GCA-TR-75-32-G (8)
ASSESSMENT OF FORMALDEHYDE
AS A POTENTIAL AIR POLLUTION PROBLEM
VOLUME VIII
FINAL REPORT
Contract No. 68-02-1337
Task Order No. 8
Prepared For
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park
North Carolina 27711
January 1976
GCA TECHNOLOGY DIVISION
BEDFORD, MASSACHUSETTS 01730
-------
GCA-TR-75-32-G(8)
ASSESSMENT OF FORMALDEHYDE
AS A POTENTIAL AIR POLLUTION PROBLEM
Volume VIII
by
Robert M. Patterson
Mark I. Bornstein
Eric Garshick
GCA CORPORATION
GCA/TECHNOLOGY DIVISION
Bedford, Massachusetts
January 1976
Contract No. 68-02-1337
Task Order No. 8
EPA Project Officer
Michael Jones
EPA Task Officer
Justice Manning
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park
North Carolina 27711
-------
This report was furnished to the U.S. Environmental Protection Agency by the
GCA Corporation, GCA/Technology Division, Bedford, Massachusetts 01730, in
fulfillment of Contract No. 68-02-1337, Task Order No. 8. The opinions,
findings, and conclusions expressed are those of the authors and not neces-
sarily those of the U.S. Environmental Protection Agency or of the cooperating
agencies. Mention of company or product names is not to be considered as an
endorsement by the U.S. Environmental Protection Agency.
-------
ABSTRACT
This report is one of a series which assesses the potential air pollution
impacts of 14 industrial chemicals outside the work environment. Topics
covered in each assessment include physical and chemical properties,
health and welfare effects, ambient concentrations and measurement meth-
i
ods, emission sources, and emission controls. The chemicals investigated
in this report series are:
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
Volume VIII
Volume IX
Volume X
Volume XI
Volume XII
Volume XIII
Volume XIV
Acetylene
Methyl Alcohol
Ethylene Bichloride
Benzene
Acetone
Acrylonitrile
Cyclohexanone
Formaldehyde
Methyl Methacrylate
Ortho-Xylene
Maleic Anhydride
Dimethyl Terephthalate
Adipic Acid
Phthalic Anhydride.
iii
-------
CONTENTS
Page
Abstract
List of Tables
v
Sec t ions
I Summary and Conclusions •,
II Air Pollution Assessment Report 3
Physical and Chemical Properties 3
Health and Welfare Effects 3
Ambient Concentrations and Measurements 9
Sources of Formaldehyde Emissions 12
Formaldehyde Control Methods 14
III References -10
Appendix
A Formaldehyde Manufacturers 21
iv
-------
TABLES
No- page
1 Significant Properties of Formaldehyde 4
2 Acute Sensory Response of Man to Formaldehyde Vapors 4
3 Deaths of Mice From Exposure to Formaldehyde/Aerosol
Mixtures 9
4 Estimated Formaldehyde Consumption - 1974 12
5 Sources and Emission Estimates of Formaldehyde - 1974 13
6 Emission Control Devices - Silver Catalyst Process 16
7 Emission Control Devices - Mixed Oxide Catalyst Process 17
-------
SECTION I
SUMMARY AND CONCLUSIONS
Formaldehyde is a colorless gas with a pungent, irritating odor. It
is produced from methyl alcohol by catalytic vapor-phase oxidation or
by an oxidation-dehydration process, and its main use is as an inter-
mediate in the preparation of explosives, dyes, synthetic lacquers, and
resins. Formaldehyde polymerizes in the presence of air and moisture
to form the solid paraformaldehyde. This solid is easily decomposed
to yield aqueous formaldehyde solutions, x-j-hich are available commer-
cially in a solution containing 37 percent 50 percent formaldehyde
by weight.
Inhalation of formaldehyde at about 10 ppm causes rapid and severe
irritation of the eyes, nose, and upper respiratory tract. The odor
detection threshold is 0.05 ppm, while eye irritation has been reported
at 0.01 ppm. The U.S. occupational standard is 3 ppm for an 8-hour
time weighted average, while the American Conference of Governmental
Industrial Hygienists has recommended a threshold limit value (TLV) of
o
3 mg/m (2 ppm). Aerosols have a synergistic effect on human response
to formaldehyde. Formaldehyde is known to be a component of photochemical
smog formation.
Simple diffusion modeling estimates place the likely maximum 1-hour
average ambient concentration at about 2 ppm. The maximum 24-hour
average ambient concentration might be expecte^d to be about 1 ppm.
