Journal of the Air Pollution Control Association

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A Caustic Scrubber System for the Control

of Phosgene Emissions: Design, Testing, and
Performance

Stephen Kistner , Daniel Lillian , John Ursillo , Norval Smith , Kenneth

Sexton , Michael Tuggle , George Esposito , George Podolak & Steven Mallen

To cite this article: Stephen Kistner , Daniel Lillian , John Ursillo , Norval Smith , Kenneth Sexton ,
Michael Tuggle , George Esposito , George Podolak & Steven Mallen (1978) A Caustic Scrubber
System for the Control of Phosgene Emissions: Design, Testing, and Performance, Journal of the
Air Pollution Control Association, 28:7, 673-676, DOI: 10.1080/00022470.1978.10470644

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 A Caustic Scrubber System for the
Control of Phosgene Emissions:
Design, Testing, and Performance
Stephen Kistner, Daniel Lillian, John Ursillo,
Norval Smith, Kenneth Sexton, Michael Tuggle,
George Esposito, George Podolak, Steven Mallen
U. S. Army Environmental Hygiene Agency,
Aberdeen Proving Ground, Maryland
The body of information presented in this paper is directed toward
those individuals involved with handling hazardous materials, whether
in actual use of such chemicals, or in monitoring atmospheric emis-
sions. Although specifically relating experience in the design and
testing of phosgene emission control equipment, it attempts to es-
tablish general guidelines for effectively dealing with emissions of
hazardous materials. An approach for handling chemical pollutants
having no established air quality emission standards is developed.
The paper presents a technique for establishing process emissions
at acceptably low levels to insure the health and safety of the general
population as well as that of the process workers themselves.
Methods, suitable for measuring phosgene at these low levels, have
been investigated, and problems associated with such an investigation
are discussed. While complete theoretical scrubber design criteria
are beyond the scope of this paper, many of the "real world" problems
which affected scrubber performance are presented. Finally, the
practical aspects of process emissions control are illustrated by actual
results from the system test.
In its demilitarization program to dispose of obsolete and
retrograde chemical agents and munitions, the U. S. Army is
often faced with unique engineering and environmental
challenges. In many instances these problems are unprece-
dented in nature and not specifically covered by State and/or
Federal guidelines and regulations. Similar to industries de-
veloping new technology, processes, and prototypes, the Army
must develop cost-effective air pollution control systems when
the potential exists for emissions of deleterious compounds.
In consonance with Army Regulation 200-1 which mandates
the overall policy of the Army regarding environmental
matters, considerable emphasis is placed on environmental
safeguards, incorporating state of the art technology into the
design of the control systems, the establishment of emission
guidelines, and the development of comprehensive emissions
monitoring programs. The ongoing demilitarization of some
2 million pounds of phosgene stockpiled at Rocky Mountain
July 1978 Volume 28, No. 7
Arsenal (RMA), Colorado, is an illustrative example of a
comprehensive, environmentally conservative, and accord-
ingly, a successful program to control emissions of a hazardous
substance. Many of the principles developed and much of the
technology evaluated in this program should experience wide
application for controlling emissions of hazardous air pollu-
tants in general, with specific application to the rapidly
growing phosgene industry with a projected 1978 demand of
1.63 billion lb.
General
Phosgene (or carbonyl chloride) was originally purchased
by the Army as a chemical warfare agent. In the early 1960's
this chemical was declared an obsolete agent. Approximately
7.7 million lb of phosgene were collected from the demilitar-
ization of munitions at RMA during the period from No-
vember 1965 to February 1967 and sold to two purchasers.
These two companies shipped approximately 5.7 million lb
