Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.

com, ISSN 1743-3541

Qualification test program for emergency

chlorine scrubber systems
M.R. Gonzalez," R.C. Jain*
"Department of Fire Technology, Southwest Research
Institute, 6220 Culebra Road, San Antonio, Texas, USA
*R.J. Environmental, San Diego, California, USA

ABSTRACT

Industries worldwide are being charged with assessing the safety and environmental
hazards of their operations as a result of increasingly stringent regulations. The
widespread use of chlorine in industrial processes including water purification,
sanitation of industrial waste and sewage, and manufacture of chlorinated
hydrocarbons present concernsrelativeto human health effects and environmental
contamination from accidental chlorinereleases.Regulations have been developed
which require the use of emergency treatment systems in response to these releases
and identify minimum chlorine acceptance levels at the point of discharge into the
atmosphere.

The United States Uniform Fire Code describes regulations for the
safeguarding of life and property from the hazards of fire and explosion arising
from the storage, handling, and use of hazardous substances, materials, and devices.
The primary requirements include operating hazardous material storage rooms in
a negative pressure in relation to the surrounding area, and directing the exhaust
ventilation from accidental releases to an exhaust treatment system. The exhaust
treatment system is required to reduce the maximum allowable discharge
concentration of chlorine gas to one-half IDLH (Immediate Danger to Life and
Health) which is equivalent to 15 parts per million (ppm) at the point of discharge
into the atmosphere.

This paper describes a successful qualification test program for emergency

chlorine scrubber systems conducted under controlled chlorine release conditions
with on-line data collection. Performance evaluations of the scrubbers were based
on worst case scenarios and included chlorine release rates of up to 100 pounds per
minute as defined in the Southwest Research Institute test protocol. The test results
provided vital information on the behavior of chlorine spills, release rates,
temperature profiles, flow characteristics, scrubber efficiency, and exhaust stack
chlorine emissions recorded from the new scrubber system design.
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

748 Air Pollution

INTRODUCTION

Since its commercial production began in 1890, chlorine has been used by the
textile, electric power, and chemical industries for a variety of purposes including
bleaching, prevention of biofouling, manufacture of chlorine compounds, and water
and waste water treatment as presented by G. C. White [1]. Chlorine usage in the
United States increased from 2 million tons of chlorine gas and one million tons
of liquid chlorine to 12.3 million tons of gas and 7.3 million tons of liquid during
the period between 1950 and 1979. Prior to 1950, chlorine was primarily used by
the textile industry for bleaching purposes, however, the chemical industry currently
uses over 50 percent of the chlorine produced today for the production of over 35
chlorine compounds. These compounds have over 50 end uses ranging from rocket
fuel to the manufacture of food products. The largest single use for chlorine
compounds has been for the production of ethylene oxide and glycol which are
used to make antifreeze fluids and synthetic fibers.

As the use of chlorine by industry increased, the need to have safe storage
and handling of chlorine containers becomes a primary concern with regard to
personnel safety, public health, and protection of the environment Safety criteria
have been established in a fire code for the design of indoor storage rooms for
compressed toxic gasses and the use of exhaust treatment equipment to handle
accidental chlorine releases. It is through the implementation of these types of
codes and employee knowledge of the chlorine characteristics that will enable
industry to control the number of accidents and their severity as well as minimize
injuries to people and damage to the environment

Chlorine gas is recognized as a hazardous and toxic material which is

corrosive and can cause injury or death if inhaled in significant quantities. The gas
is primarily a respiratory irritant, however, sustained exposure at increased
concentrations can cause severe reactions and possibly death through suffocation.
Two types of gassings can occur as a result of inhaling chlorine vapors, one
involves chlorine gas in the dry state while the other involves fumes from an
aqueous solution. The more dangerous gassing occurs from a chlorine solution leak
since the moisture makes the fumes somewhat more tolerable thus allowing a more
excessive amount to be inhaled. Inhaling large doses of chlorine vapors can lead
to death due to pulmonary edema causing drowning. Table 1 provides the degree
of hazard associated with the chlorine concentrations in air.

Chlorine releases can occur from a variety of sources including start up

operations, maintenance, equipment malfunction, or component failure. Minor
releases can be attributed to gasket failures, valve packing adjustment whereas
major leaks result from container rupture, pipeline breaks, broken connections, and
possible combustion due to exposure of the containers to excessive temperatures.
Several major accidents involving significant releases of chlorine have occurred due
to container rupture and improper handling operations. The most common type of
containers used for shipping chlorine are the 150 pounds, one ton, and bulk tanks
which can carry as much as 16, 30, or 85 tons. Accidents involving chlorine
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

Air Pollution 749

TABLE 1. EFFECT OF CHLORINE CONCENTRATIONS

Chlorine
Concentration Degree of Hazard
in Air

1,000 ppm May be fatal with a few deep breaths.