These estimates assume a location about 300 meters from the largest
production facility, and are more than 2.5 times the estimated concentra-
tion near the next largest facility. Average ambient concentrations of
0.05 ppm have been measured in Los Angeles, with peak values being about
0.15 ppm.
1
-------
Almost 6 billion pounds of formaldehyde .solution (37 percent formalde-
hyde by weight) were produced in 1974, with about 30 percent of this
being used for the production of urea-formaldehyde resins. Production is
expected to increase at 7.5 percent per year through 1978. Phenolformal-
dehyde resin manufacture consumed about 24 percent of production. The
primary emission sources in descending order are production, end product
manufacture, and bulk storage. Total emissions of formaldehyde are
estimated to have been abput 10 million pounds in 1974.
Emissions from manufacture by the silver catalyst process occur mainly
from the absorber vent gas and the fractionator off-gas vent. These
«•
are uncontrolled at most U.S. plants. Control methods which are currently
used for absorber vent emissions are thermal incineration and redirection
of vent gases to plant boilers for use as a fuel supplement. The only
device reported for the fractionator vent is a water absorber. Systems
that are feasible but not currently employed are plume burners (no
supplemental fuel required) and catalytic incinerators.
Emissions from manufacture by the mixed catalyst process occur primarily
from the absorber vent gas, and one firm is currently controlling these
using a water scrubber. Other feasible control methods are thermal and
catalytic incineration, and a flare system.
Based on the results of health effects research presented in this report,
and the ambient concentration estimates, it appears that formaldehyde in
air may produce eye and respiratory tract irritation in sensitive members
of the general population. This applies especially to those living near
the largest production facility; however, eye irritation from photochemical
smog must be due, in part, to formaldehyde. A small-scale sampling pro-
gram might be undertaken at two or three locations (near the plant and
near the population centroid) in conjunction with a public response sur-
vey to determine ambient concentrations and to determine if irritating
effects are occurring.
-------
SECTION II
AIR POLLUTION ASSESSMENT REPORT
PHYSICAL AND CHEMICAL PROPERTIES
Formaldehyde is a colorless gas with a pungent, irritating odor. Its
aqueous solution is referred to as formalin. Industrially it is made
from methanol by catalytic vapor-phase oxidation or by an oxidation-
dehydration process. Its largest use is as an intermediate in the
preparation of explosives, dyes, synthetic lacquers, and resins. Because
of its antiseptic properties it is used in the medical, brewing, and agri-
cultural industries.
In the presence of air and moisture at room temperature, formaldehyde
polymerizes to paraformaldehyde, a solid with the molecular formula
(CH~0) H-0. The polymer can be easily decomposed to yield aqueous
formaldehyde solutions. Commercially, formaldehyde is available in a
37 percent - 50 percent by weight aqueous solution, with up to 15 per-
cent methanol added to prevent polymerization. The toxicity of
2
paraformaldehyde is similar to that of formaldehyde. Significant
physical properties are listed in Table 1.
HEALTH AND WELFARE EFFECTS
Effects on Man
Acute Poisoning Human sensory response to formaldehyde inhalation is
summarized in Table 2. The inhalation of formaldehyde even at low
-------
Table 1. SIGNIFICANT PROPERTIES OF FORMALDEHYDE
Synonyms
Methanal, oxumethane, oxymethane
Chemical formula
Molecular weight
Boiling point
Vapor density
Solubility
Explosive limits
Ignition temperature
Flash point of a 37% formaldehyde
solution with 15% methanol
At 25°C and 760 mm-Hg
HCHO
30.03
-19.5°C
1.067 (air = 1)
Very soluble in water, alcohol, ether,
and most organic solvents
7% to 72% by volume in air
136°C
50°C (closed- cup)
1 ppm vapor = 1.227 mg/m
1 mg/m vapor = 0.815 ppm
Table 2. ACUTE SENSORY RESPONSE OF MAN TO FORMALDEHYDE VAPORS
Dose,
ppm
0.01
0.05
0.5
1.0
2.0-3.0
4.0-5.0
10.0
10.0-20.0
20.0
20.0
20.0
50-100
Time
5 min.
8 hours
10-30 min.
few min.
15-30 sec.
30 sec.
1-2 min.
5-10 min.
Response
Eye irritation threshold
Odor threshold
Throat irritation
Detectable by nearly all people
Tolerable; mild irritation of eyes,
nose, and posterior pharynx
Intolerable to most people;
mild lachrymation;
throat irritation
Profuse lachrymation
Burning of nose, throat, trachea;
coughing
Lachrymation
Nose and throat irritation
Sneezing
May cause serious injury;
serious bronchial inflammation
Ref.
