.
Both dimethyl ether and carbon monoxide were analyzed using a Beckman Model
GC-2A gas chromatograph. A 20 foot molecular sieve was used for carbon
monoxide, while a column containing 107<> triethyl acetyl citrate was used for
dimethyl ether. Stack gas flow was monitored during sampling by a flow meter
permanently installed in the plant.
The information summarized above is not sufficiently complete to allov
a detailed evaluation of the stack sampling techniques used. Considering the
information known as to the expected composition of the stack gases, accurate
sampling and analysis by glass bulb-gas chromatographic techniques should be
readily available. No developmental work appears warranted by the EPA unless
a standard method is desired.
A tabular summary of the reported analytical techniques is presented
in Table FM-17.

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TABLE FM-17
SUMMARY OF
SAMPLING AMD ANALYTICAL METHODS
Plant
Conponent
Method
Make
Model
Column Length - Ft.
Column Pscking/Abporbent
14-2
All
De«lgn values used




14-16
HCHO
All others
Sodium sulfite (Walker)
Chronatograph
Microtek
DSS/161
18
107. ethofat, columnpak T
14-17
All
No analytical data offered




14-19
CH3OH
CO
Dimethyl ether
HCHO
Chronatograph
Chronatograph
Chronatograph
Colorimetric
F 5. M
Backnan
Becknan
720
CC-2A
CC-2A
20
20
Ethofat
Mole sieve
107„ trlethyl acetyl citrate
14-21
All
Ex pilot plant or design data




14-22
HCHO
All others
Sodium sulfite (Walker)
Design values used




14-23
All
Ex pilot plant or design data





-------
FM-47
XVII. Emergency Action Plan For Air Pollution Episodes
A.	Types of Episodes
The .alleviation of Air Pollution Episodes as suggested by the U.S.
Environmental Protection Agency is based on a 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 Emissions
As outlined in the foregoing in-depth study of formaldehyde manufac-
ture by the Mixed Oxide Catalyst process there are three continuous and
two intermittent vent streams to the atmosphere.
1. Continuous Streams
(a)	Absorber Vent - This stream constitutes the greatest
potential for air pollution. It consists of the gross
converter effluent after cooling and absorption of the
product formaldehyde. On most plants surveyed this stream
exhausts directly to the atmosphere. The few exceptions
use mist eliminators in the tops of the absorber with
at least one plant employing a major emission control
system in the form of a water scrubber.
(b)	Dowtherm System Vent - This stream is relatively
insignificant in its contribution to air pollution.
A direct venting to the atmosphere would suggest a
"breathing" type of emission. It is, however, reported
as a continuous flow that could result from pressure
control equipment such as a vacuum ejector.
(c)	Storage Tank Vents - The majority of storage tanks
associated with reporting formaldehyde facilities vent
directly to the atmosphere. In some cases vapor conser-
vation devices are employed.

-------
FM-48
2.	Intermittent Air Emissions
(a)	Catalyst Activation Vent - This stream is the result of
a catalyst reactivation procedure whereby relatively
large quantities of nitrogen, oxygen and carbon dioxide
are vented to the atmosphere for about 24 hours once
per year. The stream probably contains trace amounts
of ammonium chloride and catalyst dust. However, due to
the infrequency of the operation and the low concentration
of contaminants, pollution from this source would appear
to be negligible.
(b)	Compressor Exhaust - Only one respondent reported emissions
from this source. Although its purpose is not clear, its
composition (N2, O2, CO and water) would indicate that it
may be from the discharge of the air compressor. Since
the reporting plant is a recycling operation, with the
recycle stream routed to the suction of the air compressor,
the composition would resemble the absorber vent stream.
Further, it is stated that during upset conditions which
may last for 20-30 minutes, contaminants may leave this
source. This would imply that the direct source could be
from an "anti-pumping" device on the compressor discharge.
3.	Fugitive Emissions
As in any processing plant there are emissions that result from
leaks and safing or purging of equipment in preparation for maintenance
and spills during loading of rail or truck tankers. These types of
emission should be small, infrequent in nature, and, with good
housekeeping, negligible as an air pollution source.
C. Abatement Techniques
As the various levels of the pre-planned episode reduction scheme are
declared (Alert, Warning and Emergency) a progressive reduction in the
amount of air pollutants emitted must be made. This could ultimately
lead to total curtailment of pollutant emissions if the emergency level
becomes imminent.
The extent of required cutback in emissions from formaldehyde plants
will depend on the relative amounts of air pollutants contributed by
formaldehyde production to the overall emissions which resulted in the
pollution episode. This, plus other factors, will be used by the
Governing Environmental Protection Authority in determining the cutback
to be made in all air pollution sources during the various episodes.
Formaldehyde manufacturing facilities, via the mixed oxide catalyst
process, consist of plants containing a converter, where the reaction
takes place, in a multiplicity of tubes filled with catalyst and an
absorber with its'associated appendages. In most instances formaldehyde
manufacturing facilities by the mixed oxide route utilize a recycle of