100 ppm May be lethal.
40 to 60 ppm Exposure for 30 to 60 minutes may cause
serious injury.
30 ppm "IDLH" - Immediate Danger to Life and Health;
coughing, shortness of breath, chest pain, possible nausea
and vomiting.
20 ppm Very offensive; will cause person to exit from area
immediately resulting in coughing and other discomfort.
6 to 15 ppm Throat irritation.
3 ppm Short term exposure limit
1 to 3 ppm Definite odor, irritation of eyes and nose.
1 ppm OSHA ceiliing (8 hour time weighted exposure).
Household bleach odor concentration.
0.2 to 0.5 ppm No noxious long-term effects.
0.002 to 0.2 Odor threshold.
ppm

releases have caused serious injury and in some cases death as well as damage to
animal and plant life. Damage to equipment can also occur due to the corrosive
nature of chlorine shorting out electrical contacts and relays which can ignite fires
at the plant facilities.

Chlorine accidents
Some of the more significant accidents have occurred during the transport of
chlorine containers as well as by the consumers. The most severe accidents have
occurred due to the derailment of rail tank cars which resulted in significant
releases of chlorine into the atmosphere. In 1981, a total of 385 tons of chlorine
leaked from seven rail tank cars when the train derailed in Estacion Montana, San
Luis, Potosi, Mexico. The tank cars were either ruptured or had their valves and
protective housings damaged. As a result of this accident, the Mexican government
no longer allows this many chlorine cars in a freight train, In 1978, a freight train
carrying several tank cars of hazardous waste along with two cars of chlorine
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

750 Air Pollution

derailed near Youngstown, Florida which resulted in 50 tons of chlorine released

into the atmosphere. The leak caused 8 fatalities and 138 injuries from a chlorine
cloud that measured 3 miles wide, 4 miles long, and 100 feet high.

Consumer accidents have occurred primarily at water and wastewater

treatment facilities due to mishandling of the chlorine containers or leaks attributed
to faulty gaskets or connections. One of the more recent accidents occurred at a
waterfilterplant in Morristown, Tennessee. Approximately 2,400 to 3,000 pounds
of gas escaped in a leak from two one ton cylinders which were connected through
a manifold. This leak forced the evacuation of 4,000 people due to a chlorine cloud
that was 5 miles long, one mile wide, and 30 feet thick. Several plant personnel and
emergency response team members suffered respiratory irritation and chemical
burns. The chlorine vapors caused corrosion of electrical contacts and relays which
resulted in a fire in the plant's transformer room. The power to the plant was shut
down which could have caused untreated water to be released.

In response to these accidents, the Western Fire Chiefs Association pub-

lished the Uniform Fire Code (UFC) which mandates that indoor storage rooms for
compressed toxic gases be equipped with an exhaust treatment system that can
handle the contents of the largest cylinder or tank stored. The storage rooms must
be designed to operate at a negative pressure to prevent leaks into the atmosphere
and direct the exhaust ventilation to an exhaust system. The exhaust treatment
system must be capable of diluting, adsorbing, absorbing, containing, neutralizing,
burning, or otherwise processing the entire contents from the largest cylinder or
tank. The treatment system must reduce the maximum allowable discharge concen-
tration of the gas to one-half DDLH at the point of discharge to the atmosphere.
Sizing of the system must allow for processing of the worst case release of gas.

Exhaust ventilation systems

The most common types of exhaust ventilation systems used to date for chlorine
storage rooms include dispersion, packed tower scrubbers, emergency chlorine
scrubber systems, and the once through emergency scrubber systems. The disper-
sion system operates by continuously exhausting the entire room to the surrounding
atmosphere without neutralizing the chlorine vapors. This type of system provides
protection for the plant personnel but jeopardizes the public living in the nearby
communities. This system is the most outdated and fails to meet the UFC.