3
4
4
5
5
5,6
5
5
7
7
7
5
-------
concentrations causes rapid and severe irritation of the eyes, nose,
and other portions of the upper respiratory tract. Symptoms of ex-
posure may include lachrymation, sneezing, coughing, a feeling of
suffocation, rapid pulse, headache, and fluctuations in body temper-
ature. A concentration of 0.01 ppm is the lowest reported eye irrita-
tion value, and 0.05 ppm is the lowest reported value for the detection
of the odor. People acclimated to exposure may not complain of irrita-
tion until concentrations above 1 ppm are reached as is the case in
most industrial exposure. Men exposed to 13.8 ppm for 30 minutes
tolerated the exposure, despite considerable nasal and eye irritation
and lachrymation. The eye irritation was not severe and wore off after
Q
10 minutes in the test chamber. Sensory response to formaldehyde will
vary among individuals, with the values in Table 2 given as typical
lower limits.
At exposure to between 10 and 20 ppm, normal breathing becomes difficult.
Lachrymation subsides promptly after removal from exposure, but nasal
and respiratory irritation may persist for an hour. Inhalation of higher
concentrations can cause laryngitis, bronchitis, and bronchopneumonia.
The vapor may cause skin irritation, but skin rensitization to formalde-
hyde in the vapor state is rare. Individuals who have already developed
a sensitivity to formalin will show skin irritation upon exposure to
gaseous formaldehyde.
No significant toxic effects from oral exposure were seen in humans
despite the daily ingestion of 22 to 200 mg over a period of 13 weeks.
Higher doses caused moderate irritation of the upper digestive tract.
Very high doses may result in respiratory depression and death.
Chronic Poisoning - The U.S. occupational standard for exposure to
formaldehyde is 3 ppm for an 8-hour time weighted average, with ex-
9
posure between 5 ppm and 10 ppm permissible for 30 minutes. The
-------
American Conference of Governmental Industrial llygicnists just reduced
their recommended threshold limit value from 5 ppm to 2 ppm for an
8-hour workday. These standards are based on acute sensory response
data and are low enough to prevent respiratory damage, but they may not
be low enough to prevent all chronic irritation.
Recent studies indicate chronic exposure to formaldehyde below 2 or
3 ppm may cause health problems. A Russian study mentions hypotonicity,
chronic anxiety neurosis, and neurocirculatory asthenia among workers
chronically exposed to concentrations of 0.48 ppm. There have been
complaints in fabric shops where the concentration has been measured
12
at 0.13 to 0.45 ppm. A study of einbalmers exposed to average concen-
trations varying -from 0.25 to 1.30 ppm daily shows a high incidence of
respiratory irritation such as eye and nose burns, sneezing, coughing,
and headaches. Sleepiness, weakness, and tightness in the chest
were not encountered; these are characteristics of higher, more toxic
concentrations.
Dermatitis is only seen in chronic vapor exposure when people have
had previous exposure to formalin or paraformaldehyde powder for
sensitization.
Effects on Animals
Acute Poisoning - Animal studies reveal that in addition to causing
severe eye and respiratory tract irritation, the inhalation of high
concentrations of formaldehyde vapor may result in lung injury and
damage to other organs. In one study the LC,-n for rats for a 30-minute
13
inhalation exposure was determined to be 800 ppm. Rats exposed to
such concentrations became listless and showed lachrymation with in-
creased secretion from the nose. Autopsies typically revealed hemor-
rhages and pulmonary edema, and signs of kidney and liver damage.
Death was due to lung injury, not to an induced narcotic effect on the
-------
central nervous system. Those rats that survived appeared to recover
normally in 2 to 3 days. Groups of 50 mice, 20 .guinea pigs, and 5
rabbits were exposed to 16 ppm for 10 hours. ' Deaths took place
after exposure, with autopsies showing expanded edematous and hemor-
rhagic lungs, fluid in the pleural and peritoneal cavities, distended
alveoli, ruptured alveolar walls, and enlarged livers. A concentration
of 250 ppm inhaled over 4 hours caused death in rats.
Low levels of formaldehyde can cause cessation of ciliary activity.
Exposure to 3 ppm for 50 seconds or 0.5 ppm for 150 seconds caused
cessation of the ciliary beat in the respiratory tract in anesthetized,
tracheotomized rats.