-------
FM-49
the absorber overhead. This results in a lower emission rate than
would otherwise be possible. It also provides for increased
flexibility to effect a partial reduction in air pollutant
emissions during an air pollution alert. There are significant
differences in design of the various plants. In general, however,
on those plants employing a recycle mode of operation, a reduction in
emissions can be realized by an increase in the percentage of recycle.
This can best be accomplished by decreasing the throughput and
increasing the percentage of effluent gas recycle which will result
in a reduction in emissions. For those plants that do not conduct a
recycle type of operation a partial reduction in emissions can be
obtained by an appropriate turndown in production.
It should be noted that the oxidation of methanol is an exothermic
reaction with the exotherm consumed within the process to generate
steam. Consequently, a significant turndown of plant production could
re6ult in a steam deficient condition in the confines of the plant.
Reduction in operating rates result in reductions in emissions
from the absorber tail gas. Limited information indicates that
emissions decrease at a rate that is more than a linear proportion at
lower operating levels. Under normal operation conditions a turndown
to a predetermined rate can be accomplished within a twenty-four hour
period. There would, however, be a progressive decrease during this
period. A shutdown of a methanol converter and its associated equipment
in terms of air emissions could be immediate. Startup, however, would
depend on conditions maintained during the shutdown. If reaction
temperature conditions were maintained through use of the startup
heater,then resumption of operation could be immediate. If the unit
was allowed to cool to ambient temperature/then startup would require
ten to twelve hours.
With one exception,no major emission control devices are reported
by the respondents. The exception (14-19) being a water scrubber in
use for both the absorber vent gas and storage tank vents prior to
discharge to the atmosphere. In plants employing this type of pollution
control equipment,it is desirable to maintain design water circulation
rates in the scrubber during air pollution episodes. With a reduction
in total flow of the absorber vent gas, the scrubbing efficiency should
be improved over that obtained at normal formaldehyde 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 manufacturers of the alert condition, it may be deemed
necessary by the Environmental Protection Authorities to
somewhat reduce emissions from formaldehyde manufacture in
order to prevent further increases in pollution level which
could result in warning or emergency episodes. This reduction
would be accomplished by a turndown in plant production as
previously discussed. The time required to effect the reduction

-------
FM-50
will be approximately as stated in the preceding discussion.
This will reduce the principal source of emission, represented
by the absorber vent stream. The other continuous sources of
emissions represented by the dowtherm system and storage tank
vents are relatively insignificant in their contribution to
air pollution. It would be expected that storage tank vent
losses would be reduced to some lesser degree by virtue of
the reduction made in the producing equipment.
The intermittent emissions represented by the catalyst
activation vent and the compressor exhaust should be curtailed
if possible during an air pollution episode. In the case of
the compressor exhaust it is indicated that this stream is
emitted during upset conditions. With a reduction in the
producing equipment it is unlikely that this source of emission
would become activated. In any event every effort should be
made to prevent a discharge from this source. Usually the
alert condition can be expected to continue for twelve hours
or more.
2.	Declaration of Warning Condition - When the air pollution
warning episode is announced a substantial reduction of air
contaminants is desirable even to the point of assuming
reasonable economic hardship in the cutback of production and
allied operations. This could involve a 50-60% decrease in
formaldehyde production.
3.	Emergency Condition - When it appears that an air pollution
episode is imminent, all air contaminants may have to be
eliminated immediately by ceasing production and allied
operations to the extent possible without causing injury to
persons or damage to equipment.
D. Economic Considerations
The economic impact on formaldehyde 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 usual duration of air pollution episodes is 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 set forth in the early paragraphs of this section.
Normally since the alert level does not require a cutback in production,
it will not influence plant economics. Therefore in discussing economic
considerations resulting from the air pollution abatement plan, it is
only necessary to estimate the frequency and number of warning and
emergency episodes. For the economic study, it has been assumed that
three warning and no emergency episodes occur per year. Each warning
episode is assumed to require a 50% reduction in air contaminants for
a period of 5-1/2 days. This equates to a complete loss in plant
production of about eight and one-half days per year.

