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Feature Report
Engineering Practice 6

Designing
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Safer
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Process Plants
Several often-overlooked strategies 1. Process design
2. Basic controls, process alarms and

to increase inherent safety are discussed here operator supervision


3. Critical alarms, operator supervision
and manual intervention
Victor H. Edwards, P.E., Aker Solutions 4. Automatic action safety-instrumented

M
systems (SIS) or ESD
any individuals and organi- energy transfer to achieve chemical 5. Physical protection (relief devices)
zations have made impor- transformation 6. Physical protection (dikes)
tant contributions to the cre- • Some manufacturing processes pro- 7. Plant emergency response
ation of inherently safer (IS) duce benign products but require 8. Community emergency response
products, processes and process plants hazardous chemical intermediates
[1–3]. A brief survey of successful case in their manufacture FIGURE 1. Shown here are some
typical layers of protection that can be
histories shows that most reported For these reasons, rigorous process employed in a modern process plant [4].
applications relied on only a few of and product safety practices must be At the core is an inherently safe process
the core IS principles. This paper em- used throughout the lifecycle of pro- design. Moving outward from the core,
phasizes the opportunities presented cess plants and must be applied to the proposed options move through the
by three particular — and often-over- their associated raw materials and spectrum from inherent to passive to
active to procedural or administrative
looked — possibilities for inherently products. In recent years, this has controls, which are considered to be
safer processes. led to major efforts in green chemis- progressively less reliable
The methods proposed here ensure try and engineering to develop prod-
integration of IS methods beginning ucts, manufacturing processes, and objectives of a number of creative indi-
with process conception and continu- plants that are safer for both people viduals and organizations since Kletz’s
ing through process plant engineering and the environment. path finding proposal, with many no-
design. Particular emphasis is given Before green chemistry and engi- table successes.
to matching the IS principles with the neering achieved prominence, there Complete coverage of the entire prod-
state of the project. For example, sub- were pioneering insights in the de- uct/process/plant lifecycle is needed to
stitution is best applied during prod- sign of safer process plants. Early ap- assure optimum health, safety and en-
uct and process research, while limita- proaches to safer processes often em- vironmental performance of a chemi-
tion of effects is most effective during ployed additional instrumentation and cal enterprise.
plot plan layout and equipment ar- procedures. These measures were often This article focuses on how to en-
rangement. helpful and necessary, but instrumen- sure maximum incorporation of IS
The chemical process industries tation and operators can fail, especially processes into the creation of a pro-
(CPI) face the challenge of working when faced with complexity. cess plant by beginning at the product
with processes and products that Trevor Kletz [1] recognized that and process research stages and con-
present many hazards, such as “What you don’t have can’t leak”, when cluding with the detailed design. No
the following: he first proposed the concept of the effort is made to address the applica-
• The manufacture of fuels uses and inherently safer chemical processes tion of inherently safer principles be-
produces products that burn with in 1977. His approach placed an em- yond plant design, although these are
significant energy release phasis on the inherent nature of the also important.
• Certain basic chemicals, such as process. Since then, important related
mineral acids and halogens are toxic concepts such as product design for Layers of protection
and/or corrosive safety and safer products, process and The classical onion diagram (Figure
• Many manufacturing processes ei- plant lifecycles have also advanced. 1) illustrates the safety layers that
ther release or require significant Creation of IS processes has been the technical professionals throughout
44 Chemical Engineering www.che.com April 2011
Often-overlooked IS concepts
Three underutilized IS concepts are
presented here and illustrated with
examples:
1. Hybridization or transforma-
tion. One relatively new IS concept is
based on the recent innovative work
by Chen [5] who reports an inherently