Chronic Poisoning Fifteen rats, thirteen rabbits, three monkeys and
two dogs were exposed continuously for 90 days to 3.8 ppm formalde-
hyde vapor. Only one rat died, with the other animals showing normal
hematological values and no signs of illness. The lungs of all exposed
species showed varying degrees of interstitial inflammation.
Pregnant rats were continuously exposed to 0.1 ppm and 0.83 ppm formalde-
hyde vapor. The mean duration of pregnancy was prolonged 14 to 15
percent as compared to pregnant control rats, with a decrease in the
number of fetuses per female at 0.83 ppm. The lungs and liver, the
organs directly affected by inhalation, weighed less than those of the
control offspring. More work must be done in determining the toxic
effects of chronic exposure to formaldehyde and relating the results
to set chronic exposure standards for humans.
Effects on Vegctation
Not many studies have been done illustrating the phytotoxicity of
formaldehyde. Alfalfa was not damaged after exposure to 2 ppm for
2 hours, but there was some leaf damage after exposure to 0.7 ppm for
-------
1 R
5 hours. Irradiation of formaldehyde at 5.6 and 6.1 ppm for 4 hours
with nitrogen oxides present did not damage pinto beans, tobacco wrapper,
!9
and petunias.
A Russian study indicates that some plants may be sensitive to formalde-
3 20
hyde concentrations in the magnitude of 0.017 ppm (0.02 mg/m ). This
value represents the formaldehyde concentration that did not produce a
decrease in photosynthesis in several tree species during a 5-minute
exposure.
Other Effects
Formaldehyde and Aerosols The effects of formaldehyde inhalation may
be increased in the presence of an aerosol. Mice were exposed to
21
12.5 ppm formaldehyde in the presence of nine different aerosols.
The formaldehyde/aerosol mixtures had a synergistic effect, resulting
in an increase in deaths and the severity of pulmonary edema. Specific
results of the study are shown in Table 3.
Guinea pigs were exposed to formaldehyde concentrations between 0.07
3
and 47 ppm with and without the presence of 10,000 pg/m 0.04-micron
22
diameter sodium chloride aerosol. Statistically significant increases
in "respiratory work" were found as a result of aerosol exposure with
a formaldehyde concentration above 0.3 ppm. The formaldehyde/aerosol
mixture delayed recovery after discontinuation of exposure. The in-
creased toxicity may be due to the concentrating effect of the aerosol
on formaldehyde, resulting in locally high formaldehyde levels on each
aerosol.
Formaldehyde and Photochemical Smog Formaldehyde is a product of the
atmospheric photochemical reactions of many hydrocarbons, and it serves
as an indication of the intensity of smog as measured by eye irritation.
It can be photooxidized with a nitrogen oxide mixture in air to yield
23
ozone, toxic to man and implicated in plant damage.
-------
Table 3. DEATHS OF MICE FROM EXPOSURE TO
FORMALDEHYDE/AEROSOL MIXTURES21
Aerosol
Triethylene glycol
Ethylene glycol
Mineral oil
Glycerin
Sodium chloride
Dicalite
Diatomaceous earth
Absorptive clay
Silica gel
Size,
microns
1.8
2.0
2.1
2.0
2.6
3.3
2.9
3.3
2.7
Aerosol
concentration,
Ug/liter
2,210
2,920
1,420
1,280
2,320
420
360
960
310
ST50'a
min
71
168
72
114
114
118
102
157
145
Significance of
increased
death rate
-H-
0
4+
+
+
+
•H-
0
0
ST - is the time for 50 percent survival of mice. For 12.5 ppm
formaldehyde in the absence of aerosols, the ST,-n was 147 minutes.
Significance code:
0 = no significance
+ = significant
H- = highly significant.
AMBIENT CONCENTRATIONS AND MEASUREMENTS
Formaldehyde concentrations in Los Angeles on 26 days from September
24
25
through October 1966 averaged 0.05 to 0.12 ppm.*''"' Earlier measurements'
in the fall of 1961 averaged 0.04 ppm with the average daily maximum
0.06 ppm. About 13 percent of the daily maximum values were over 0.10 ppm,
and the highest concentration measured during the period was 0.16 ppm.
Ambient Concentration Estimates
The largest installation for formaldehyde production is located in a
town of about 3,700 population, and it has a capacity of about 1,300
million Ib/yr. Assuming a 0.1 percent loss, this converts to an emis-
sion rate of:
-------
(0.001 emission factor) (1300 x 1Q6 Ib/yr) (453.6 g/lb)
3.1536 x 107 sec/yr
= 18.7 g/sec of formaldehyde.