-------
FM-51
The Financial impact resulting from this loss in production is shown
in Table FM-18 which presents comparative manufacturing costs for a
typical existing 100 MM lbs./year facility without extensive pollution
control (Table FM-12) and a typical existing or new plant of the same
capacity but having an absorber vent gas incinerator (Table FM-13).
Economics are shown for each of these plants with methanol feed at 12 and
17 cents per gallon with and without the financial impact accredited to
the air pollution episodes. It should be noted that whereas the proposed
cutback in formaldehyde production for emission control appears small
(2.5 percent on a yearly basis), it reduced net profit by 4.0 to 4.5
percent.
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 with no pollution control
equipment. However, special considerations should be provided in the
EPA for Air Pollution Episode Avoidance for existing plants that install
control devices which substantially reduce emissions and also for future
plants that are equipped with the "latest state of the art" emission
control equipment.
The following presents estimated air emissions for typical present-day
systems without control devices and a typical existing or new plant that
incorporates thermal incineration on the absorber vent gas.
Typical Present-Day Typical New or Existing Pi
System Without With Thermal Incineration
Pollutant	Control Devices		(No Heat Recovery)
Emissions, Lb./Lb.
Hydrocarbons	0.0092	.0005
Carbon Monoxide	0.0158
Total	0.0250	.0005
As noted in the above, total emissions for the plant with an incineratoi
have been reduced to two percent of that estimated for the uncontrolled
plant. However, for both the new and modified plants with incineration,
some NOx emission would be expected.
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. If NOx is the offending material,then a reduction in
production from plants with incinerators may be required as outlined
under "Declaration of Alert Condition". In this case NOx would be
reduced as the cutback in production is made.
If the offending pollutants are in the form of hydrocarbons or carbon
monoxide, the degree of cutback on the typical new plant or the modified
existing plant could be proportionally less severe than on the uncontrolled
facility.

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TABLE FM-18
FINANCIAL IWACT OF AIR POLLUTION' EPISODES
ON MANUFACTURING COSTS
FOR 10Q W LBS/YEAR FORMALDEHYDE MANUFACTURING FACILITIES
VIA TOE MIXED OXIDE CATALYST PROCESS
Sheet 1 of 2


TYPICAL EXISTING PLANT

TYPICAL NEW
PLANT UTILIZING THERMAL INCINERATOR






(NO HEAT RECOVERY)



(FROM TABLE
FM-12)


(FROM TABLE
FM-13)


Methanol §
17*/Gal.
Methanol 6
12*/Gal.
Methanol £
17*/Gal.
Methanol e
12
-------
TABLE FM-18
General Expenses
Administration, Sales, Res.,
and Finance
Cost
Ex Works
Delivery
Total Delivered Costs
Product Value, M j/Yr.
37% HCHO . Uhinhibited
@ 3.5*/Lb. (Dlvd.)
Profit Before Taxes
Profit After 52% Tax
Cash Flow
KOI
FINANCIAL IMPACT OF AIR POLLUTION EPISODES
ON MANUFACTURING COSTS
FOR 100 W LBS/YEAR FORMALDEHYDE MANUFACTURING FACILITIES
VIA THE MIXED OXIDE CATALYST PROCESS
PAGE 2 - CONTINUED
Sheet 2 of 2

TYPICAL EXISTING PLANT

TYPICAL NEW
PLANT UTILIZING THERMAL INCINERATOR





(NO HEAT RECOVERY)


(FROM TABLE FM-12)


(FROM TABLE FM-13)