using commercial transportation before shipments were
suspended in 1969 with the enactment of public laws (PL)
91-121 and 91-441 which mandated the detoxification of
chemical warfare agents prior to transport. Accordingly, the
balance of approximately 2 million lb or 1294 ton containers
(TC) of the carbonyl chloride at RMA reverted to government
control. In October 1973, the Department of Defense an-
nounced that all lethal agents and munitions at RMA would
undergo disposal action. Subsequently, specific Congressional
approval was obtained which permitted disposition of the
phosgene by sale, providing that stringent requirements were
met to insure safety considerations and environmental in-
tegrity in its transport.
For the commercial sale and transportation of the phosgene
stored at RMA, the TC's had to be modified and tested to
meet Department of Transportation specification 106A500X,
agent R. M. Graziano's Tariff No. 29, ("Hazardous Materials
Regulation of the Department of Transportation").1 Such
modification and testing required empty containers, and ac-
cordingly, a means and system for transferring phosgene from
Copyright 1978-Air Pollution Control Association
673
donor TC's to modified and tested receiver TC's had to be
developed. When working with a relatively hazardous com-
pound such as phosgene, even a rather simple hydrostatic
transfer from a donor TC to a receiver TC required detailed
evaluations of potential emission ranges corresponding to
normal phosgene transfer, emission ranges corresponding to
maximum credible accident (MCA), and resulting downwind
ground level phosgene concentrations which would be envi-
ronmentally acceptable. And finally, a candidate control
system had to be developed which could accommodate, with
a margin of safety, the projected phosgene challenge and
provide the required level of control.
Emission Guidelines
The initial step in the solution to a problem of this nature
is to determine just what degree of control is required to insure
a completely safe operation. Since it is the Army's policy to
comply with all applicable air quality standards in conducting
such operations, Colorado's Regulation No. 8, "Regulation to
Control Emissions of Chemical Substances and Physical
Agents,"2 was applicable. Briefly, this regulation uses a value
of y3oth of the Threshold Limit Value (TLV) as the supposed
maximum ground level concentration not to be exceeded
downwind of the emission point. From this value, the esti-
mated plume rise, and predictive modeling techniques, an
allowable emission rate for the process of interest is calculated.
Using the TLV for phosgene of 0.2 mg/m3 along with the es-
timated effective stack height for the stack to be employed,
the calculation resulted in a maximum allowable emission rate
of 536 mg/sec (with subsequent blower design resulting in a
maximum stack concentration of 114 mg/m3). However, a
review of the methodology employed in Regulation No. 8 re-
quired that this approach be modified. The nomograph pro-
vided to assist in the determination of the allowable emission
rate is predicated on the assumption that the existing mete-
orology is approximately D stability with a wind speed of 4
m/sec. However, as more severe meteorology is applied to the
situation, that is, as wind speeds become less than 4 m/sec
and/or atmospheric conditions become more unstable, ground
level concentrations greater than Vsoth of the TLV will result.
Accordingly, to insure that a ground level concentration
greater than Vaoth of the TLV is not exceeded during adverse
meteorological conditions, further dispersion modeling was
conducted using Turner's fumigation model.3 This modeling
established a maximum allowable stack concentration of 50
mg/m3. Additionally, to afford operational implementation
of this emission guideline, a tiered control strategy was es-
tablished. Thus for an emission concentration of 20 mg/m3,
remedial action would be initiated; for an emission concen-
tration of 40 mg/m3, shutdown procedures would commence
so that an emission concentration of 50 mg/m3 would never
be exceeded.
Analytical Methods
One of the major concerns in the establishment of an air
emission control program for a hazardous substance is the