The packed tower system uses an induced draft fan to move the chlorine
vapors through packed towers which are irrigated from the top with a neutralizing
agent such as caustic. The disadvantage of this system is that it allows a certain
percentage of untreated chlorine vapors to be exhausted into the atmosphere at
levels which do not meet thefirecode requirements. The time required to wet the
packed towers under certain leak scenarios allows for the untreated vapors to be
released. Chlorine vapor concentrations are the highest during the first minute of
a catastrophic failure and because of the time required to wet the packing, the
scrubber efficiency is the lowest. The tower heights present the need for special
housings and create unattractive sights.
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

Air Pollution 751

The third system actually represents the true emergency scrubber system
since it is a total containment recycle system that treats the chlorine vapors and
returns them back to the room. The system utilizes an ejector-venturi which allows
for a quick response and guarantees caustic to chlorine contact for neutralization.
The scrubber efficiency allows some amounts of chlorine back into the room which
in turn can cause a pressure build up. During large leaks, this pressure could allow
for chlorine to be released into the atmosphere through the dampers designed to
prevent over pressurization. The scrubber design can be installed within normal
room heights.

The fourth system is a once through scrubber that combines the use of the
ejector-venturi to evacuate the room and a pack tower to allow for the treated
exhaust to be released into the atmosphere within the limits required by the fire
code. The exhaust can be released into the atmosphere at a greater rate than the
chlorine gas rate thus create a negative pressure in the storage room. The chlorine
vapors are directed into a caustic storage tank for neutralization and then directed
through a packed tower which can be of significant height.

Recently a new scrubber system was developed which is a once-through

three stage absorption system, consisting of one horizontal spray scrubbing stage
followed by two horizontal cross flow packed bed sections. An induced draft fan
pulls vapors through the scrubber, where intimate contact with a recirculating
caustic solution results in the complete absorption and removal of chlorine. A high
efficiency mist eliminator is located in the gas stream, prior to exhaust, to remove
any residual caustic solution. The induced draft fan provides a negative pressure
throughout the room, ducting, and scrubber.

Equipment qualification program

Southwest Research Institute, an independent research and development organiza-
tion located in San Antonio, Texas was contracted to conduct a qualification test
program for this new scrubber design. The full scale tests included simulating
chlorine leaks of 150, 550, and 1800 pounds to confirm that the scrubber design
would meet the UFC requirements for chlorine levels of less than 15 ppm from the
scrubber exhaust stack and maintain a negative pressure throughout treatment of the
chlorine vapors.

The tests conducted for the qualification of the system represented significant
quantities of chlorine leaked at catastrophic leak rates which had not been
performed before on an emergency chlorine scrubber system.

Emergency chlorine scrubber system

The scrubbers tested included a system designed to handle a 150 to 300 pound
chlorine leak and another designed to handle a one ton leak. Each one of these
systems is a once through three stage absorption system which was sized
accordingly to provide the appropriate ventilation rates and supply of caustic
solution.
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

752 Air Pollution

The scrubber components included a three stage absorber, caustic storage

tank, air exhaust fan, caustic recirculating pump, electric control panel, and
associated piping. The absorber is placed at the top of the vessel which also
contains the integral caustic storage tank. A pump circulates the 20 percent caustic
solution through the scrubber which drains to the storage tank by gravity. The
exhaust fan was placed downstream from the absorber to ensure that the absorber
also operates under a negative pressure to prevent chlorine leakage.

The test setup for the chlorine leaks included the chlorine cylinders
mounted on a load cell to monitor weight loss, a flash room to provide for con-
trolled leaks, the scrubbers, instrumentation to monitor the temperatures, pressures,
and flow rates, and a data acquisition system that would collect data at five second
intervals throughout the tests. A schematic of the test layout is provided in Figure
1 which also provides the location of the pressure transducers and thermocouples.
The flash room measured 12 x 13 ft with an 11-ft ceiling and contained an 8 x 8-ft
and 1-ft deep metal pan to contain the liquid chlorine spill. Sealed windows in the
flash room provided complete visible access to the liquid leak discharge and the
vaporization of the chlorine at all times. The flash room was coated and caulked
with appropriate material to prevent both leakage and chlorine absorption into the
wall surface.

T-l Intake air to flash room T-9 RJ-2000 Air outlet

T-2 Hash room T-10 RJ-2000 Sump
T-3 Flash room T-ll Ambient (room)
T-4 Flash room T-12 Open
T-5 RJ-150 Air inlet P-l Flash room pressure
T-6 RJ-150 Air outlet Wt Load cell
T-7 RJ-150 Sump Cl, Exhaust stack chlorine
T-8 RJ-2000 Air inlet

Figure 1. RJ Environmental Chlorine Scrubber Test Process Flow Diagram

 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

Air Pollution 753

The test apparatus and equipment were instrumented to record the

following data:

a. Flash Room Static Pressure: The static pressure was monitored with a
pressure transducer with an accuracy of + 0.01 inch w.c.