safer process for the partial oxidation
of cyclohexane. Partial oxidation pro-
cesses often involve hazardous condi-
tions, as illustrated by the Flixborough,
England, tragedy in 1974 — which
killed 28 people, destroyed a plant, led
to new process safety regulations, and
FIGURE 2. The Flixborough tragedy ushered in a new era in process safety [6] inspired Trevor Kletz to propose his
inherently safer design concept. The
the CPI use to prevent process plant Basic concepts Flixborough plant carried out liquid-
incidents. This diagram helps to ex- Inherently safer process concepts are phase oxidation of large inventories of
plain the following four basic process summarized below [1]: hot cyclohexane in large pressurized
risk-management strategies: Inher- • Substitution vessels. When containment was lost, a
ent, passive, active, and procedural or • Minimization or intensification large flammable vapor cloud formed,
administrative • Moderation or attenuation ignited, and exploded with devastating
Inherent safety is at the core of the • Simplification effect (Figure 2, from Mannan [6]).
onion — the process design. A process • Limitation of (hazardous) effects The traditional cyclohexane-oxida-
that cannot have a major fire, explo- • Avoiding knock-on effects tion process to produce a mixture of cy-
sion or toxic release is inherently safer • Making incorrect assembly impossible clohexanone and cyclohexanol (K/A oil
than one that could if one or more lay- • Make status clear or ketone/alcohol oil) was operated at
ers of protection were to fail. • Tolerance of error low conversion rates (typically 3–5%)
Passive safety layers represent the • Ease of control to avoid formation of unwanted byprod-
addition of such safety features as a • Administrative controls or proce- ucts. The K/A oil was subsequently con-
dike or a blast wall. Because passive dures verted into adipic acid and caprolactam
layers of protection require no active In 2007, the Center for Chemical for the production of nylon.
intervention by a human or by a ma- Process Safety (CCPS) of the Ameri- Oxidation of cyclohexane with air
chine, they are deemed more reliable can Institute of Chemical Engineers instead of oxygen is common practice
than active layers of protection or (AIChE) concluded that these eleven to reduce risks of transition from a
procedural layers of protection. None- basic concepts could be reduced to the partial oxidation reaction to an un-
theless, the ability to make an explo- following four principles [2]: controlled deflagration in bubbles
sion impossible — when possible — is • Minimize or in the vapor space in the reactor.
clearly better than trying to mitigate • Substitute Low conversions and reaction
the effects of a potential explosion by • Moderate rates led to large inventories of liquid
adding a blast wall. • Moderate and simplify cyclohexane.
Active layers of protection repre- This more concise set of principles During systematic research on the
sent such features as the basic process makes IS practices simpler to under- flammability and deflagration haz-
control system, a safety-instrumented stand and easier to apply. The excel- ards of cyclohexane, air and oxygen
system, and mechanical interlocks. lent new CCPS book (2009) goes on to mixtures, Chen [5] discovered that the
Procedural or administrative distinguish between first-order and addition of a small amount of water
safety layers are generally considered second-order IS: — which is inert and does not par-
to be the least reliable and include op- • First-order IS efforts change the ticipate in the reaction — helped to
erating procedures and operator inter- chemistry of a process inert the otherwise flammable vapors.
vention. Depending on the site-specific • Second-order IS efforts change the Cyclohexane and water are known to
hazard, procedural or administrative process variables form minimum-boiling azeotropes.
controls may be entirely appropriate. As can be seen by a survey of the pro- The increase in the vapor pressure of
In general, the preferred ranking cess safety literature, most published the cyclohexane/water liquid results
of methods to control process risks is work has applied one or more of the from the increased vapor pressure of
shown below: first four concepts of the eleven cited the water. The water vapor inerts the
by Kletz and Amyotte [1] For this vapor mixture by lowering the upper
Inherent > passive > active > proce-
reason, this article emphasizes three flammable limit of the vapor [5].
dural or administrative
other promising concepts. Chen’s work suggests that it will be
Chemical Engineering www.che.com April 2011 45
Qheat generated
E
B
Engineering Practice Qout
Qout Heat removed
3
Qout

