Overview of Process Safety, Green Engineering, and Inherently Safer Design

Harry J. Toups LSU Department of Chemical Engineering with significant material from SACHE 2003 Workshop presentation entitled: Inherently Safer Design, by Dennis Hendershot Rohm and Haas Company

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Three Elements of Process Safety

Behavior

Process Safety
Systems Process
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Process Safety Milestone Practices

Pre-1930s Pre-1970s Identify who caused the loss and punish the guilty

Behavior Process

Find breakdown in, and fix man-machine interface

1970s, 80s Development of risk assessment techniques and systematic approaches

Mgmt Systems

1980s +

Performance-, risk-based standards, regulations; green and inherent designs

Comprehensive

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Causes of Losses in Large Plant Accidents

44

Process Design
Accidents (%) 22

12

11 5 5 1

Mechanical

Operator Error

Unknown

Process Upsets

Natural Hazards

Design

Sabotage and Arson

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Green chemistry and engineering A Definition

The design, commercialization, and use of chemical processes and products, which are feasible and economical while minimizing:
1) generation of pollution at the source, and 2) risk to human health and the environment.
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New paradigm for the environment

Traditional environmental approach
End of pipe waste treatment Waste minimization an advance, but we can go further

Green chemistry and engineering

Eliminate or dramatically reduce hazards to the environment
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Many of us learned this as children

Dr. Suess The Cat in the Hat Comes Back

Once you get something dirty, the only way to get it clean is to make something else dirty.
The best way to keep the world clean is to not get it dirty to begin with.
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Inherently Safer Design A Definition

The design of chemical processes and products with specific attention to eliminating hazards from the manufacturing process rather than relying on the control of these hazards

Notice the common philosophy to Green Engineering?

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New paradigm for safety

Traditional safety approach
Add on safety features
Prevent - alarms, safety interlocks, procedures, training Mitigate sprinkler systems, water curtains, emergency response systems and procedures

Inherently safer design

Eliminate or significantly reduce process hazards
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Inherently safer design, green chemistry, and green engineering

Inherently Safer Design Green Chemistry and Engineering

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Why are we interested in inherently safer design?

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Flixborough, England (1974)

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Flixborough, England (1974)

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Henderson, Nevada, (1988)

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What is inherently safer design?

Inherent - existing in something as a permanent and inseparable element...
safety built in, not added on

Eliminate or minimize hazards rather than control hazards More a philosophy and way of thinking than a specific set of tools and methods
Applicable at all levels of design and operation from conceptual design to plant operations

Safer, not Safe

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Hazard
An inherent physical or chemical characteristic that has the potential for causing harm to people, the environment, or property (CCPS, 1992). Hazards are intrinsic to a material, or its conditions of use. Examples
Phosgene - toxic by inhalation Acetone - flammable High pressure steam - potential energy due to pressure, high temperature
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To eliminate hazards:
Eliminate the material Change the material Change the conditions of use

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Chemical Process Safety Strategies

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Inherent
Eliminate or reduce the hazard by changing to a process or materials which are non-hazardous or less hazardous Integral to the product, process, or plant cannot be easily defeated or changed without fundamentally altering the process or plant design EXAMPLE
Substituting water for a flammable solvent (latex paints compared to oil base paints)

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Passive
Minimize hazard using process or equipment design features which reduce frequency or consequence without the active functioning of any device EXAMPLE
Containment dike around a hazardous material storage tank

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Active
Controls, safety interlocks, automatic shut down systems Multiple active elements Sensor - detect hazardous condition Logic device - decide what to do Control element - implement action Prevent incidents, or mitigate the consequences of incidents EXAMPLE High level alarm in a tank shuts automatic feed valve Caution: Even protective systems can cause incidents! (See Hendershot et al handouts)
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Procedural
Standard operating procedures, safety rules and standard procedures, emergency response procedures, training EXAMPLE
Confined space entry procedures

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Batch Chemical Reactor Example

Hazard of concern Runaway reaction causing high temperature and pressure and potential reactor rupture