b. Chlorine Concentration: The chlorine concentration at the outlet of the

scrubber was monitored with an Enterra Model 4000 chlorine analyzer calibrated
and certified by the manufacturer. The analyzer was field checked frequently
against a calibration kit provided by Enterra.

c. Chlorine Release Rate: The chlorine release rate was calculated from the
measured chlorine cylinder weight loss versus time. The weight of the chlorine
cylinder was monitored continuously with the use of a calibrated load cell.

d. Temperature: Temperatures of the ambient air, flash room, scrubber inlet,

scrubber outlet, and scrubber sump were measured with type "K" thermocouples.

e. Scrubber Pressure Drop: The scrubber pressure drop was determined with
a magnehelic differential pressure gauge.

f. Scrubber Air Flow: Volumetric air flow rates were measured with an ori-
fice plate at the inlet of the scrubber. The orifice plates were calibrated against a
standard pitot tube in accordance to Environmental Protection Agency Method 2.

TEST PROGRAM

A total of seven tests were conducted on the scrubber systems to provide functional
checks as well as confirm the performance specifications. The tests were scheduled
to provide for a gradual increase in severity level based on the amount of chlorine
released into the flash room. Due to the nature of chlorine, precautions were taken
which included informing the test personnel of the safety procedures invoked,
providing safety equipment such as breathing apparatus, minimizing the number of
personnel in the area of the chlorine cylinders, and closely monitoring the
instruments to ensure that the allowable chlorine levels were not being exceeded.

Test No. 1, 2. and 3

The first test was a functional check out of the test apparatus, instrumentation, and
data acquisition system by utilizing available room air and nitrogen. Once the
functional check was completed, a second test was performed using a 150 pound
chlorine cylinder and leaking 19 pounds of chlorine in one hour and 22 minutes to
ensure that the scrubbers were properly operating and were in fact performing the
scrubber operation. The chlorine level measured from the scrubber exhaust stack
during this test was 0.1 ppm. The third test included a release of 75 pounds of
chlorine into the flash room over a period of one hour and 27 minutes. The
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

754 Air Pollution

chlorine level measured from the exhaust stack during this test was a maximum of
0.2 ppm. These three tests were mandatory before any full scale tests would be
allowed.

Test No. 4
This test was conducted with the one ton scrubber and had a one ton chlorine
cylinder plumbed to the test apparatus. The chlorine leaked into the flash room
reached a maximum leak rate of 52 pounds per minute. The test ran for a period
of two hours and 21 minutes and leaked a total of 1767 pounds of liquid chlorine.
Table 2 shows a summary of the test results and the chlorine release rates as a
function of time. The temperature profiles for the flash room, scrubber inlet,
scrubber outlet, and the scrubber sump are shown in Figure 2.

TABLE 2. 1 TON RELEASE

Time, Release Exhaust Flash Scrubber Scrubber Scrubber

min Rate Chlorine Room Inlet Outlet Sump
Ib/min ppm Temp. Temp. Temp. Temp.

1 52 0.0 48 47 84 81
2 42 0.0 41 44 84 82
3 40 0.0 37 45 85 82
4 39 0.0 30 47 85 82
5 37 0.0 27 45 85 82
10 37 0.0 22 46 88 86
15 35 0.0 22 45 92 90
20 35 0.0 21 47 97 95
25 33 0.0 28 55 107 105
30 34 0.0 27 49 104 102
45 29 0.0 72 55 111 110
60* - 0.0 72 63 114 113
120 - 0.0 69 61 109 108
180 - 0.0 71 65 106 105
240 - 0.0 67 62 106 104
300 -- 0.0 71 70 105 103
360 - 0.0 74 74 101 98

"Chlorine Release stopped at 51 minutes after start

 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

Air Pollution 755

120 f
Release from 1 ton cylinder
110 - Ambient
Release Rate = 52 Ib/min Scrubber Outlet
Temp-71 F
100
90
80
70
60
50
40
30
20
10
0
10 15 20 25 30 35 40 45
TIME (min)

Figure 2. Temperature Profiles

As indicated by the temperature readings recorded, the temperature of the

flash room dropped instantly, once the chlorine was released into the room and
reached a temperature below freezing in about four minutes. Once the chlorine
cylinder was emptied, the temperature in the flash room returned to ambient As
expected, the temperature of the scrubber sump gradually increased due to the heat
of thereaction.Figure 3 shows the static pressure of the flash room over time.
0.0
Release from 1 ton cylinder
-0.1 Release Rate - 52 Ib/min
Room Volume - 1,600 ft
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
o
o
er -0.8
-0.9
-1.0
-1.1
5 10 15 20 25 30 35 40 45 50 55 60
TIME (min)

Figure 3. Flash Room Static Pressure

 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

756 Air Pollution

The flash room was maintained under negative pressure throughout the test thus
meeting thefirecode requirements. The chlorine levels measured from the exhaust
stack was zero thus indicating that the scrubber had removed 100 percent of the
chlorine from the vapors.

