Risk Analysis of a Chlorine Handling Facility

Dennis C. Hendershot
Rohm and Haas Company
Engineering Division
P.O. Box 584
Bristol, PA 19007

Presentation to the Technical Seminar on Safety

and Health in the Petrochemical Industry
Edmonton, Alberta, Canada
November 13-17, 1994
Session #4: “Risk Assessment”

Abstract

Process hazard analysis and quantitative risk analysis are valuable tools for risk management of a hazardous
chemical facility. A liquid chlorine storage facility is used to illustrate the use of hazard identification,
consequence modeling, and quantitative risk for initial design, and for evaluation of design and operating
modifications. The example demonstrates the use of risk analysis as an engineering design tool for identifying
risk management strategies, both in design and operation.
I. Introduction

Process hazard analysis and quantitative risk assessment provide valuable input both for the initial design
and for the continuing operation of chemical processing facilities. In this example, a process expansion
increasing the usage of liquid chlorine at a plant provided a good opportunity to upgrade an existing chlorine
handling facility. Qualitative hazard analysis tools including Hazard and Operability (HAZOP) studies and
quantitative methods such as fault tree analysis, accident consequence models, and risk estimation models,
were used to determine the most appropriate of many available options for improving the design of the
existing system.

The quantitative risk analysis methods used in this example estimate the risk from single short term
exposures to toxic vapors such as chlorine. They do not address other concerns which might arise from
long term exposure to lower concentrations of atmospheric contaminants. The risk analyses in this study
are therefore intended to estimate the risk arising from relatively rare, but potentially larger, releases of
chlorine resulting from a significant loss of containment accident. They do not address concerns from long
term exposure to small emissions from the plant.

II. Description of the Plant

The plant studied in this example is located in a medium sized town. It is bordered on one side by a river,
and by industrial, commercial, and residential areas on the other sides. The chlorine unloading operations
are located on the size of the plant bordering the industrial area. Figure 1 shows the general layout of the
facilities.

Chlorine is brought into the plant in tank trucks, which are taken to the unloading station immediately upon
arrival. The original unloading station was an outdoor facility, which fed chlorine directly to a manufacturing
building located about 200 feet from the truck, over a period of several days. A proposed plant expansion
would increase the usage of chlorine, and add a second manufacturing building located approximately 400
feet from the unloading station. The increased number of trucks and the additional long transfer line
potentially increase the risk associated with chlorine handling in the plant. It was recognized that the
proposed increase in chlorine usage could increase risk. Therefore, the initial proposed design included
enclosing the chlorine unloading station in a building with forced air ventilation to a scrubber as a means of
reducing overall risk while increasing chlorine usage.

Figure 2 is a schematic diagram of the original installation. The initial proposed modifications associated
with the expansion in chlorine usage are shown schematically in Figure 3. In both systems chlorine is kept
in the truck at approximately 11 bars total pressure with nitrogen. Liquid chlorine is fed to the
manufacturing building as required using the pressure from the truck as the driving force. For the proposed
upgraded installation, all unloading equipment is located in a building which operates at negative pressure
and is ventilated to a caustic scrubber. The scrubber is designed to remove any chlorine vapors resulting
from a leak up to a specified design basis leak rate.

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III. Objectives of the Analysis

The intent of the design modifications was to

reduce risk associated with chlorine handling by
improving the system, while increasing the total
chlorine usage to satisfy manufacturing require-
ments. The plant modifications provided a good
opportunity to upgrade the existing unloading
equipment. In the time since the original plant had
been designed and built, the chemical industry has
gained a greater understanding of the potential
impact of toxic releases off site. There are also
improved design alternatives which can reduce
Figure 1: Map of plant and
these impacts surrounding area

IV. Outline of Hazard Identification and

Risk Analysis

The proposed chlorine unloading system design was the subject of a series of reviews and analyses
including:

Preliminary design reviews to define issues of concern and potential alternatives among
the plant and design personnel.