Btu/h
D
safe and practical to use pure oxygen other oxidations include
1
for cyclohexane oxidation. Benefits in- chlorination and bromi- 2
clude both IS operation and improved nation reactions, for ex- C
productivity. They also suggest that ample. And there may be A
this approach could be extended to other examples of vapor-
safer processes for partial oxidation of liquid reactions, such as
Reactor temperature
other liquid hydrocarbons using pure hydrogenation reactions,
oxygen. where addition of a new FIGURE 3. Heat-generation (Q
heat generated) and heat-
Chen’s approach is a first-order IS chemical could improve removal (QOut) rates as a function of reactor temperature
process innovation because it changes the safety of the process. for three different heat-removal designs [9]. Heat gen-
the chemistry of the gas phase in a Addition of an ad- eration is equal to heat removal at points A, C, D, E, and
gas-liquid reaction and prevents the ditional compound to a B, so steady state operation is possible. However, the
reactor is not stable at point D without the addition of
unwanted side reaction of combustion reaction mixture to min- controls or a modification of the design
from occurring in the gas phase. imize hazardous reac-
Although reference [5] did not claim tions may add complexity to the puri- in the process variables and is a form
to have demonstrated a new IS con- fication process, but it may be justified of Moderate, a second-order inherently
cept, Chen’s work is different from the by the increased safety. safer design.
classical definition of the Substitute Chen’s [5] paper on cyclohexane CCPS [2] also cites the work of
principle because the same reactants, oxidation illustrates transformation Luyben and Hendershot [8] that high-
chemical reactions, and products are or hybridization, in which the basic lights how minimization or intensifi-
involved. If the name Substitute were chemistry is maintained, but the ad- cation in a reaction system that is in-
broadened to names such as Change dition of another chemical component tended to improve process safety may
in Chemistry or Hybridize, then it transforms a potentially hazardous re- lead to less robust processes with the
could be lumped in with the many suc- action process into a much safer one. opposite effect.
cessful applications that are possible 2. Create a robust process to sta- I propose here that Stabilize or En-
when using the Substitute concept. bilize or ensure dynamic stability. sure Dynamic Stability be added to
Chen’s innovation permits rapid cy- Not all process designs are inherently the list of IS concepts to be sure that
clohexane oxidation at lower tempera- stable, and if the process design is to be it is not overlooked in the quest for in-
tures and pressures, and could thus safe, the process engineer must ensure herently safer processes.
be said to be an example of the inher- dynamic stability as well as ensuring Application of some of the other IS
ently safer principle Moderate. How- that the steady-state mass and energy principles can adversely affect the dy-
ever, Chen’s approach enables more balances are achieved. A number of namic stability of a process. For exam-
moderate conditions by narrowing the processes exist that have narrow safe- ple, reduced liquid inventories (Mini-
flammability limits through the addi- operating limits but have been made mize) in a distillation train make the
tion of a new component, water. It is stable by the addition of control sys- process inherently safer from one per-
thus an example of supplementation tems. Dynamic stability and control spective because the smaller process
or hybridization. of chemical processes has been exten- inventory decreases the consequences
Although not proposed by Chen [5] sively studied [7]. of loss of containment. However, the
himself, his work suggests that there Designing the process to be more smaller inventory also shortens the
may be many other opportunities inherently stable to process upsets response time of the distillation sys-
for transformation or hybridization with and without control systems is tem to process upsets, increasing the
of other potentially hazardous reac- clearly inherently safer, although this risk that the basic control system will
tions to make them inherently safer. principle is not addressed in most dis- not be able to restore the distillation
Although water would be high on any- cussions of IS. The IS principle Ease of system to the desired operating condi-
one’s list as a potentially transform- Control has usually been interpreted tions and avoid a potentially unsafe
ing additive, it probably will not help to mean a process with a control sys- operating condition and/or an un-
many potentially hazardous reactions. tem that the operator can understand scheduled process shutdown [2].
However, there are many other chemi- clearly and manage effectively. Chemical reactors carrying out
cals that may be inert to the reaction CCPS briefly mentions the advan- exothermic chemical reactions are
and thus also be capable of inerting the tages of designing processes that are perhaps the best known examples of
vapor phase involved in an otherwise inherently more stable or robust [2]: processes that can be dynamically
reactive liquid-vapor reaction. For in- “It is inherently safer to develop unstable. Harriott [9] provides the il-
stance, there are many examples of processes with wide operating limits lustration of an irreversible first-order
azeotropic mixtures in the literature that are less sensitive to variations in chemical reaction being conducted in
and there are many compounds that the operating parameters...Sometimes a continuous-flow, stirred-tank reactor
could prove inert to oxidation reac- this type of process is referred to as a (CSTR). Figure 3 shows the heat-gen-
tions (such as, certain halocarbons). forgiving or robust process.” eration rate by the chemical reaction
Applications are not limited to Designing a robust process increases as a function of reactor temperature.
partial oxidation with air or oxygen; inherent safety by imposing a change Heat-generation rates are low at low
46 Chemical Engineering www.che.com April 2011
Tools for Inherently Safer Process Plant Design
• P rocess hazards reviews • Dynamic process simulation • O ccupied building evaluation
• Chemical interaction matrices • Inherent safety analysis and design
• Dow Fire and Explosion Index and • Area electrical classification
Chemical Exposure Index • P eriodic design reviews during • Safety integrity level assessments
• Fire, explosion and toxic-release product and process research, and safety instrumented systems
consequence modeling and risk development and design • Human factors reviews
assessments • R
 eviews of plant siting, plot plan, • Ergonomics reviews
• Layer of protection analysis equipment arrangement and 3-D • Safety case development
• Spacing tables for units and for computer models • The design process itself
process equipment