Test No. 5
This test was setup to simulate a catastrophic leak rate of 100 pounds per minute
and treating the vapors with the one ton scrubber. In order to obtain the desired
leak rate, 550 pounds of liquid chlorine was transferred into a 250 gallon pressure
vessel and pressurized with a nitrogen blanket. As a precaution, the 150 pound
scrubber was also installed in the test apparatus as a back up system should the one
ton scrubber need assistance during the scrubbing operation.

The fifth test ran for a period of one hour and 44 minutes with a total of
550 pounds leaked into theflashroom. Due to a maximum leak rate of 100 pounds
per minute shown in Figure 4, the temperature in the flash room dropped to below
freezing much sooner than Test No. 4. The flash room maintained a negative
pressure throughout the test as shown in Figure 5. The temperatures in the flash
room during the release are shown in Figure 6. The chlorine levels measured from
the scrubber exhaust stack ranged from 0.1 to 0.6 ppm, which was well below the
allowable limits set by the fire code.

120

100

80
550 Ib release
60

One Ton Release

20

150 Ib release
10 20 30 40 50 60 70
TIME, min

Figure 4. Chlorine Release Rates

 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

Air Pollution 757

Release from 550 pound cylinder

Release Rate - 99 Ib/miru
Roora Volume-1.600 ft

10 15 20
TIME (min)

Figure 5. Flash Room Static Pressure

Release from 550 pound cylinder

Release Rate = 99 Ib/min
Ambient Temp. = 67 F

10 15 20
TIME (min)

Figure 6. Temperature Profiles

Test No. 6
For this test, the 150 pound scrubber was used to treat a release from a 150 pound
cylinder. The maximum release rate obtained during this test was 28.5 pounds per
minute as shown in Table 3. The scrubber air flow rate was 280 cubic feet per
minute. The entire contents of the cylinder were leaked into the flash room and the
maximum chlorine levels measured from the scrubber exhaust was 1.3 ppm.
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

758 Air Pollution

TABLE 3. 150 LB CHLORINE RELEASE

Tlme/min Release Rate Ib/min Exhaust Chlorine ppm

1 28.5 0.0
2 25.8 0.0
3 25.8 0.0
4 23.2 0.0
5 23.2 0.0
6 19.6 0.0
7 6.2 0.4
8* 03 0.7

Tank empty

Test No. 7
This test was conducted as a demonstration test to industry representatives and
consisted of a leak: from a 150 cylinder using the one ton scrubber as the treatment
system. The results of this test were witnessed by engineers from the various
companies as part of the education process for understanding the behavior of
chlorine leaks. The chlorine levels measured from the exhaust stack were well
within the limits set by the fire code.

CONCLUSION

In meeting the requirements of the Uniform Fire Code for storage of compressed
toxic materials, the performance testing of the emergency chlorine scrubber systems
provided not only confirmation that the performance specifications were met but
also gave industry additional information on the behavior of chlorine spills. For
example, the amount of flashing that occurs from the liquid chlorine is estimated
at 20 percent, however, during the initial stages of the leak, ICO percent flashing
can occur. This places a significant load on the scrubber system and requires
appropriate sizing of the system. Another example involves the anticipated
temperature rise in the caustic solution during catastrophic leak rates. Temperatures
were generally discussed asrisingtoo high and thus causing scrubber damage. The
testing program revealed that the temperature rises were well within the operating
parameters of the scrubbers.

In performing these tests, industries which use chlorine in their processes

have exhaust treatment equipment available which represents improved efficiency
and has been thoroughly tested. Continued improvements to safety and pollution
prevention equipment will help industry address the safety and environmental
concerns facing their business operations.
 Transactions on Ecology and the Environment vol 1, © 1993 WIT Press, www.witpress.com, ISSN 1743-3541

Air Pollution 759

REFERENCE

1. White, G.C. 'Handbook of Chlorination and Alternate Disinfectants/

Chapter 1, Chlorine: History, Manufacture, Properties, Hazards, and Uses.
pp. 1-88, Van Nostrand Reinhold, New York, 1992.