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Passive
Maximum adiabatic pressure for reaction determined to be 150 psig Run reaction in a 250 psig design reactor Hazard (pressure) still exists, but passively contained by the pressure vessel
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Active
Maximum adiabatic pressure for 100% reaction is 150 psig, reactor design pressure is 50 psig Gradually add limiting reactant with temperature control to limit potential energy from reaction Use high temperature and pressure interlocks to stop feed and apply emergency cooling Provide emergency relief system
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Procedural
Maximum adiabatic pressure for 100% reaction is 150 psig, reactor design pressure is 50 psig Gradually add limiting reactant with temperature control to limit potential energy from reaction Train operator to observe temperature, stop feeds and apply cooling if temperature exceeds critical operating limit
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Inherent
Develop chemistry which is not exothermic, or mildly exothermic
Maximum adiabatic exotherm temperature < boiling point of all ingredients and onset temperature of any decomposition or other reactions

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Which strategy should we use?

Generally, in order of robustness and reliability:
Inherent Passive Active Procedural

But - there is a place and need for ALL of these strategies in a complete safety program
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Inherently Safer Design Strategies

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Inherently Safer Design Strategies

Minimize Moderate Substitute Simplify

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Minimize
Use small quantities of hazardous substances or energy
Storage Intermediate storage Piping Process equipment

Process Intensification

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Benefits
Reduced consequence of incident (explosion, fire, toxic material release) Improved effectiveness and feasibility of other protective systems for example:
Secondary containment Reactor dump or quench systems

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Semi-batch nitration process

Catalyst (usually sulfuric acid) feed or pre-charge Organic Substrate and solvents pre-charge Nitric acid gradual addition

Batch Reactor ~6000 gallons

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How can Process Intensification be used in this reaction?

Mixing bringing reactants into contact with each other Mass transfer from aqueous phase (nitric acid) to organic phase (organic substrate) Heat removal
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CSTR Nitration Process

Raw Material Feeds

Organic substrate Catalyst Nitric Acid

Reactor ~ 100 gallons Product

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One step further: Do this reaction in a pipe reactor?

Raw Cooled continuous Material mixer/reactor Feeds Organic substrate Catalyst Nitric Acid
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Scale up

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Scale out

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On-demand phosgene generation

Continuous process to produce phosgene Phosgene consumers are batch processes No phosgene storage Engineering challenges Rapid startup and shutdown Quality control Instrumentation and dynamic process control Disposal of tail gas and inerts

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Moderate
Dilution Refrigeration Less severe processing conditions Physical characteristics Containment
Better described as passive rather than inherent

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Dilution
Aqueous ammonia instead of anhydrous Aqueous HCl in place of anhydrous HCl Sulfuric acid in place of oleum Wet benzoyl peroxide in place of dry Dynamite instead of nitroglycerine

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Effect of dilution
Centerline Ammonia Concentration, mole ppm 20,000 (B) - Release Scenario: 2 inch transfer pipe failure

10,000

Anhydrous Ammonia

28% Aqueous Ammonia

0 0 Distance, Miles 1

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Less severe processing conditions

Ammonia manufacture
1930s - pressures up to 600 bar 1950s - typically 300-350 bar 1980s - plants operating at pressures of 100-150 bar were being built

Result of understanding and improving the process Lower pressure plants are cheaper, more efficient, as well as safer
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Substitute
Substitute a less hazardous reaction chemistry Replace a hazardous material with a less hazardous alternative

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Substitute materials
Water based coatings and paints in place of solvent based alternatives
Reduce fire hazard Less toxic Less odor More environmentally friendly Reduce hazards for end user and also for the manufacturer

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Simplify
Eliminate unnecessary complexity to reduce risk of human error
QUESTION ALL COMPLEXITY! Is it really necessary?

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Simplify - eliminate equipment

Reactive distillation methyl acetate process (Eastman Chemical) Which is simpler?
Acetic Acid Methanol Catalyst Methyl Acetate

Methyl Acetate Acetic Acid

Reactor Solvent Recovery

Methanol Recovery

Splitter Extractive Distillaton Water

Sulfuric Acid Methanol Reactor Column Impurity Removal Columns

Color Column

Decanter Extractor

Heavies

Azeo Column

Flash Column

Water
Heavies

Flash Column Water Water

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Modified methyl acetate process

Fewer vessels Fewer pumps Fewer flanges Fewer instruments Fewer valves Less piping ......