Methanol t
17
-------
FM-54
Re ferertces
1.	Walker, J. B. , "Formaldehyde", ACS Monograph Series, Reinhold
Publishing Corporation, 1964.
2.	"Own Your Ovn Formaldehyde Plant", Chemical Week, July 10, 1965,
pages 81 - 84.
3.	Stobaugh, R. B., et al: "Methanol: How, Where, Who -- Future";
Hydrocarbon Processing, June, July, August, September, 1970.
4.	"A Lively Rivalry for Licensees", Chemical Week, November 19, 1969,
pages 79 - 82.
5.	"Formaldehyde Chemical Profile", Chemical Marketing Reporter,
May 1, 1972.
6.	"Chemical Economics Handbook', Stanford Research Institution,
August, 1970.
7.	Hahn, Albert, "The Petrochemical Industry: Markets and Economics",
McGraw-Hill Inc., 1970, pages 75 - 88.
8.	Kirk-Othmer, "Encyclopedia of Chemical Technology", 2nd Edition,
1966, Volume 10, pages 86 - 90
9.	"Air Pollution Survey Production of Ten Petrochemicals", MSA
Research Corporation for Environmental Protection Agency,
Contract No. EHSD 71-12, Mod. I, Task II, July 23, 1971.
10.	Long, F. W., "U. S. Petrochemicals", pages 87 - 89.
11.	"Formaldehyde from Methanol", Modern Chemical Processes, Volume III,
pages 79 - 80.
12.	''Materials for Making Formaldehyde", Chemical Engineering,
January 15, 1968, pages 182 - 188.
13.	"More - Methanol Formaldehyde Route Boasts Many Benefits",
Chemical Engineering, March 9, 1970, pages 102 - 104.
14.	Rolke, R. W., et al; "Afterburner Systems Study", by Shell
Development Company for Environmental Protection Agency (Contract
EHAS 71-3).
15.	"Formaldehyde Producers Move to Ease Shortage of Materials; Borden,
Reichhold Expanding", Oil Paint and Drug Reporter, April 7, 1969,
pages 5 - 30.
16.	"Directory of Chemical Producers", Stanford Research Institute.
17.	"Easy Way to Formaldehyde", Chemical Engineering, November, 1954,
pages 109 - 110.
18.	U. S. Patent No. 2,43 6,287, Brondyke et al.
19.	"Guide for Air Pollution Episode Avoidance", Environmental Protection
Agency Office of Air Programs, Publication No. AP-73, June, 1971.

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APPENDIX I
BASIS OF THE STUDY
I. Industry Survey
The study which led to thi6 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 wa6 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 Dichloride (two processes)
Ethylene Oxide (two processes)
Formaldehyde (two processes)
Glycerol
Hydrogen Cyanide
Maleic Anhydride
Nylon 6
Nylon 6,6
"Oxo" Alcohols and Aldehydes
Phenol
Phthalic Anhydride (two processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene .Rubber
Terephthalic Acid (i)
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 SEl'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 Dichloride) from Ethylene.

-------
TABLE I
EMISSIONS SUMMARY
Page 1 of 3



ESTIMATED W CURRENT
AIR EMISSIONS. .>
¦IK LBS./YEAR

(3\
Hydrocarbons * '
Particulates
Oxides of Nitrogen
Sulfur Oxides
Carbon Monoxide
Total
Acetaldehyde via Ethylene
1.1
0
0
0
0
1.1
via Ethanol
0
0
0
0
27
27
Acetic Acid via Methanol
0
0
0.01
0
0
0.01
via Butane
40
0
0.04
0
14
54
via Acetaldehyde
6.1
0
0
0
1.3
7.4
Acetic Anhydride via Acetic Acid
3.1
0
0
0
5.5
8.6
Acrylonitrile (9)
183
0
5.5
0
196
385
Adipic Acid
0
0.2
29.6
0
0.14
30
Adiponltrile via Butadiene
11.2
4.7
50.5
0
0
66.4
via Adipic Acid
0
0.5
0.04
0
0
0.54
Carbon Slack
156
8.1
6.9
21.6
3,870
4 ,060
Carbon Disulfide
0.15
0.3
0.1
4.5
U
5.1
Cyclohexanone
70
0
0
0
7/. 5
148
Dimethyl Tcrephthalatc (+TPA)
91
1.4
0.1
1.0
53
146.5
Ethylene
15
0.2
0.2
2.0
0.2
17.6
Ethylene Dlchloride via Oxychlorination
95.1
0.4
0
0
21.8
117.3
via Direct Chloriaation
29
0
0
0
0
29
Ethylene Oxide
85.8
0
0.3
0.1
0
86.2
Formaldehyde via Silver Catalyst
23.8
0
0
0
107.2
131
via Iron Oxide Catalyst
25.7
0
0
0
24.9
50.6
Glycerol via Epichlorohydrin
16
0
0
0
0
16
Hydrogen Cyanide Direct Process
0.5
0
0.41
0
0
0.91
leocyanates
1.3
0.8
0
0.02
86
88
Maleic Anhydride
34
0
0
0
260
294
Nylon 6
0
1.5
0
0
0
1.5
Nylon 6,6
0
5.5
0
0
0
5.5
Oxo Process
5.25
0.01
0.07
0
19.5
24.8
Phenol
24.3
0
0
0
0
24.3
Phthallc Anhydride via 0-Xylene
0.1
5.1
0.3
2.6
43.6
51.7
via Naphthalene
0
1.9
0
0
45
47
High Density Polyethylene
79
2.3
0
0
0
81.3
Lov Density Polyethylene
75
1.4
0
0
0
76.4
Polypropylene
37.5
0.1
0
0
0
37.6
Polystyrene
20
0.4
0
1.2
0
21.6
Polyvinyl Chloride
62
12
0
0
0
74
Styrene
4.3
0.07
0.14
0
0
4.5
Styrene-Butadiene Rubber
9.4
1.6
0
0.9
0
12
Vinyl Acetate via Acetylene
5.3
0
0
0
0
5.3
via Ethylene
0
0
TR
0
0
TR
Vinyl Chloride
17.6
0.6
_0	
_0	
0
18.2
Totals
1,227.6
49.1
94.2
33.9
4,852.6
6,225.9 O
Total Weighted
86
27
1
3,215
490
253
15,000
1,190
3,200
30
17,544
120
5,700
7, A 60
1,240
7,650
2,300
6.B80
1,955
2,070
1 ,280
5 6
231
2,950
90
3 30
440
1,940
422
160
6,400
6,100
2,950
1,650
5,700
355
870
425
TR
1,460
(5)