Some assumptions must be made regarding this formaldehyde release to
the atmosphere. First of all, the emissions do not all come from one
source location, but rather from a number of locations within the plant
where formaldehyde leaks to the atmosphere. Thus, the emissions can
be characterized as coming from an area source which will be taken to
be 100 meters on a side. Secondly, the emissions occur at different
heights, and an average emission height of 10 meters is assumed.
Ground level concentrations can then be estimated at locations downwind
26
of the facility. To do this a virtual point source of emission is
assumed upwind of the facility at a distance where the initial horizontal
dispersion coefficient equals the length of a side of the area divided
by 4.3. In this case:
o- = 100m/4.3 = 23.3m
yo
Assuming neutral stability conditions (Pasquill-Giff^rd Stability
Class D) with overcast skies and light winds, the upwind distance of
the virtual point source is approximately 310 meters. With consideration
of the plant boundary, it is reasonable to assume that the nearest
receptor location is thus about 500 meters from the virtual point
source. Finally, taking 2 m/sec as an average wind speed, the ground
level concentration may be calculated from:
un0yoz
10
-------
or / ,„ \2
i. / 10
] g 7 _> - [
(2) ir (36") (18.5) e ' \18'5
= 3.86 x 10~3 g/m3
for a 10-minute average concentration. Over a period of an hour this
becomes 3.86 x 10~3 g/m3 (0.72) = 2.78 x 10~3 g/m3 or 2.3 ppm 1-hour
average concentration. Over a 24-hour period, the average concentration
might roughly be expected to be about 1.3 ppra.
Measurement Techniques
Several methods are available for measuring formaldehyde concentrations
in ambient air and from emission sources. The source methods are the
potassium hydroxide method, the sodium bisulfite method, the acidified
'distilled water method and the methylatnine hydrochloride method. The
ambient air sampling procedures are the phenylhydrazine hydrochloride
method, and the water method. Specific details of the ambient air
sampling procedures are given below.
Formaldehyde in concentrations from 2 to 20 ppm can be determined by
27
collection in a solution of phenylhydrazine hydrochloride. After
the sample is collected it is treated with potassium ferricyanide
and hydrochloric acid. The resulting magenta-stained solution is read on
a spectrophotometer at 515 rapt and is compared to a calibration curve.
Iron in any form will interfere, and other aldehydes will cause some
degree of interference.
Another method for determining formaldehyde concentrations involves
28
collecting the air sample in a midget impinger containing water.
A solution of sodium sulfite in sodium tetrachloromercuratc is added
to the sample, followed by addition of an acidic solution of
pararosaniline hydrochloride, which produces a blue-violet color.
11
-------
The color is then read on a spcctrophotomctcr at 560 mp. This method
is accurate to 0.01 ppm. The only interferences are from acetaldehyde
and propionaldehyde.
SOURCES OF FORMALDEHYDE EMISSIONS
Formaldehyde Production and Consumption
The production of formaldehyde in solution in 1974 was 5,846 million
29
pounds (37 percent formaldehyde by weight) and is expected to increase
30
at 7.5 percent per year through 1978. The largest end use of formal-
dehyde is for the production of urea-formaldehyde resins, accounting for
30 percent of total production. Urea-formaldehyde is primarily used in
adhesives, textile, and paper treating and coating; and in surface coat-
ings as a cross linking agent. Phenol-formaldehyde resin, the second
largest end use for formaldehyde, consumed an estimated 24 percent of the
total production. It is primarily used as an adhesive for the plywood
industry. The consumption of formaldehyde for all other end products is
shown in Table 4. This table also shows the expected growth rates for
each sector of the market.
Table 4. ESTIMATED FORMALDEHYDE CONSUMPTION - 1974
31
"rca-formaldchytic resins
I'lienoJ-fovRvildC'liyde resins
tfi'lnmine-forronldehydc resins
Pent.iorylhritol
Hex jme thy lone cot ramine
Acctnl resins
Uri ;i-f orr,!,-> 1 deliyde concent rates
Acrylic esters
Tr i i.v tlivl ul ptop.'ine
Text i !.<• nv.-i; ini; applications
T'.-l r.ihyJrotumn
Cln- !,:! ii'i- ;l;ynt
Ac dy U' a U: clu-micals
4 , 4-i'iit.iyJeiK'iH.ini line
Pinei-
ro I ;il
Millions of
pounds solution
1,728
1,420
223
367
339
511
142
81
95
104
189
18<>
lay
142
J27
5, «•'>(>
% annual
growth
12
7
5
3.5
6
8
3
0
8
3
7
7
5
5
5
7.5
12
-------
Formaldehyde! Sources and Emission Kstimates
Primary sources of emissions of formaldehyde occur from formaldehyde pro-
duction, end product manufacturing, and bulk storage. Total emissions of
formaldehyde are estimated to be 10.14 million pounds (100 percent formal-
dehyde), representing 0.47 percent of total production. Table 5 shows the
breakdown by source type.