temperatures, but as temperature more than it increases the rate of heat of both the uncontrolled process and
increases, the reaction rate increases removal by the reactor cooling system, the controlled process to ensure a ro-
rapidly because of the exponential so the reactor temperature increases bust process.
dependence of the reaction rate co- more instead of cooling back to the de- 3. Limit hazardous effects during
efficient on temperature. At higher sired operating point. conceptual and detailed engineer-
reactor temperatures, the shrinking This further increase in reactor tem- ing. David Clark published a seminal
concentration of reactant (due to con- perature then leads to an even larger paper [10] on the limitation of effects
version to product) reduces the reac- rate of heat generation rate by the when siting and designing process
tion rate and partially overcomes the reactor and additional heating of the plants. He reminds us that there is a
still-increasing reaction-rate coeffi- reactor. Without any effective control strong, non-linear decrease of fire, ex-
cient. The heat-generation rate even- actions, the reactor temperature will plosion, and toxic effects with separa-
tually reaches a constant maximum tend to increase to point E in Figure 3 tion distance. Comparatively small de-
value when the reaction has reached before it stabilizes. creases in separation distance have a
complete conversion. Similarly, in Figure 3 a decrease in major effect, while larger increases in
Figure 3 also shows three different reactor temperature at point D could separation offer diminishing returns.
straight lines for the heat-removal eventually lead to the reactor temper- Methods, such as the Dow Fire and
rate from the reactor for three differ- ature and conversion dropping back to Explosion Index [11] and the Dow
ent reactor-cooling-system designs. To point C. Chemical Exposure Index [12, 13], pro-
achieve a steady-state energy balance, Clearly, of the three reactor cooling- vide quantitative screening estimates
the rate of heat generation (Qheat gen- system designs represented by the of the hazards from various parts of a
erated) by the chemical reaction must three straight lines in Figure 3, the chemical process. Other indices have
equal the rate of heat removal (Qout) reactor cooling system represented by been developed and evaluated to per-
by the reactor cooling system. That line CDE is the least desirable from form a similar objective to the Dow in-
energy balance occurs when the heat a dynamic-stability perspective. Ad- dices [1, 2, 14]. These screening tools
generation curve intersects the heat dition of an effective control system can identify those parts of a process
removal curve (where Qheat generated might be able to provide dynamic sta- where increased separation distances
= Qout). In Figure 3, the three differ- bility — but at the cost of installation are needed to limit potential escala-
ent heat-removal-rate lines intersect and maintenance of the control sys- tion of an incident.
the reactor heat generation rate curve tem and at the cost of residual risk if In one typical plant design, a 10%
at five points. At four of these points the control system fails. increase in separation distances for
(A, B, C, E), the steady-state energy Another example of potential all units increases total plant invest-
balance solution is stable. At each of sources of process instability results ment cost by only 3%. Similarly, dou-
these points, if there is an increase in from efforts to improve energy effi- bling the separation distance for a
temperature, the rate of heat removal ciencies in distillation trains through hazardous unit representing 10% of
increases more rapidly than the rate heat integration. In these cases, the the investment cost of the plant would
of heat generation by the reaction and feed to a column may be preheated cost only 3% more. Because of the non-
the reactor temperature tends to re- by the bottoms product of a second linear effect of separation distance,
turn to the desired operating point. downstream column. This may in- doubling the separation distance for a
Similarly, if the temperature drops crease the risk of process upsets due hazardous unit could reduce explosion
slightly at one of these four operating to increased interactions between the overpressures on the adjacent units
conditions, the rate of heat removal two columns. by a factor of four or more.
decreases more than the rate of heat While avoidance of add-on controls The strong decrease in hazardous
generation by the reactor and the tem- has always been a goal of inherently effects with modest increases in sepa-
perature trends back up to the desired safer design, achievement of that goal ration distances will often more than
operating condition. has seldom mentioned the concepts justify increased capital cost.
In contrast, point D in Figure 3 is an of Ensure dynamic stability or Stabi- Spacing also offers important ben-
inherently unstable operating condi- lize as tools of the process engineer. It efits in crane and other maintenance
tion even though the steady state rate should be considered when consider- access, ergonomic advantages and
of heat generation by the reactor equals ing other means to assure inherently decreased risk of incident escalation.
the rate of heat removal by the reactor safer processes during process design. Future plant expansions or process
cooling system. At point D, an increase The process engineer should work improvements are also facilitated, al-
in reactor temperature increases the closely with the control systems engi- though expansions that decrease spac-
rate of heat generation by the reactor neer to address the dynamic stability ing may increase hazardous effects.
Chemical Engineering www.che.com April 2011 47
Engineering Practice