110,220 t?)
(1)	In BDRt instances nunbers arc based on lets than 100% survey. All based on engineering judgement of best current control. Probably has up to 10% lov bias.
(2)	Assumes future plants ulll employ best current control techniques.
(3)	Excludes methane, includes H2S and all volatile organics.
(4)	Includes non-volatile organics and'inorganics.
(5)	Weighting factors used are: hydrocarbons - 80, particulates - 60, N0X - 40, S0X - 20, and CO - 1.
(6)	Referred to elaevhere in this study as "Significant Emission Index" or "SEX",
(7)	Totals sre not equal acroas and dovn due to rounding.
(9)	Emissi ons based on vhst is nov an obsolete catalyst. See Report No. EPA-450/3-73-006 b for up-to-date information.

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TABLE I
EMISSION SUMMARY
Page 2 of 3



ESTIMATED ADDITIONAL (2>
AIR EMISSIONS IN
1980, MM LBS./YEAR


Hydrocarbons
Particulates
(4)
Oxides of Nitrogen
Sulfur Oxides
Carbor. Xonoxide
Total
Total Weighted
Acetaldehyde via Ethylene
1.2
0

0
0
0
1.2

via Ethanol
0
0

0
0
0
0
0
Acetic Acid via Methanol
0
0

0.04
0
0
0.C4
2
via Butane
0
0

0
0
0
0
0
via Acetaldehyde
12.2
0

0
0
2.5
14.7
980
Acetic Anhydride via Acetic Acid
0.73
0

0
0
1.42
2.15
60
Aerylonitrilc (9)
284
0

8.5
0
304
596
23,000
Adipic Acid
0
0.14

19.3
0
0.09
19.5
7 79
Adiponitrile via Butadiene
10.5
4.4

47.5
0
0
6? .4
3,010
via Adipic Acid
0
0.5

0.04
0
0
0.54
30
Carbon Black
64
3.3

2.8
8.9
1,590
1 ,670
7 ,200
Carbon Disulfide
0.04
0.07

0.03
1.1
0
1.24
30
CyclDhexanDne
77.2
0

0
0
B5.1
162
6,260
Dimettiyl Terephthalate (+TPA)
73.8
1.1

0.07
0.84
42.9
118.7
6,040
Ethylene
14.8
0.2

0.2
61.5
0.2
77
2,430
Ethylene Dichloride via Oxychlorination
110
0.5

0
0
25
136
8,800
via Direct Chlorination
34.2
0

0
0
0
34.2
2 ,740
Ethylene Oxide
32.8
0

0.15
0.05
0
33
2,650
Formaldehyde via Silver Catalyst
14.8
0

0
0
66.7
81.5
1 ,250
via Iron Oxide Catalyst
17.6
0

0
0
17.0
34.6
1,445
Glycerol via Epichlorohydrln
8.9
0

0
0
0
8.9
700
Hydrogen Cyanide Direct Process
0
0

0
0
O
0
0
Isocyanatcs
1.2
0.7

0
0.02
a;
87
225
Maleic Anhydride
31
0

0
0
241
272
2,720
Nylon 6
0
3.2

0
0
0
3.2
194
Nylon 6,6
0
5.3

0
0
0
i.3
310
Oxo Process
3.86
0.01

0.05
0
14.3
18.2
325
Pheno1
21.3
0

0
0
0
21.3
1,704
Phthalic Anhydride via O-Xylene
0.3
13.2

0.8
6.8
113
134
1,100
via Naphthalene
0
0

0
0
0
0
0
Hifih Density Polyethylene
210
6.2

0
0
0
216
17,200
Lou Density Polyethylene
262
5

0
0
0
267
21,300
Polypropy Lenc
152
0.5

0
0
0
«/">
CSI
«/">
12,190
Polystyrene
20
0.34

0
1.13
0
21.47
1,640
Polyvinyl Chloride
53
10

0
0
0
63
4,840
Styrcne
3.1
0.05

0.1
0
0
3.25
225
Styrene-Butadiene Rubber
1.85
0.31

0
O.lfi
0
2.34
170
Vinyl Acetate via Acetylene
4.5
0

0
0
0
4.5
360
via Ethylene
0
0

TR
0
0
I?.
TR
Vinyl Chloride
26.3
0.9

0
0
0
27.2
2.170
Totals
1.547.2
55.9

79,5
80.5
2,588
4,351.9
134,213 <'')
(1)	In most instances nuabers are based on les6 than 100% survey. All based on engineering judgement of best current control.
(2)	Assumes future planes will employ beat current control techniques.