Safety, Health and Environmental (SHE) Review- This review is a standard company
procedure once a preliminary design has been developed. It includes participation by
design and operating personnel as well as safety, health and environmental professionals

Figure 2: Schematic diagram of the Figure 3: Schematic diagram of the

existing chlorine unloading facility proposed chlorine unloading facility

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 from the local operating plant and corporate staff. Theprocedure is a “What If” type of
review similar to that described by CCPS1. One of the major functions of the SHE review
is to identify areas where more sophisticated hazard evaluation techniques are justified.

Hazard and Operability (HAZOP) Study - The SHE Review determined that the
chlorine handling operation should be the subject of a qualitative HAZOP review. This
study used the guide word approach as described by CCPS1, The Chemical Industries
Association2, and others. The HAZOP review is intended to identify specific potential
accident scenarios associated with the chlorine facility as designed, qualitatively evaluate
them, identify potential corrective actions, and address the concerns identified. In this case
the HAZOP identified a number of specific improvements in piping, control and
instrumentation, and operating procedures.

Initial Quantitative Risk Assessment - To evaluate whether or not the design objective
of reducing risk had been met, a quantitative risk assessment of both the existing installation
and the proposed design was completed. This assessment used the results of the SHE
Review and HAZOP to identify release incidents, fault tree analysis to estimate their
frequency, and various releases, vapor dispersion, and toxicity models to estimate the
impact of releases. The frequency and consequence results were combined to give
quantitative estimates of risk for both the existing and initial proposed design.

Follow Up Quantitative Risk Analysis - During detailed design of the new installation
further modifications were found to be necessary. In order to ensure that these
modifications did not compromise the design objective of reducing risk, the original
quantitative risk assessment was updated. This update was completed late in the plant
construction, when details of the design and operating procedures had been well
established.

The primary focus of the following discussion is on the quantitative risk analyses, and their use to identify
effective strategies for managing risk. The ability to identify the major contributors to risk and evaluate the
benefits of design alternatives is a major strength of quantitative risk estimation methodologies.

V. Initial Quantitative Risk Assessment

Following the HAZOP review, a quantitative risk analysis was done to determine if the proposed design
of the expanded chlorine facility met the design objective of risk reduction. If the design did not meet this
objective, the risk analysis would provide guidance on what further design and operating modifications
would be needed to meet that objective. Also, the risk analysis would lead to a better understanding of
the sources of risk, with possible identification of further design and operating alternatives which might
provide additional risk reduction. The quantitative risk analysis closely followed the Chemical Process

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Quantitative Risk Analysis (CPQRA) methodology outlined by the Center for Chemical Process Safety
(CCPS)3.

The first step in the quantitative risk analysis was to generate a list of potential release events, using the
results of the Safety, Health and Environmental review, the HAZOP study, and plant and other operating
experience as the primaryresources. This step is extremely important, because potential accident scenarios
whichare not identified cannot be included in the subsequent quantitative calculations. The identified events
were then grouped to combine incidents of similar size and consequence. The resulting representative list
of release incidents was used for the detailed analysis.

Fault trees were developed to estimate the frequency of each representative release incident. Design and
operating personnel thoroughly reviewed the fault trees to make sure that they accurately reflected the
actual intended operation of the plant.

The next step in the analysis was the modeling of release rate, atmospheric dispersion, and impact on
people (using toxicity models) to estimate the effects of the representative events. Because this study was
intended to compare alternative designs, relatively simple toxicity models were judged to be adequate. The
entire range of actual weather conditions was represented by a small number of atmospheric stability class
-- wind speed combinations.

The final step in quantitative risk assessment is combining the results of the frequency and consequence
analyses, along with weather and population information, to generate risk estimates. For this study societal
risk was estimated using the Frequency - Number (F-N) curve to display and compare the risk of the
original installation to the proposed design. As a measure of societal risk, the F-N provides an estimate
of the risk of accidents which affect a large number of people. The methodology for generating an F-N
curve from incident frequency, incident consequence, weather, and population data is described by CCPS3
and also by the IChemE4.

