Presented Before the Division of Environmental Chemistry

American Chemical Society

Washington, D. C. August 21-25, 1994
Paper No. ENVR-135

CHEMISTRY - THE KEY TO INHERENTLY SAFER

MANUFACTURING PROCESSES

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

The American College Dictionary defines “inherent” as “existing in something as a permanent and
inseparable element, quality, or attribute.”1 Thus an inherently safer process is safer because of its essential
characteristics, which belong to the process by its very nature. I have intentionally described processes
as “inherently safer," rather than as “inherently safe.” An object or activity can be described as safer than
something else relatively easily, and with some chance of general agreement. However, characterizing
something as safe is much more difficult. "Safe" is difficult to define, and the definition necessarily involves
personal, institutional, or societal values and judgements.

The pop-top soda can provide an excellent example of inherently safer design from everyday life. Some
of us can remember when soda in cans was first introduced. A separate device was required to open these
cans, and the first “pop-tops” represented a major advance in convenience. The original pop-tops were
scored tear strips in the can top with attached rings or levers to grasp and tear the metal tab from the can.
When the can was opened the top was completely removed from the can and discarded. These tabs were
environmental hazards when discarded. Some people would dispose of the tab by placing it into the can
before drinking the soda. Occasionally the tab would be swallowed when drinking from the can, and it
sometimes had to be surgically removed. Clearly the current design of the pop-top soda can, where the
tab remains an integral part of the can after opening, represents an inherently safer design. While the tab
can be removed by flexing it back and forth until the metal fails, it requires some additional effort to do this.
It is easier to use the can safely. We need to design chemical processes and plants like the modern pop
top can - they should be safe by their very nature, and the easiest way to operate them must also be the
safest way - “User Friendly Plants.” The description of the development of the pop-top can, as well as
many other common everyday objects, can be found in Henry Petroski's The Evolution of Useful

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Things2. There are many other examples of inherent safety in Petroski’s description of the evolution of
common technological artifacts such as the paper clip, the stapler, and the table fork.

In a 1988 report, the National Research Council identified inherently safer plant design as a critical element
in the ongoing efforts for continuing improvement of safety in the chemical processing industries. In
particular the report acknowledges the key role of process selection, stating that "few basic decisions affect
the hazard potential of a plant more than the initial choice of technology."3 The process chemistry is the
foundation of this initial technology choice.

Chemical process safety strategies may be categorized as follows:

Inherent - eliminating the hazard by using materials or processing conditions which are
nonhazardous

Passive - eliminating or minimizing the hazard by process or equipment design features which do
not eliminate the hazard, but reduce risk without the need for any device to actively function

Active - using controls, safety interlocks and emergency shutdown systems to detect potentially
hazardous deviations and take corrective action before the deviation becomes serious enough to
result in an incident

Procedural - using operating procedures, administrative controls, emergency response and other
management approaches to prevent incidents or minimize the impact of an incident after it occurs

All these approaches have their place in a complete risk management program. The approaches in the
inherent and passive categories are generally regarded as inherently safer than active and procedural
approaches. Marshall4 categorizes safety approaches as “strategic” and “tactical.” Inherent and passive
approaches are strategic, must be implemented early in the facility development, and have broad and wide
ranging impacts on the process design. Tactical approaches, including the active and procedural categories,
can be implemented late in the design process and are characterized by repetition and high costs associated
with maintenance.

These categories can also be illustrated by an example from everyday life. Falls on stairs are a common
cause of household injuries. An inherently safer approach to this household hazard would be to build a
ranch house - a single story with no steps. A passive approach would be to design the steps to reduce the
likelihood and consequence of falls. For example, well anchored and padded carpet could be installed on
the steps instead of waxed hardwood. An active approach is more difficult to envision for this example,
but perhaps one could design some kind of a "fall detector" which could release something like an
automobile air bag which would catch people when they fell. The procedural approach would be to require
everybody to walk slowly on the steps, to take one step at a time, to firmly grip the hand rails, to wear low
heeled, rubber soled shoes, and to require regular training on the proper way to go up and down steps.

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Kletz5 divides inherently safer design strategies into five basic categories:

Intensification - Using hazardous substances in small quantities

Example: Development of continuous reactors for nitroglycerine manufacture, reducing

reactor volume by orders of magnitude5, 9

Substitution - Using less hazardous materials

Example: Use of aqueous latex emulsion paints in place of solvent based paints9

Attenuation - Using materials under less hazardous conditions

Example: Refrigerated storage of materials such as chlorine, methylamine, and butadiene

as refrigerated liquids at atmospheric pressure rather than pressurized liquids
at ambient temperature6, 7, 9

Limitation of effects - Minimizing the release of hazardous material or energy

Example: Semi-batch processing for exothermic reactions, such as polymerization

reactions, feeding a limiting reagent (usually the monomer) over a period of
time such that it is consumed as it is fed, minimizing the inventory of material
available for reaction and the energy available for release in case of loss of
temperature control8

Simplification/error tolerance - facilities which make errors less likely, or are forgiving of errors
if they are made

Example: Designing processes which have wide safe operating limits and which are
forgiving of deviations from intended operating conditions5

While process chemistry has a potential impact on all these categories, its major contribution is in the areas
of intensification, substitution and attenuation. Innovative process chemistry options using less hazardous
materials, rapid and efficient reactions allowing smaller manufacturing equipment and eliminating product
purification steps, and operating at less extreme conditions of temperature and pressure will be inherently
safer. Interestingly, a list of process attributes which might be expected to result in an economic advantage
would contain these same characteristics. Thus in many cases a process which is inherently safer is also
economically more attractive.