(3)	Excludes methane, includes H2S and all volatile organics.
(4)	Includes non-volatile organics and inorganics.
(5)	Weighting factors uaed are: hydrocarbons - 80, particulates - 60, NO* - 40, S0X - 40, and CO - 1.
(6)	Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
(7)	Totals are not equal across and down duv to rouoding,
(9)	See sheet 1 of 3.
Probably has uo to 10% low bias.

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TABLE I
EMISSIONS SUMMARY
Page 3 of 3

Emissions
(2), MM Lbs ./Year

Total Estimated capacity



Estimated Number of New plants

MM Lbs./vear

Total bv 1980
Total Weighted (5) bv 1980
(1973 - 1980)
Current
Bv 1980
Acetaldehyde via Ethylene
2.3
182
6
1,160
2,4 60
via Ethanol
27
27
0
966
966
Acetic Acid via Methanol
0.05
3
4
4 00
1,800
via Butane
54
3,215
0
1,020
500
via Acetaldehydc
22
1,470
3
875
2,015
Acctlc Anhydride via Acetic Acid
10.8
313
3
1,705
2,100
AeryLonltrlle (9)
980
38,000
5
1,165
3,700 (8)
Adlplc Acid
50
1,970
7
1,430
2,200
Adiponltrllc via Butadiene
128.8
6,210
4
435
845
via Adlplc Acid
1.1
60
3
280
550
Carbon Black
5,730
24,740
13
3,000
5,000 (8)
Carbon Disulfide
6.3
150
2
871
] ,100
Cyclohexanone
310
11,960
It)
1,800
3,bOO
Dimethyl Terephthalate (+TPA)
265
13,500
8
2,865
5,900
Ethylene
94
3,670
21
22,295
40,000
Ethylene Ulchlorlde via Oxychloriaatlon
253
16,450
8
4,450
8,250 (8)
via Direct Chlorination
63
5,040
10
5,593
11,540
Ethylene Oxide
120
9,530
15
4,191
6,800 (8)
Formaldehyde via Silver Catalyst
212.5
3,205
40
5,914
9,000
via Iron Oxide CatalyBt
85
3,515
12
1,729
3,520 (8)
Glycerol via Eplchlorohydrln
25
2,000
1
245
380
Hydrogen Cyanide Direct Process
0.5 (10)
28 (10)
0
412
202
laocyanates
175
456
10
1,088
2,120
Malelc Anhydride
566
5,670
6
359
720
Nylon 6
4.7
284
10
486
1,500
Nylon 6,6
10.8
650
10
1,523
3,000
Oxo Process
43
765
6
1,727
3,000
Phenol
46
3,640
11
2,363
4,200
Phthallc Anhydride via O-Xylene
186
1,522
6
720
1,800 (8)
via Naphthalene
47
160
0
603
528
High Density Polyethylene
297
23,600
31
2,315
8,500
Low Density Polyethylene
343
27,400
41
5,269
21,100
Polypropylene
190
15,140
32
1,160
5,800
Polystyrene
43
3,290
23
3,500
6,700
Polyvinyl Chloride
137
10,540
25
4,375
8,000
Styrene
7.4
610
9
5,953
10,000
Styrane-BJtadiene Rubber
14
1,040
4
4,464
5,230
Vinyl Acetate via Acetylene
9.8
785
1
206
356
via Ethylene
TR
TR
4
1,280
2,200
Vinyl Chloride
45
3.630
10
5,400
13,000
Totals	10,605 t?)	244,420
(1)	In most instances Quakers are based on less than 1007. survey. All based on engineering judgement of best current control. Probably has up to 10% low bias,
(2)	Assumes future plants will employ best current control techniques.
(3)	Excludes methane, includes H2S and all volatile organics.
(4)	Includes non-volatile organics and inorganics.
(5)	Weighting factors used are; hydrocarbons - 60, particulates - 60, N0X * 40, S0K - 20, and CO * 1.
(6)	Referred to elsevhere in this study as "Significant Emission Index" or "SEI".
(7)	Totals are not equal across and down due to rounding.
(8)	&y 1985.
(9)	See sheet 1 of 3
(10)	Dub to anticipated future shut down of marginal plants.