Table I. Methods comparison.

Specifi- NIOSH- Manual Automated

cation recommended10 colorimetry colorimetry Gas chromatography Infrared spec. Tape monitor

Alarm set for 0.2 ppm none none, but adapt- none none, but adaptable yes
able
Response <90 sec for 30 min (samp./ 10-20 min 3—6 min 30 sec 5—15 sec
time alarm anal.)
Drift <l%fullscalein drift corrected l%/24 hr >l%/24hr <l%/24hr <l%/24 hr
24 hr
Noise <l%fullscale 0.5% 1% 10% at 0.2 ppm F. S. 0.25%
Accuracy ±10% of signal, ±20% ±15% ±15% i ±10% ±15%
0.05 to 0.4
ppm
Precision ±5% fullscale ±15% ±6% ±10% ±4% ±6%
Specificity if interferences, specific specific specific trichloroethylene, specific
known response known
responses
Operating 0—0.4 ppm 0—0.4 ppm 0—0.4 ppm 0—0.4 ppm 0—0.4 ppm 0—0.4 ppm
range
Operation 168 hr contin- 24 hr contin- 8 hr continuous with 168 hr continuous 168 hr continuous
uous uous auto sampling
valve
Explosion safe in explosion yes, with G2- yes, with G2- no yes, with G2- yes
hazard hazard areas approved approved approved
pump pump pump
Detection <0.05 ppm 0.05 ppm 0.001 ppm 0.0001 ppm 0.02 ppm 0.005 ppm
limit
Operating 25 ppm 1 ppm 5 ppm 300 ppm 40 ppm
limit
Calibr. 30 days 24 hr 8hr 7 days 7 days
freq.
Operator every 30 min once daily manual op.: con- once weekly — daily once weekly — daily
attention stant; automated: checks recommended checks recommended
once daily
Downtime none occasional occasional very infrequent very infrequent
Sample 1 1pm 1 lpm 0.5 cc injection 2-5 lpm 0.4 lpm
rate
Operator minimal moderate skilled minimal minimal
expertise
Portability depends on portable — portable portable portable
spectro- 150 1b
photometer

674 Journal of the Air Pollution Control Association

 Monitoring Monitoring
po nt
Primary l Secondary point
tower
Transfer
booths
To
atmosphere
Ventilation
Container
hold
room
Scrubbing
liquor sump
Figure 1. Phosgene scrubber system schematic.
availability of a suitable monitoring technique. The ideal
process in-stack monitor should be sensitive enough to mea-
sure below the established guidelines, real time, relatively
accurate, continuous, simple to operate, and able to withstand
the conditions which exist in the work area environment. For
the purposes of monitoring phosgene from the transfer op-
eration, five different methods were investigated.4 Initially,
the techniques studied in the laboratory were infrared spec-
troscopy, gas chromatography, automated colorimetry, di-
ethylphthalate (DEP) bubblers, and a colorimetric tape
monitoring method. Standard phosgene concentrations were
obtained from permeation tubes, and potential interferences
from ammonia, trichloroethylene, water vapor, carbon diox-
ide, and hydrogen chloride were examined. Also, to assess
these analytical methods under more realistic conditions, they
were evaluated on a common manifold at RMA.5 Tests in-
cluded mixing phosgene from permeation tubes and/or cyl-
inders with air from a caustic scrubber to simulate an inter-
ferent matrix frequently associated with phosgene emission
control systems. Results of this study indicated that the per-
meation devices were well suited for accomplishing routine
calibration; that all the proposed analytical methods provided
acceptable results; also that additional testing would be re-
quired once the actual scrubber system was completed. A
summary of this preliminary field study is contained in Table I.
Scrubber Design
Concurrent with the evaluation of monitoring methods, a
literature search was conducted and developmental studies
were performed on a pilot packed column. As little data were
available in the literature on packed towers for phosgene
scrubbing, the kinetics and mass transfer data obtained from
the pilot work provided the basis for the design of the columns
at RMA. However, in the pilot studies conducted, there was
no indication of complications which would arise once the