In order to accomplish the objectives of the analysis it was first necessary to estimate the risk of the existing
facility, using the procedures described above. Then, the risk of the proposed design for the expanded
operation was estimated using the same methodology, models, and assumptions. Societal risk F-N curves
resulting from these analyses are shown in Figure 4. The results of the analysis estimate about the same
total societal risk (based on the area under the F-N curve) for the expanded facility as compared to the
original, despite the increase in chlorine usage. An inspection of the societal risk F-N curve in Figure 4
shows significant reduction in risk of smaller incidents. This reduction is a result of enclosing the chlorine
unloading facility in a building. Unfortunately, however, the proposed design has a higher risk of
intermediate size incidents. The analysis showed that this increase in intermediate incident risk was a result
of the new transfer line to the new process building. For the largest incidents, the existing installation and

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 Figure 4: Societal risk F-N curves for proposed
Figure 5: Societal risk F-N curves for the
alternative designs for the chlorine facility
existing plant and the proposed modifications

proposed designs have essentially the same risks, because these incidents result from the potential
catastrophic rupture of a chlorine truck. The frequency and consequences of this type of release are not
significantly affected by the differences between the two systems. Thus the initial quantitative risk analysis
identified an area (intermediate size incidents) where the proposed design did not meet the objectives of
the analysis

Quantitative risk assessment is also a powerful tool for identifying the sources of risk in a facility. This
information is essential in order to effectively direct efforts to reduce risks toward those parts of a plant
where those efforts will be most effective. For each identified incident it is possible to compute an
importance -- the contribution that incident makes to the total risk. For a societal risk estimate using the
F-N curve as the risk measure, the importance may vary with N, the number of people affected. For
example, a specific small pipe break may be the major contributor to risk of incidents affecting one or two
people, because of a relatively high frequency. However, the same incident may make little or no
contribution to the risk of incidents affecting a large number of people because the release does not impact
a large geographical area.

For the chlorine installation under study, the quantitative risk assessment also provided information on why
the proposed design resulted in an increased risk of intermediate size release incidents. An evaluation of

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the contribution of the various representative release incidents revealed that the dominant contributors to
the risk of intermediate size incidents were the two transfer lines between the unloading station and the
manufacturing buildings. The initial proposed design increased the total length of the transfer lines, thereby
increasing the estimated frequency potential of failure. Also, for the longer of the two lines, the amount of
chlorine released in the event of a failure would be increased. Because these risks dominated the risk of
intermediate size incidents, the increase was directly reflected in the F-N curve for the entire system.

Having identified the transfer lines as the source of increased risk of intermediate size incidents, it was then
possible to suggest design changes to reduce this risk. The risk assessment itself does not directly identify
ways to reduce risk. Instead, by identifying sources of risks, it directs the efforts of process engineers and
others expert in the technology to those areas where improvements will have the most effect. Identification
of specific risk reduction measures results from the application of chemical engineering tools to the problem
of reducing the frequency and/or consequence of the incidents which are major risk contributors. Risk
assessment techniques can then be used to evaluate the effectiveness of various proposed designs.

For the chlorine facility, a large number of possible modifications to the transfer lines was suggested. Some
of these addressed the frequency component of risk; for example, using higher strength piping and more
rigorous installation techniques, protecting vulnerable sections of the transfer lines in the pipe rack, or
locating the transfer lines in protected underground trenches. Others addressed the consequence
component of risk-reducing the inventory of chlorine which could be released by providing additional
isolation valves, reducing transfer line size, transferring gaseous chlorine rather than liquid chlorine, or
enclosing the transfer lines in a second pipe and venting the annular space to the unloading building
scrubber. Some of the ideas could be used in combination, while others were mutually exclusive designs.
It was not at all clear from a qualitative evaluation which of the various proposals represented the best and
most cost effective strategy for reducing the system risk.