Applying different IS principles from changes in the chemistry of a Acknowledgments


As discussed, the different IS prin- process that reduces the hazards I gratefully acknowledge the process safety in-
sights from my colleagues at Aker Solutions and
ciples are best applied at different of the chemicals used or produced. at the leading operating companies whose facili-
stages of the process plant timeline. Substitute or Hybridize efforts lead ties we have helped to design, from Professors
Sam Mannan, Trevor Kletz, Ron Darby, Harry
Although IS checklists are often used to first-order inherent safety West and the Mary Kay O’Connor Process Safety
at the screening process hazards anal- • Second-order inherent safety results Center at Texas A & M University, and from
many others in the community of process safety
ysis (PHA) level, much more is needed from changes in the process vari- professionals. The financial support of Aker So-
lutions is also appreciated.
throughout the development and de- ables. Examples include Minimize,
sign of a process plant. Simplify and Stabilize the opera-
For example, Substitute is best tions.
done during the product and process It is also helpful to distinguish be- Author
research phases before significant tween IS processes and IS plants. Victor H. Edwards, P.E.,
is director of process safety
investments of time and resources in Even when hazards cannot be for Aker Solutions Ameri-
a particular product and process are eliminated from the chemistry of cas Inc., (3010 Briarpark
Drive, Houston, TX 77042;
made. Hybridize or Transform is best the process, the plant using the po- Phone: 713-270-2817;
Fax: 713-270-3195; Émail:
done during process research and de- tentially hazardous process can be vic.edwards@akersolutions.
velopment, as is Moderate. made inherently safer through ju- com). In his 28 years with
Aker, Edwards’ experience
Minimize, Simplify, and Error tol- dicious design. includes process engineering,
erance have the best result when ap- Note also that even with IS process safety management and pro-
cess, biochemical and environmental technolo-
plied during the process development, chemistry, it is essential to employ gies. He has received numerous accolades in the
conceptual design and detail design IS principles during the process and areas of safety and environmental engineering,
including five DuPont awards, and has contrib-
phases. Stabilize or Ensure Dynamic plant design to ensure an IS plant. uted extensively to the engineering literature.
His earlier experience includes assistant pro-
Stability is also best done during de- fessor of chemical engineering at Cornell Uni-
sign development. Tools for IS plant design versity, an assignment at the National Science
Foundation, pharmaceutical research at Merck,
Limitation of effects, which is closely There are a number of tools available alternate energy research at United Energy
related to passive protection, has its to aid in designing process plants that Resources, visiting professor at Rice University
and process engineering at Fluor Corp. Edwards
greatest impact during development are inherently safer (Box, p. 18). Al- earned his B.A.Ch.E from Rice University and
of the plot plan and equipment ar- though inherently safer reviews are a his Ph.D. in chemical engineering from the Uni-
versity of California at Berkeley. A registered
rangement. valuable tool for identifying opportu- professional engineer in Texas, he is an AIChE
Fellow, and a member of ACS, AAAS, NFPA,
nities for improvement, it is important NSPE, and the N.Y. Academy of Sciences.
IS processes and plants to keep the principles of inherently
As mentioned previously, the CCPS [2] safer in mind throughout the design Note: This article is based on a paper presented
defines two levels of inherent safety: process. n at the Mary Kay O’Connor International Sym-
posium, Texas A & M University, October 27-28,
• First-order inherent safety results Edited by Suzanne Shelley 2009.

References 10. Clark, David G., Applying the ‘limitation of ef-


fects’ inherently safer processing strategy when
4. Gupta, J.R., and Edwards, D.W., Inherently
safer design — Present and future, “Process
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Plants – a Handbook of Inherently Safer De- Progress, Vol. 27, No. 2, 121–130, June 2008. actions of the Institution of Chemical Engineers
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48 Chemical Engineering www.che.com April 2011

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