columns had been constructed.
Theoretical design parameters to include a substantial
safety factor resulted in two-counter cur rent packed towers
arranged in series, each 39 ft tall. The initial packed beds
consisted of 14.5 ft of 1 in. plastic pall rings. Separate pumps
pulling from a common 4000 gallon sump are used to provide
aqueous sodium hydroxide scrubbing liquor to the tops of the
packed sections at up to 500 gpm per tower. Design liquid flow
rate was approximately 200 gpm per tower. Pilot data indi-
cated an optimum caustic range of 3 to 8% by weight. The
system air flow was to be set at 10,000 cfm to be divided be-
tween the TC holding room and the four transfer booths.6 (See
Figure 1). Solely on theoretical considerations, the scrubber
system was designed for 99.9993% efficiency. (This corre-
July 1978 Volume 28, No. 7
sponds to a TLV stack emission concentration which would
result from an estimated maximum credible accident*
scrubber challenge. A design scenario much more stringent
than legally required). However, initial system testing resulted
in scrubber efficiencies considerably lower than had been
anticipated. Actual efficiencies were at least one order of
magnitude below the design level.
Additionally, as a test run proceeded, the efficiency de-
creased drastically with time. Extensive system testing indi-
cated that both the caustic and sodium carbonate concen-
trations were much more critical than had been determined
from the pilot studies. During the course of a test run, the
carbonate concentration would build up gradually as a result
of caustic reaction with both phosgene and atmospheric car-
bon dioxide. Also, as a test run proceeded the caustic content
was gradually depleted. Both effects tended to lower scrubbing
efficiency.
Based on these results, several process modifications were
made to try to effect an improvement in system performance.
Since the packing height of the towers was fixed and could not
be readily increased, that option was not available. However,
the operating liquid flow rate was increased from 200 to 500
gpm; the caustic makeup was maintained at a level of 4-5%
by weight; and the column packing size was increased to 1.5
in. As a consequence of these rather extensive changes, the
design air flow rate had to be reduced from 10,000 cfm to 6000
cfm.
Initial efficiencies, after these modifications, were not sig-
nificantly improved (i.e., it was still an order of magnitude
below designed efficiency). However, the drastic decrease in
efficiency with time observed in the unmodified system was
much less severe. Nevertheless, because of over design these
extended efficiencies were adequate to meet the established
emission guidelines over the duration of an operational
day.
System Testing
Validation testing was required to select the monitoring
technique which would be used to measure phosgene emis-
sions under actual process conditions and also to verify
scrubber performance for controlling phosgene emissions.7
Challenge runs were conducted on a wide range of phosgene
emission rates. These rates were selected to determine the
lower level of detectability of the monitoring techniques, and
to evaluate the upper level of control provided by the scrubber
Correlation coefficient=0.93
Phosgene challenge to system = 62.82 g/sec
x-Tape monitor
• -Infrared
0 5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
Figure 2. Phosgene concentration (ppm) vs. time (min).
* This corresponds to rupture of a ton container valve, emptying of the container contents
into the transfer booth, and theoretical thermodynamically controlled evaporation of
phosgene into the scrubber («130 g/sec).
675
 Table II. Scrubber efficiencies3
Primary Primary Secondary Total
Challenge Inlet scrubber scrubber scrubber system
rate cone. cone. efficiency cone. efficiency
Date (g/sec) (ppm) (ppm) (%) (ppm) (%)