Table 5. SOURCES AND EMISSION ESTIMATES OF FORMALDEHYDE - 1974
Formaldehyde production
Silver catalyst process
Mixed oxide catalyst process
End product manufacture
Bulk storage
Total
Million pounds-
100% basis
5.04
4.50
0.54
10.14
The major source of emissions of formaldehyde results from formaldehyde
production. Formaldehyde is produced solely from methanol in the United
States. Two processes are dominant, the mixed oxide catalyst process
and the silver catalyst process, the latter accounting for an estimated
77 percent of the total production. Currently, 35 plants are using the
silver catalyst process and 19 plants are using the mixed oxide catalyst
process. Names and locations of the production facilities are listed in
Appendix A.
A study concerning emissions from the formaldehyde industry has recently
estimated losses from both processes.30'32 It is reported that approxi-
mately 0.001 pounds of formaldehyde are lost from the absorber vent gas
and the fractionator off-gas vent per pound of formaldehyde solution pro-
32
duced using the silver catalyst process. Using this factor and the
13
-------
production figure for this process (4.5 billion pounds) results in 4.5
million pounds of formaldehyde emitted.
The emission factor reported for the mixed oxide catalyst process is
0.0004 pounds lost per pound of formaldehyde solution produced. Using
this factor and the estimated production (1.345 billion pounds) by this
process results in 0.54 million pounds of formaldehyde lost to the
atmosphere.
Since there are no data readily available in the. literature concerning
emissions of formaldehyde from end product manufacturing, it is estimated
that emissions from this category will be similar to emissions from
formaldehyde products; or 5.04 million pounds.
The last major emission source is from bulk storage. It has been reported
that most tanks storing formaldehyde do not use any type of control
equipment, and have an emission rate of 0.00001 pound emitted per pound
stored. Using this factor, total evaporative emissions are 0.06 million
pounds.
FORMALDEHYDE CONTROL METHODS
It appears from information reported in two recent studies that the
30 32
majority of U.S. plants do not employ emission control devices. '
However, in a few isolated cases some control devices are used and are
described below.
Emissions from the silver catalyst process are primarily from the absorber
vent and the product fractionator vent. Control devices that are currently
used on the absorber vent are thermal incinerators and the redirection
of the vent gases (both 99+ percent efficient) to the plant boiler as a
fuel supplement. The only control device currently reported for the frac-
tionator vent j.s a water absorber (94 percent efficient).
14
-------
Systems that are feasible but not currently employed are plume burners and
catalytic incinerators
presented in Table 6.'
catalytic incinerators. Cost data for all five methods of control are
32
Emissions from the mixed catalyst process result primarily from the
absorber vent gas. It has been reported that only one firm is currently
30
using control equipment on this stream: a water scrubber. The effi-
ciency of this equipment is indicated to be approximately 67 percent.
Other systems that are currently feasible but not employed are thermal
incinerators, catalytic incinerators, and a flare system. Cost data
30
and their expected efficiencies are presented in Table 7.
15
-------
Table 6. EMISSION CONTROL DEVICES - SILVER CATALYST PROCESS
a,32
Number of units
Capacity of each unit, %
Feed
Total flow, Ib/hr
scfm
Combined effluent
Total flow, Ib/hr
scfm
Total capital investment, $
Total operating cost, $/yr
Efficiency, %
Type of emission control device
Water
scrubber
1
100
8,146
2,170
8,109
2,163
28,700
10,420
94.6
Thermal
incinerator
1
100
8,146
2,170
15,132
3,515
58,500
12,840
99+
Catalytic
incinerator
1
100
8,146
2,170
22,979
5,244
54,700
17,920
99+
Plume
burner
1
100
8,146
2,170
>2,200
35,600
8,640
89+
Boiler house
vent gas burner
7
8,146
2,170
15,000
3,500
55,900
-3,940
99+
*j
Costs updated to first quarter of 1975.
Note: Values based on 100 MM Ib/yr formaldehyde production.