Early identification and evaluation of process chemistry options are keys to the development of inherently
safer processes. It has been estimated that the first 10-15% of the work in developing a new product or

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process commits 50-85% of the final cost. I believe that similarly, the first portion of the total effort of
product/process development defines most of the risk inherent in the operation of the manufacturing facility.
Early decisions on the process route become difficult to change as product development continues.
Chemistry changes may change product properties in large or subtle ways. Impurities and by-products in
the product may change. Customers and end users of the product may have to adjust their products and
processes, and a large amount of rework may be needed in the development process, costing both money
and time. Therefore, consideration of inherently safer options early in the process development is critical
to the development of such processes.

There are many excellent examples of inherently safer process chemistry options. Kletz5, Englund8, and
CCPS9 offer many examples. A few examples are included here.

Polymer or other supported systems

Many useful reagents, functional groups, or catalysts can be immobilized by attachment to a polymer or
other solid support. This reduces the vapor pressure of a volatile material and reduces or eliminates the
hazard of absorbing a toxic material through the skin or lungs. Some examples include:

- The use of polystyrenesulfonic acid in place of sulfuric acid to catalyze the reaction of methanol
and isobutene to manufacture methyl t-butyl ether (MTBE).10

- Similar polymer supported acid catalysts used for esterification reactions.

- Use of clay supported metal ions to replace Lewis acid catalysts such as aluminum chloride for
Friedel-Crafts reactions.11

Use of catalysts

Improved catalysts allow the use of less reactive (and therefore generally less hazardous) materials and
milder processing conditions. Catalysts also often give greater selectivity, productivity and yield resulting
in smaller production equipment and the reduction in size or elimination of purification or recycle equipment.
Some examples include:

- Acrylate esters were formerly manufactured using the Reppe process, reacting acetylene,
carbon monoxide and an alcohol in the presence of nickel carbonyl catalyst to produce the
corresponding acrylate ester. The newer propylene oxidation process catalytically oxidizes
propylene to acrylic acid, which is then esterified with the appropriate alcohol to make the
ester12.

- Methylamines are produced by the catalytic reaction of ammonia with methanol. The reaction
produces a mixture of mono-, di-, and trimethyl amines. Unfortunately the reaction equilibrium

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 favors production of trimethylamine, but the largest product demand is for dimethylamine. The
development of improved Zeolite catalysts has allowed better control of the product ratio,
greatly reducing the size of equipment to separate and recycle trimethylamine.13

- DuPont has developed a catalytic oxidative-dehydrogenation process for producing methyl

isocynate (MIC) which allows MIC to be produced and converted to the final agricultural
chemical product in-situ, eliminating the need to store large inventories of MIC.14

- Improvements in processes for the manufacture of ammonia, including catalyst improvements,

have reduced the operating pressures in ammonia plants. In the 1930s a typical ammonia plant
operated at a pressure of 450-600 bar; with current technology, operating pressures are as
low as 100-150 bar.15

Solvent substitution

Solvents can often be replaced with less toxic, volatile, or flammable alternatives. For example, many
polymers can be manufactured as aqueous suspensions or emulsions instead of in organic solvents. Phase
transfer catalysis can sometimes allow the use of less solvent or no solvent.9

Supercritical extraction and other processing

Supercritical extraction offers the potential for replacing organic extraction solvents with less hazardous
materials such as water or carbon dioxide. This represents an interesting example of safety tradeoffs and
conflicts. Supercritical extraction often requires high temperatures and pressures, an inherent safety
disadvantage, but may allow the use of less toxic or flammable solvents.

Supercritical processing also presents opportunities for new and interesting chemistry options. At
supercritical conditions many materials have significantly different physical and chemical characteristics.
For example, for water, the dielectric constant decreases from 80 to 5, diffusion coefficients increase
significantly, two-thirds of hydrogen bonds are destroyed, and hydrophobic effects whichlimit the solubility
of organic compounds disappear. It may be possible to use temperature and pressure to control the
properties of supercritical water to imitate those of many organic solvents, making supercritical water a
potential replacement for these organic solvents.16

Biochemistry

One of the objectives in designing an inherently safer process is to operate under less severe temperature
and pressure conditions. Biological systems are capable of producing many complex organic chemicals
at very mild conditions. Inherently safer manufacturing technology for some materials might involve
fermentation or other biological systems directly. Alternatively, a thorough understanding of the chemical

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reaction paths and mechanisms involved in biological systems opens the possibility of application of those
paths and mechanisms in non-biological systems.