27 April 2.68 237 0.761 99.68 0.015 99.99+

10.32 911 6.46 99.29 0.050 99.99+
18.93 1671 26.8 98.40 0.470 99.97
28 April 1.00 88 1.17 98.67 0.019 99.98
9.79 864 9.31 98.92 0.132 99.98
29 April 33.11 2922 0.648 99.98
48.07 4242 2.52 99.94
62.83 5545 7.72 99.86
30 April 130.7 11534 6.82 99.94
133.8 11808 10.3 99.91
a
All concentrations and efficiencies are calculated at the end of a challenge run.

system in the event of an unforeseen accident and/or spill. A References

typical test run is illustrated in Figure 2. From these test runs,
along with experience gained in the previous pilot test phase,
it was determined that:
• The gas chromatography and DEP bubblers suffer
the disadvantage of not providing a continuous phosgene
measurement. In addition, the bubbler technique does not
provide a real time analysis.
• The automated colorimetric method, although very
sensitive, was slow, and required considerable time and effort
for reagent preparation.
• The infrared technique provided the most accurate
and reliable results, however, because of the degree of skill
required to operate the instrument, it was not considered
practical as a routine process monitor.
• The colorimetric tape monitor would be employed as
the in-stack method of measuring phosgene emissions. All
indications were that the instrument was continuous,
"quasi-real-time," simple to operate, able to withstand the
work area environment, and displayed sufficient accuracy and
sensitivity to meet all the monitoring requirements. However,
it was decided to employ DEP bubblers solely as a backup
technique.
• And finally, the scrubber system performed satis-
factorily for the 1 to 2 hour test runs, as illustrated in Table
II. However, at maximum credible accident challenges, the
scrubbing efficiency drops off more rapidly than at expected
challenge rates. This effect is attributed to the markedly in-
creased temperatures in the scrubbers. The length of time
available to implement corrective action varies from ap-
proximately 45 minutes with a fresh sump condition (i.e., low
carbonate concentration) to about 15 minutes with a high
carbonate concentration in the sump (indicative of scrubber
conditions at the end of a day). Special emergency procedures
have been developed to cope with this type of situation should
it ever occur.
Summary and Conclusions
As this paper is being written, the transfer operation is
approximately half finished. It is estimated that 3 more
months will be required to complete the entire project in an
environmentally responsible manner.
As hazardous substances continue to pose serious technical
problems in the areas of control and/or disposal, methodolo-
gies will be required to find solutions to these problems sys-
tematically. Many industries and regulatory agencies have
already begun to recognize these facts.8-9 It is hoped that the
basic procedure presented herein will be of assistance not only
for application to the phosgene industry, but as a more general
approach to defining and solving technical problems associ-
ated with many types of hazardous materials.
1. Draft Environmental Impact Statement, Department of the
Army, subject: Disposition by Sale of Carbonyl Chloride (Pho-
segene)," Jan. 1976.
2. "Regulation to Control Emissions of Chemical Substances and
Physical Agents," Regulation No. 8, State of Colorado Depart-
ment of Health, Air Pollution Control Commission, Denver, CO,
Adopted 27 Nov. 1973, as amended 5 Dec. 1974.
3. D. Bruce Turner, Workbook of Atmospheric Dispersion Esti-
mates, Office of Air Programs, Environmental Protection Agency,
Revised 1970.
4. "Phosgene Analysis Methods Development," U. S. Army Envi-
ronmental Agency, Feb. 1976.
5. "Air Pollution Engineering Special Study No. 99-041-75/76,
Phosgene Measurement, Rocky Mountain Arsenal, Denver,
Colorado, 22 September-3 October 1975," U. S. Army Environ-
mental Hygiene Agency, 29 Apr. 1976.
6. John A. Ursillo, "Caustic Scrubbing of Lethal Chemical Agent
CG (Phosgene) at Rocky Mountain Arsenal, Denver, Colorado,"
Demilitarization Directorate, Rocky Mountain Arsenal, CO,
undated.
7. "Air Pollution Engineering Special Study No. 99-041-75/76,
Phosgene Measurement, Rocky Mountain Arsenal, Denver,
Colorado, 19-30 April 1976," U. S. Army Environmental Hygiene
Agency, 5 Aug. 1976.
8. "Estimates of Permissible Concentrations of Pollutants for
Continuous Exposure," Office of Research and Development, U.
S. Environmental Protection Agency, Publication No. EPA
600/2-76-155, June 1976.
9. W. L. O'Connell, "How to attack air-pollution control problems,"
Chemical Engineering Deskbook, 18 Oct. 1976.
10. "Criteria for a Recommended Standard . . . . Occupational Ex-
posure to Phosgene," US Department of Health, Education and
Welfare, National Institute for Occupational Safety and Health,
HEW Publication No. (NIOSH) 76-137,1976.
Messrs Kistner, Esposito, Podolak, and Dr. Tuggle are
with the U. S. Army Environmental Hygeine Agency, Aber-
deen Proving Ground, MD 21010. Dr. Lillian's present ad-
dress is U. S. Department of Energy, Washington, D. C. Mr.
Ursillo is now at the Rocky Mountain Arsenal, Denver, CO.
Mr. Smith is with the U. S. Environmental Protection Agen-
cy, Region III. Philadelphia, PA. Mr. Sexton is with the
School of Public Health, Chapel Hill, NC. Mr. Mallen is at
Tooele Army Depot, Tooele, UT.
The opinion or assertions contained herein are the private
views of the authors and are not to be construed as official or
as reflecting the views of the Department of the Army or the
Department of Defense. The presentation contains no mate-
rial that warrants its disapproval for security or policy rea-
sons.
This is a revised version of Paper No. 77-19.6 which was
presented at the 70th Annual Meeting of APCA at Toronto
in June 1977.

676 Journal of the Air Pollution Control Association