Quantitative risk analysis techniques were used to evaluate the various risk reduction strategies which had
been suggested. The risk of proposed alternative designs was estimated using the same techniques, models
and assumptions used for the original risk assessment. Again, the F-N curve was used as a measure of
societal risk to compare the different alternatives. Results of the analysis for several of the options
considered are shown in Figure 5. This information and other data were used as input to the management
decision making process on which of the proposals to implement. After further study Option B was found
not to be technically feasible at this time. Option A was chosen for implementation. This Selected Design
used a chlorine transfer line of one half of the diameter of the original (thereby reducing the chlorine
inventory by a factor of four), added additional isolation valves to minimize the size of a potential release,
and enclosed potentially vulnerable outdoor sections of the chlorine transfer line in a double piping system.

VI. Follow Up Quantitative Risk Assessment

Quantitative risk assessment is also useful in the ongoing management of risk in a hazardous facility. The
results and conclusions of a risk analysis are only valid if the actual operation of the facility is consistent with

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the assumptions of the analysis. Thus a risk analysis is not a one time review which can be filed away and
forgotten once the final report is written and the recommendations implemented. To obtain the full benefits
of the analysis, it must serve as a reference document for continuing plant operations. In particular, it is
necessary to continually review operations for consistency with the assumptions of the analysis, to ensure
that the results of the analysis represent actual operation as closely as possible. The risk analysis is also
a valuable tool in understanding the effects of deviations from normal or expected operations, or the effect
on risk of future proposed plant modifications. If an incident or near miss occurs in the plant, the risk
analysis should be consulted to determine if that incident had been identified and considered in the analysis.
If it was included, the analysis should be reviewed to determine if the frequency and consequence estimates
are consistent with the actual incident. If the incident was not included in the analysis, this omission
represents an error in the analysis, and may result in an incorrect understanding of the risk from the facility.

For the chlorine handling system, the risk analysis of the Selected Design (Option A) was based on a
preliminary design concept. As the detailed design of the actual facility was completed, several changes
were made in the mode of operation of the containment building and the scrubber treating the air discharged
from the building. These changes were in response to operating problems which had not been anticipated
when the preliminary design concept was developed. A review of the original quantitative risk assessment
showed that these parts of the design were important in achieving the objective of reducing the risk of the
chlorine system. Therefore it was decided that the original risk assessment would be updated to reflect the
“as built” design and operation of the building and scrubber. Also, in the time since the original quantitative
risk analysis had been completed, the technology for modeling incident consequences and estimating risk
had been improved. The updated risk analysis took advantage of these advances and used the improved
tools.

A new list of representative potential release events for the “as built” plant was constructed from the list
used in the original identification studies which were done in the course of the detailed plant design. These
reviews included a study of the facility design following the techniques of the Rohm and Haas Major
Accident Prevention Program (MAPP)5, which utilizes a “What If/Checklist”1 hazard identification
technique. The new release event list was basically the same as the list from the original risk assessment.
There were some modifications due to changes in the design, including reduction of the size of several lines
in the unloading area and changes due to modifications in the operation of the building ventilation and
scrubber. The update also re-evaluated risk for the original installation for purposes of comparison with
the “as built” facility. The same list of representative potential release events used for the original
quantitative risk analysis was used to update the original installation risk estimates.

The risk assessment update evaluated societal risk using the F-N curve, and also estimated individual risk
in the area in and around the plant. The individual risk estimates were presented in the form of risk
contours connecting points of equal individual risk on a local map. This risk presentation format conveys
information about the geographic distribution of risk in the vicinity of the plant. It also allows the
contribution of various potential sources individual risk at particular locations (for example, at the control
room) to be evaluated.

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 The results of the risk assessment update, shown
in Figure 6, confirmed that the changes in the
building ventilation and operation of the scrubber
had not compromised the design objective of
reducing risk. The F-N curve for the as built
installation in Figure 6 shows the modifications as
actually built and operated are estimated to have
a similar or lower risk for incidents of all size
when compared to the original analysis based on
the preliminary design.