Mixing and physical considerations

Chemical reactions are often very fast once the reacting molecules actually get together. The rate limiting
step is often mass or heat transfer. Innovative reactor designs can overcome these limitations resulting in
a much smaller reactor. Some examples include:

- Buss loop/jet reactors for chlorination9

- Loop reactors for emulsion polymerization17
- Tubular reactors for Caro's Acid 18
- Antibiotic intermediate manufacture in a centrifugal extractor/reactor19
- Optimization of agitation to maintain a nonflammable atmosphere in a fermentation reactor20
- Use of static mixers as reactors9

Summary

The basic process chemistry is the key to the development of inherently safer chemical manufacturing
processes. Chemistry options must be identified early in the development process, and the inherent safety
and environmental friendliness of the process must be one of the criteria used to evaluate the various
options. If inherent safety is one of the goals of chemical process development, then innovative new
chemistry options will be developed to achieve this goal. Perhaps we can succeed in realizing a vision
described by Benson and Ponton21 of a future chemical industry based on small, inherently safe,
environmentally friendly, unobtrusive chemical plants using common utility raw materials and other non-
hazardous feedstocks, and providing product on demand and at the point of demand reliably and with no
need for significant storage.

References

1. The American College Dictionary, Random House, New York, 1967.

2. Petroski, H., The Evolution of Useful Things, Vintage Books, New York, 1992.

3. “Design of Inherently Safer Plants”, Chemical Engineering Progress, Sept. 1988, p. 21.

4. Marshall, V. C., “The Social Acceptability of the Chemical Industry”, Transactions of the
Institution of Chemical Engineers, Vol. 68, Part B, May 1990, pp. 83-93.

5. Kletz, T. A., Plant Design for Safety, Hemisphere Publishing Corporation, New York, 1991.

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6. Marshall, J., et. al., “The Relative Risk of Pressurized and Refrigerated Storage for Six
Chemicals”, 1994 American Institute of Chemical Engineers Summer National Meeting,
August 14-17, 1994, Denver, CO, Paper No. 47e.

7. Melhem, G. A., “Hazard Reduction Benefits from Reduced Storage Temperature of

Pressurized Liquids”, Prevention and Control of Accidental Releases of Hazardous Gases,
V. Fthenakis, ed., Van Nostrand Reinhold, New York, 1993, pp. 411-437.

8. Englund, S. M., “Design and Operate Plants for Inherent Safety”, Chemical Engineering
Progress, March 1991, pp. 85-91 (Part 1) and May 1991, pp. 79-86 (Part 2).

9. CCPS, Guidelines for Engineering Design for Process Safety, Center for Chemical Process
Safety, American Institute of Chemical Engineers, New York, 1993.

10. Sherrington, D. C., “Polymer Supported Systems: Towards Clean Chemistry?”, Chemistry
and Industry, Jan. 7, 1991, pp. 15-19.

11. Calvert, C., “Environmentally Friendly Catalysts Using Non-toxic Supported Reagents”,
Environmental Protection Bulletin, No. 021, November 1992, pp. 3-9.

12. Hochheiser, S., Rohm and Haas, History of a Chemical Company, University of
Pennsylvania Press, Philadelphia, PA, 1986.

13. Blumenberg, B., “Chemical Reaction Engineering in Today's Industrial Environment”, Chemical
Engineering Science, Vol. 47, No. 9-11, 1992, pp. 2149-2162,

14. Manzer, L. E., “Toward Catalysis in the 21st Century Chemical Industry”, Catalysis Today,
Vol. 18, 1993, pp. 199-207.

15. Kharbanda, O. P., and E. A. Stallworthy, Safety in the Chemical Process Industry,
Heinemann Professional Publishing, Ltd., London, 1988.

16. Johnston, K. P., “Safer Solutions for Chemists”, Nature, 17 March 1994, pp. 187-188.

17. Wilkinson, M. and K. Geddes, “An Award Winning Process”, Chemistry in Britain,
December 1993, pp. 1050-1052.

18. Whiting, M. J. L., “The Benefits of Process Intensification for Caro's Acid Production”,
Transactions of The Institution of Chemical Engineers, March 1992, Part A, pp. 195-196.

19. Paul, E. L., “Design of Reaction Systems for Specialty Organic Chemicals”, Chemical
Engineering Science, Vol. 43, No. 8, 1988, pp. 1773-1782.

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20. Ishizaki, A., et. al., “Equipment and Operation for Fermentative PHB Production Using
Gaseous Substrate to Guarantee Safety from Explosion”, Journal of Chemical Engineering
of Japan, Vol. 26, No. 2, 1993, pp. 225-227.

21. Benson, R. S., and J. W. Ponton, “Process Miniaturisation - A Route to Total Environmental
Acceptability?”, Transactions of The Institution of Chemical Engineers, Vol. 71, Part A,
March 1993, pp. 160-168.