-------
o -
Table 7. EMISSION CONTROL DEVICES - MIXED OXIDE CATALYST PROCESS '
Number of units
Capacity of each unit, %
Feed
Total flow, Ib/hr
scfm
Combined effluent
Total flow, Ib/hr
scfm
Total capital investment, $
Total operating cost, $/yr
Efficiency, %
Type of emission control device
Thermal incinerator
No heat recovery
1
100
14,968
3,390
21,145
4,790
68,600
46,500
99+
40% heat recovery
1
100
14,968
3,390
21,145
4,790
86,400
37,600
99+
Catalytic
incinerator
1
100
14,968
3,390
18,885
4,270
38,100
33,900
99+
Flare
system
1
100
14,968
3,390
18,885
4,270
36,900
40,300
90
Water
scrubber
1
100
14,968
3,390
14,943
3,385
102,900
25,300
65
Costs updated to first quarter of 1975.
Note: Values based on 100 MM Ib/yr formaldehyde production.
-------
SECTION III
REFERENCES
1. Chemical Technology: An Encyclopedia Treatment. Volume IV.
Petroleum and Organic Chemicals, pp 538-39. Barnes and Noble
Books, New York, 1972.
t
2. American Industrial Hygiene Association: Hygienic Guide Series.
Formaldehyde. Amer Ind I-Iyg Assoc J. 26:189-92, 1965.
3. Schuck, E.A., E.R. Stephens, J.T. Middleton. Eye Irritation
Response at Lew Concentration of Irritants. Arch Environ Health.
13:570-75, 1966.
4. Stern, A.C. (ed). Air Pollution. Academic Press, New York,
1:484, 1968.
5. Fassett, D.W. Aldehydes and Acetals. In Patty, F.A. (ed.).
Industrial Hygiene and Toxicology. Interscience Publishers, New
York, 2:1970-72, 1963.
6. Preliminary Air Pollution Survey of Aldehydes. A Literature Review.
National Air Pollution Control Administration Publication No. APTD
69-24, 1969.
7. Barnes, E.G., H.W. Speicher. The Determination of Formaldehyde in
Air. J Ind Hyg Toxicol. 24:10-17, 1942.
8. Sim, U. M., R. E. Pattle. Effect of Possible Smog Irritants on
Human Subjects. J Am Med Assoc. 165:1908-13, 1957.
9. The Toxic Substances List - 1974 Edition. HEW Publication No.
(NIOSH) 74-134. p. 371.
10. Kerfoot, E. J., T. F. Mooney. Formaldehyde and Paraformaldehyde
Study in Funeral Homes. Amer Ind Hyg Assoc J. 36:533-37, 1975.
11. Shafaizier, U. In: Formaldehyde: How Much of a Hazard. Ahmad, I.
and T. C. Whitson. Ind Med Surg. 42:26-27, 1973.
18
-------
12. Bourne, H. C., Jr. and S. Scfcrian. Formaldehyde in Wrinkle-Proof
Apparel Produces Tears for Milady. Ind Med Surg. 28:232-233, 1959.
13. Skog, E. A lexicological Investigation of Lower Aliphatic Aldehydes.
I. Toxicity of Formaldehyde, Acetaldehyde Propionaldehyde and
Butyraldehyde; as well as of Acrolcin and Crontonaldehyde. Acta
Pharmacol. 6:299-318, 1950.
14. Salem, H., and H. Collumbine. Inhalation Toxicities of Some
Aldehydes. Toxicol Appl Pharcamol. 2:183-87, 1960.
15. Dalhman, T. Mucous Flow and Ciliary Activity in the Trachea
of Healthy Rats and Rats Exposed to Respiratory Irritant Gases.
Acta Physiol Scand. 36: Suppl. 123, 1956.
16. Coon, R.A., R.A. Jones, L.J. Jenkins, Jr., and J. Siegel.
Animal Inhalation Studies on Ammonia, Ethyle'ne Glycol, Formaldehyde,
Dimenthylanime, and Ethanol. Toxicol Appl. Pharmacol. 16:646-655,
1970.
17. Gofmekler, V.A. Effect of Embryonic Development of Benzene and
Formaldehyde in Inhalation Experiments (Embriotropnoe Deistvie
Benzola i Formal 'Degiela Pri Ingalyatsionnom Puti Vozdaistviya v
Eksperimente.) Hyg Sanit. 33:327-332, January-March 1968.