Figure 6 also shows good agreement between the

Figure 6: Societal risk F-N curve for the
“as built” chlorine facility
original quantitative risk assessment for the
original chlorine installation and the update analy-
sis for the same facility. These two analyses used
the same representative set of release events.
They differ only in the use of more recent sophis-
ticated consequence modeling and risk estimation
tools in the updated analysis. This good agree-
ment between the two studies increases our
confidence in our ability to estimate relative risks
of the various options.

The risk assessment also shows that the new facility reduced individual risk at all locations in and around
the plant, when compared to the original facility. Figures 7 and 8 qualitatively compare the individual risk
distribution around the plant for the original installation and the final “as built” modified facility.
Corresponding risk contours enclose a much smaller area in the modified facility, and the two highest risk
contours (A and B in Figure 7) have been completely eliminated in the modified plant (Figure 8).

The updated risk assessment also evaluated the relative contribution of various sources of risk at specific
locations in and around the plant. As would be expected, the most important contributors to risk were not
the same at all locations. For locations inside the plant near the chlorine truck and the transfer lines,
potential leaks from the transfer lines are a significant contributor to risk (about 60 percent). At the plant
fence line, potential leaks from the transfer lines are a minor contributor (less than 1 percent). Nearly all
risk (importance of about 99 percent) at these more distant locations arises from the risk of a large loss of
containment from the truck itself.

This information is extremely valuable in directing any efforts for additional risk reduction. The importance
data show that the “as built” chlorine transfer pipelines essentially eliminate this part of the installation as
a source of risk outside the plant. Improvement to the chlorine transfer lines

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 Figure 7: Individual risk contours Figure 8: Individual risk contours
for the existing chlorine facility for the “as built” chlorine facility
(risk levels A > B > C > D > E) (risk levels A > B > C > D > E)

would result in negligible risk reduction at or beyond the plant fence line. Even if the risk associated with
the chlorine transfer lines could be completely eliminated, the total risk reduction at the plant fence would
only be about one percent. Clearly, any efforts to further reduce risk outside the plant must be directed
to reducing the risk associated with potential large chlorine leaks or loss of containment directly from the
truck.

VII. Summary

This case study illustrates the use of quantitative risk assessment as an engineering tool to select the most
appropriate ways to manage risk in a hazardous material handling facility. The quantitative risk assessment
follows qualitative hazard identification procedures, if it is judged that those qualitative techniques do not
provide sufficient information for risk management and decision making. Quantitative estimates of societal
and individual risk provide a basis for comparison of different design options. This risk comparison is one
of the many factors which must be considered in the decision making process6. The quantitative analysis
also provides an in depth understanding of the sources of risk in the facility, and of their relative contribution
to the total risk. This information provides direction for identification of strategies for further risk reduction.
Knowledge of the most important sources of risk in the plant also provides important guidance for ongoing
risk management. The risk analysis provides a basis for evaluation of the impact of changes in plant
operating procedures and equipment, as well as an understanding of the potential effect on risk of process
deviations.

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References

1. Center for Chemical Process Safety (CCPS), Guidelines for Hazard Evaluation Procedures, 2nd
Edition with Worked Examples, American Institute of Chemical Engineers, New York, 1992

2. Chemical Industries Association, A Guide to Hazard and Operability Studies, London, Alembic
House, 1977

3. Center for Chemical Process Safety (CCPS), Guidelines for Chemical Process Quantitative Risk
Analysis, American Institute of Chemical Engineers, New York, 1989

4. The Institution of Chemical Engineers (IChemE), Risk Analysis in the Process Industries, IChemE,
Rugby, Warks., England, 1985

5. Renshaw, F. M., “A Major Accident Prevention Program,” Plant/Operations Progress, 9, No. 3,

194-197, July 1990

6. Center for Chemical Process Safety (CCPS), Tools for Making Acute Risk Decisions with
Chemical Process Applications, American Institute of Chemical Engineers, New York, in press
(available in late 1994)

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