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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.

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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*6 discretion.

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APPENDIX II-|.
Number of New Plants*
Attached Table 1 illustrates the format for this calculation.
Briefly, the procedure is as follows:
1.	For each petrochemical that is to be evaluated, estimate what
amount of today's production capacity is likely to be on-stream
in 1980. This will be done by subtracting plants having marginal
economics due either to their size or to the employment of an
out-of-date process.
2.	Estimate the 1980 demand for the chemical and assume a 1980
installed capacity that will be required in order to satisfy
this demand.
3.	Estimate the portion of the excess of the 1980 required capacity
over today's remaining capacity that will be made up by
installation of each process that is being evaluated.
4.	Estimate an economic plant or	unit size on the basis of today's
technology.
5.	Divide the total required new	capacity for each process by the
economic plant size to obtain	the number of new units.
In order to illustrate the procedure, data have been incorporated
into Table I, for the three processes for producing carbon black, namely
the furnace process, the relatively non-polluting thermal process, and
the non-growth channel process.
*The format is based on 1980, but any future year may be selected.

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Table
1. Number of
New Plants
by 1980




Chemical
Process
Current
Capacity
Marginal
Capacity
Current
Capacity
on-stream
in 1980
Demand
1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number of
New
Unite
Carbon Black
Furnace
4,000
0
4,000
4,500
5,000
1,000
90
11 - 12

Channel
100
0
100
100
100
0
30
0

Thermal
200
0
200
400
500
300
150
2
Notes; 1. Capacity units all in MM lbs./year.
2. 1980 demand based on studies prepared for EPA by Processes Research, Inc. and MSA Research Corporation.

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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 NO^ is somewhat more
noxious than S0X. However, there are widely divergent opinions concerning
hydrocarbons and particulates - probably due to the fact that these are
both widely divergent categories. In recent years, at least two authors
have attempted to assign tolerance factors to these five categories.
Babcock (1), based his on the proposed 1969 California standards for
one hour ambient air conditions with his own standard used for hydrocarbons.
On the other hand, Walther (2), based his ranking on both primary
and secondary standards for a 24-hour period. Both authors found it
necessary to extrapolate some of the basic standards to the chosen time
period. Their rankings, on an effect factor basis with carbon monoxide
arbitrarily used a6 a reference are as follows:
Babcock
Walther
Primary
Secondary
Hydrocarbons
Particulates
N0X
S0X
CO
2.1
107
77.9
28.1
1
125
21.5
22.4
15.3
1-
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 baBis as follows:
Average	Rounded
Hydrocarbons	84.0 80
Particulates	55.3 60
N0X	40.9 40
S0X	21.6 20
CO	11

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Table 2. Weighted Emission Rates
Chemical	
Process		
Increased Capacity		
Increased Emissions	Weighting	Weighted Emissions
Pollutant	Emissions, LbB./Lb.	Lbs ./Year	Factors	Lbs. /Year
Hydrocarbons	80
Particulates	60
NO*	40
SO*	20
CO	1
Total

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II-5
Increased Emissions (Weighted) by 1980 (continued)
This ranking can be defended qualitatively, if not quantitatively for
the following reasons:
1.	The level of noxiousness follows the same sequence as is obtained
using national air quality standards.
2.	Approximately two orders of magnitude exist between top and bottom
rankings.
3.	Hydrocarbons should probably have a lower value than in the
Walther analysis because such relatively non-noxious compounds
as ethane and propane are included.
4.	Hydrocarbons should probably have a higher value than in the
Babcock analysis because such noxious (or posionous) substances
as aromatics, chlorinated hydrocarbons, phenol, formaldehyde, and
cyanides are included.
5.	Particulates should probably have a higher value than in the
Walther analysis because national air standards are based mostly
on fly ash while emissions from the petrochemical industry are
more noxious being such things as carbon black, phthalic anhydride,
FVC dust, active catalysts, etc.
6.	N0X 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.