18. Haagen-Smit, A.M., E.F. Daily, M. Zaitlin, H. Hull, and W. Noble.
Investigation On Injury to Plants From Air Pollution in the Los
Angeles Area. Plant Physiol. 27:18-33, 1952.
19. Hindawi, I.J., A.P. Altshuller. Plant Damage Caused by Irradiation
of Aldehydes. Science 146:540-542, 1964.
20. Nikolayevsiy, V.S., A.T. Mirashnikova. The Air Pollution Levels
Permissible for Plants. (Dopustirayye Normy Zagryazneniya Vozdikha
Dlya Rasteniy). Gigiena I Sanit. 4:16-18, 1974.
21. LaBelle, C.W., J.E. Long, and E.E. Christofano. Synergistic Effects
of Aerosols. Arch Ind Health.. 11:297-304, 1955.
22. Amdur, M.O. The Physiological Response of Guinea Pigs to Atmos-
pheric Pollutants. Int J Air Water Pollution. 1:170-183, 1959.
23. Air Quality Criteria for Photochemical Oxidants. National Air
Pollution Control Administration Publication No. AP-63, 1970.
24. Air Quality Criteria for Hydrocarbons. U.S. Department of Health,
Education, and Welfare. Publication No. AP-64. 1970.
19
-------
25. Altshuller, A.P., L.J. Lcng, and A.F. Wartburg. Source and Atmo-
spheric Analyses for Formaldehyde by Chromotropic Acid Procedures.
Air and Water Pollu. 6:381-385, 1962.
26. Turner, D. Bruce. Workbook of Atmospheric Dispersion Estimates.
U.S. Environmental Protection Agency - AP-26, January 1973.
27. Hanson, N. , D. Reilly, and H. Stagg. The Determination of Toxic
Substances in Air. W. Heffer and Sons Ltd., 1965.
28. Lyles, G., F. Dowling, and V. Blanchard. Quantitative Determination
of Formaldehyde in the Parts per Hundred Million Concentration
Level, J Air Pollu Control Assoc. 15:106, 1965.
29. U.S. International Trade Commission, Preliminary Report on U.S.
Production of Selected Synthetic Organic Chemicals, May 1975.
30. Engineering and Cost Study of Air Pollution Control for the Petro-
chemical Industry, Volume 5: Formaldehyde Manufacture with the
Mixed Oxide Catalyst Process. EPA 450/3-73-006e. March 1975.
31. Chemical Economics Handbook - Stanford Research Institute, July 1974.
32. Engineering and Cost Study of Air Pollution Control for the Petro-
chemical Industry, Volume 4: Formaldehyde Manufacture with the
Silver Catalyst Process. EPA 450/3-73~006d. March 1975.
20
-------
APPENDIX A
FORMALDEHYDE MANUFACTURERS
30
Capacity,
million pounds/year
Allied
Borden
Celanese
Commercial Solvents
Du Pont
GAF
Georgia Pacific
Ironton, Ohio
Deraopolis, Ala.
Diboll, Texas
Fayetteville, N.C.
Fremont, Calif.
Kent, Wash.
La Grande, Oregon
Louisville, Ky.
Missoula, Mont.
Sheboygan, Wise.
Springfield, Oregon
Bishop, Texas
Newark, N.J.
Rock Hill, S.C.
Sterlington, La.
Seiple, Pa.
Belle, W.Va.
Grasselli, N.J.
Healing Spring, N.C.
La Porte, Texas
Toledo, Ohio
Linden, N.J.
Calvert City, Ky.
Columbus, Ohio
Coos Bay, Oregon
Crosett, Ark.
Albany, Oregon
Taylorsville, Miss.
Vienna, Ga.
Silver
process
308
80
70
200
80
70
40
70
80
120
260
1,300
30
80
485
150
200
200
320
150
Metal oxide
process
100
100
117
117
100
100
80
60
100
100
21
-------
FORMALDEHYDE MANUFACTURERS (continued)
Capacity,
million pounds/year
Gulf
Hercules
Hooker
Monsanto
Reichhold
Rohm & Haas
Skelly
Tenneco
Union Carbide
Wright
Total
Vicksburg, Miss.
Louisiana, Mo.
Wilmington, N.C.
N. Tonawanda, N.Y.
Alvin, Texas
Addyston, Ohio
Eugene, Oregon
Springfield, Mass.
Hamp ton, 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.
Bound Brook, N.J.
Acme, N.C.
Silver
process
170
95
135
150
110
100
280
36
70
40
25
105
105
Metal oxide
process
40
100
100
40
50
100
70
70
160
150
75
5,914 1,729
22
------- |