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But, it isnt simpler in every way

Reactive distillation column itself is more complex Multiple unit operations occur within one vessel More complex to design More difficult to control and operate

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Single, complex batch reactor

Large Rupture Disk A B C D E Distillate Receiver Condenser

Steam Refrigerated Brine Water Return

Water Supply

Condensate

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A sequence of simpler batch reactors for the same process

A B C Large Rupture Disk Refrigerated Brine

Water Return

Water Supply

Condenser E Distillate Receiver

Steam

Condensate

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Inherent safety conflicts

In the previous example
Each vessel is simpler

But
There are now three vessels, the overall plant is more complex in some ways Compare to methyl acetate example

Need to understand specific hazards for each situation to decide what is best
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Conflicts and Tradeoffs

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Some problems
The properties of a technology which make it hazardous may be the same as the properties which make it useful:
Airplanes travel at 600 mph Gasoline is flammable
Any replacement must have the ability to store a large quantity of energy in a compact form

Chlorine is toxic

Control of the hazard is the critical issue in safely getting the benefits of the technology
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Multiple hazards
Everything has multiple hazards
Automobile travel
velocity (energy), flammable fuel, exhaust gas toxicity, hot surfaces, pressurized cooling system, electricity......

Chemical process or product

acute toxicity, flammability, corrosiveness, chronic toxicity, various environmental impacts, reactivity.......
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What does inherently safer mean?

Inherently safer is in the context of one or more of the multiple hazards There may be conflicts
Example - CFC refrigerants
low acute toxicity, not flammable potential for environmental damage, long term health impacts Are they inherently safer than alternatives such as propane (flammable) or ammonia (flammable and toxic)?
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Inherently safer hydrocarbon based refrigerators?

Can we redesign the refrigeration machine to minimize the quantity of refrigerant sufficiently that we could still regard it as inherently safer?
Home refrigerators perhaps (<120 grams) Industrial scale applications probably not, need to rely on passive, active, procedural risk management strategies
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Multiple impacts
Different populations may perceive the inherent safety of different technology options differently Example - chlorine handling - 1 ton cylinders vs. a 90 ton rail car A neighbor two miles away? An operator who has to connect and disconnect cylinders 90 times instead of a rail car once? Who is right?
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Inherently safer = safer

Air travel
several hundred people 5 miles up control in 3 dimensions 600 mph thousands of gallons of fuel passengers in a pressure vessel .........

Automobile travel
a few people on the ground control in 2 dimensions 60 mph a few gallons of fuel

might even be a convertible .........

z z z

Automobile travel is inherently safer But, what is the safest way to travel from Washington to Los Angeles? Why?
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At what level of design should engineers consider inherently safer design?

Selecting Technology? Plant Design? Equipment Details? Operations? Best answer? All levels! Inherently safer design is not a meeting. Inherently safer design is a way of thinking, a way of approaching technology design at every level of detail part of the daily thought process.
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Questions a designer should ask when he has identified a hazard

In this order
1. Can I eliminate this hazard? 2. If not, can I reduce the magnitude of the hazard? 3. Do the alternatives identified in questions 1 and 2 increase the magnitude of any other hazards, or create new hazards? 4. At this point, what technical and management systems are required to manage the hazards which inevitably will remain?

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The Future: Inherently safer design

Some hazardous materials and processes can be eliminated or the hazards dramatically reduced. The useful characteristics of other materials or processes make their continued use essential to society for the foreseeable future we will continue to manage the risks. E.g., Air travel
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Is It Worth the Effort?

Total Recordable Injury/Illness Rate

12 10 8 6 4 2 0

Number of US workplace injuries/illnesses per 100 employees continues to drop

due to comprehensive safety strategies, including Inherently Safer Design

1973

1983

1993

2003
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END OF PRESENTATION

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