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II-6
Increased Emissions (Weighted) by 1980 (continued)
Babcock, L. F., "A Combined Pollution Index for Measurement of Total
Air Pollution," JAPCA, October, 1970; Vol. 20, No, 10; pp 653-659
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

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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, oxide6 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:
1. Completeness of Combustion Rating (CCR)
This rating is based on oxygen rather than on pollutants and is
the pounds of oxygen that react with the pollutants in the feed to
the device, divided by the theoretical maximum number of pounds that
would react: Thus a smokeless flare would receive a 100 percent
rating while a smoky one would be rated somewhat less, depending upon
how incomplete the combustion.
In utilizing this rating, it is clear that carbon dioxide and water
are the products of complete combustion of hydrocarbons. However, some
question could occur as to the theoretical completion of combustion
when burning materials other than hydrocarbons. It was recommended
that the formation of HX be considered complete combustion of halogenated
hydrocarbons since the oxidation most typically does not change the
valence of the halogen. On the other hand, since some incinerators will
be catalytic in nature it was recommended that sulfur trioxide be
considered as complete oxidation of sulfur bearing compounds.

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III-2
Efficiency of Pollution Control Devices
1.	Completeness of Combustion Rating (CCR) (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 N0X 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 iE 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:
3C2H^ + 7 02	C + 2 CO + 3 C02 + 6 H20
Thus, 14.2 lbs. of particulate carbon and 66.5 lbB. of carbon
monoxide are emitted, and 265 lbs. of oxygen are consumed.
Theoretical complete combustion would consume 342 lbs. of oxygen
in accordance with the following reaction:
^"2^4 3 02	y 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:

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III-3
Efficiency of Pollution Control Devices
2. Significance of Emiaaion Reduction Rating (SERR) (continued)
Pollutant
Hydrocarbons
Particulates
N0X
S0X
CO
Total
Weighting
Factor
80
60
40
20
1
Pounds in
Pound8 out
Actual
100
0
0
0
0
Weighted
8000
Actual Weighted
0
14.2
1
0
66.5
8000
852
40
66.5
958.5
SERR = 8000 - 958.5
8000
x 100 « 887o
Example 2 - The same aa 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 o2
¦fr 2 C02 +2 H20 + 2 HC1
This is complete combustion, by definition, therefore, the CCR is
100%. However, (assuming no oxides of nitrogen are formed), the SERR
iB less than 100% because 72.5 lbs. 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 iB followed by an efficient scrubber for HCl 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
N0X in the same unit time. The assumed reactions are:

-------
III-4
Efficiency of Pollution Control Devices
2. Significance of Emission Reduction Rating (SERR) (continued)
4 HCN + 5 O2 *2 H2O + 4 CO2 + 2 N2
N2 (atmospheric) + XO2 ¦ 1 ^ 2 N0X
Thus, CCR^ = 100% and CCR2 = 100% both by definition.
However, SERR^ = 100 x 80 - 1 x 40 ^qq _ go 57
100 x 80	' °
and SERRo = 100 x 80 - 10 x 40 		
2 	100 x 80	 * 100 - 951
Obviously, if either of these were "smoky" then both the CCR and
the SEKR would be lower, as in Example 1.
Other Pollution Control Devices
Most pollution control devices, such as bag filters, electrostatic
precipitators and scrubbers are designed to physically remove one or more
noxious substances from the stream being vented. Typically, the efficiency
of these devices is rated relative only to the substance which they are
designed to remove and for this reason could be misleading. For example:
1.	The electrostatic precipitator on a power house stack might be
997» efficient relative to particulates, but will remove little
or none of the S0X and N0X which are usually present.
2.	A bag filter on a carbon black plant will remove 99 + % 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.
4.	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
specific pollutant in	x
The second rating proposed is an SERR, defined exactly as in the case
of incinerators.
Two examples will illustrate these ratings.

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III-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 lbs. of
carbon monoxide and 10 pounds of Bulfur oxides per unit
time. It is passed through a cyclone separator where
95 pounds of catalyst are removed. Therefore,
SE = 100 - 5
100 34 100 — 95/»
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 = 897o
6400
Example 2 - Assume that an organic liquid scrubber is used to wash a
stream containing 50 pounds of SO2 per unit time. All
but one pound of the SO2 is removed but two pounds of
the hydrocarbon evaporate into the vented stream. Then
SE 5°5q 1 *100 = 98%
and SERR = (50 x 20) - (1 x 20 + 2 x 80)
(50 x 20)	x 100
= 10°°0q0180 * 100 = 827=

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