Inherently Safer Process Design

Available tools and case studies

Zulfan Adi Putra

Process Enginer
 Outline

• What Went Wrong?

• Definition of Inherently Safer Process Design
• Inherently Safer Process Design Strategy
• INSET and Index Calculation Tools for Inherently Safer Process Design in:
– Process selection
– Flowsheet development
– Process and equipment design
– Planning and scheduling
• Case Studies/Examples
– Process selection
– Flowsheet development
– Process and equipment design
– Planning and scheduling
– Inherently safer for existing plants
• Conclusion
• Future Works
• References
 What Went Wrong?
case Histories of Process Plant Disasters
 What Went Wrong?
Case Histories of Process Plant Disasters [5]

Many of incidents were the result of leaks of hazardous materials,

and the recommendations described ways of preventing leaks by
providing better equipment or procedures.
However, equipment can fail or neglected, and procedure can lapse [5]
Situations What is lacked out of many
Nypro factory, Flixborough UK, 1974. Knowledge to design highly stressed
Failure of temporary installed pipe connecting huge reactors , pipe.
releasing 50 tons of cyclohexane, mixed with air and exploded. Reduction of hazardous inventories.
Killing 28 people and destroying the plant
Carbaryl production in Bhopal, 1984. Reduction of hazardous intermediates
Intermediate chemicals, Methyl Iso Cyanate (MIC), was inventories.
leaking, causing more than 2000 people dead and injuring Awareness to select different reaction
200,000 people. routes
Keeping incompatible materials apart
Seveso, Italy, 1976. Using unnecessarily hot heating
A reactor containing an uncompleted batch of 2,4,5- medium
trichlorophenol (TCP) was left for the weekend. External
steam temperature was so high that a runaway reaction
started. Surrounding area became unfit for habitation
Inherently Safer Process Design
Definition
 Inherently Safer Process Design (1)

• A chemical manufacturing process is said as inherently safer IF:

– it reduces or eliminates one or more hazards assoc. with the materials and
operations used in the process when compared to some alternative process,
– And this reduction or elimination is accomplished by characteristics which are
permanent and inseparable parts of the process [1]
• Hazard an inherent physical or chemical characteristic that has the potential for
causing harm to people, property or the environment [1]
– Example: 10000 lb of propane holds the same amount of energy which could be
released by 28 tons of TNT [2]
• Traditional approach introduce barriers (layers of protection) [1]:
– Operator supervision
– Control system
– Alarms
– Interlocks
– Physical protection devices
– Emergency response systems
 Inherently Safer Process Design (2)

Disadvantages of traditional approach [1]:

• Barriers are expensive to build and maintain throughout the life of the process
• Any failure of the barriers could potentially result in an accident
• The hazard still exists, and if something can go wrong, it will go wrong

Inherently safer process design approach [1]:

• Reduce/eliminate hazard less barriers required less risk of barrier failures
• Best opportunities are early in the process life cycle including selection of process
routes, raw materials, process parameters, and unit operations (flowsheet
development)
• Searching for inherently safer options starts at the earliest stage and never stop

Famous phrase:
“What You Don’t Have Can’t Leak”
Inherently Safer Process Design
Strategy
 Inherently Safer Design Strategy (1)

• Inherently safer design strategy includes:

– Intensification/minimize reduce the inventories or use small quantities of
hazardous materials

– Substitution use less hazardous materials or replace with a less hazardous

one

– Attenuation/moderate use less hazardous process conditions (e.g. pressure,

temperature), less hazardous form of a material or facilities which minimize the
impact of a release of hazardous material or energy

– Simplify design facilities which eliminate unnecessary complexity and make

operating errors less likely

• INSIDE project [3] produced Inherently SHE Evaluation Tool (INSET) toolkit as a
guideline for challenging the way things done normally and suggesting alternatives.
This toolkit is applicable during the process life-cycle.
 Inherently Safer Design Strategy (2)

At earlier stages (route selection until process and equipment design relevant activities
for me):

– Alternatives are identified utilizing inherently safer design strategies within the
constraints of process and economics [3, 4, 6, 7]

– Each alternative is ranked based on their safety indices [3, 4, 6, 7]

– Optimum process is then selected based on their rank

INSET and Index Calculation Tools
for Inherently Safer Process Design
 INSET Toolkit: Stages

4 stages
Tool A – R which are
overlapped between
stages
 INSET Toolkit: Tool B (1)

Tool B is used for the entire stages

It is aimed to challenge route and alternatives in order to obtain a more inherently safer,
healthier, and more environmentally friendly (ISHE) process
 INSET Toolkit: Tool B (2)

Identify alternative
process options via guideword:
 INSET Toolkit: Tool B (3)

Identify alternative
process options via ISHE options:
 INSET Toolkit : Tool B (4)

Identify alternative unit operations via

functionality prompt list:
 INSET Toolkit : Tool B (5)

Identify alternative
for waste to
water, air, etc
 INSET Toolkit : Tool B (6)

Identify alternatives for transportation:

 INSET Toolkit : Tool B (7)

Option evaluations
INSET Toolkit: Example (1)
Stage 1: Chemistry Route Selection
 INSET Toolkit: Example (2)
Stage 2: Chemistry route detail evaluation
INSET Toolkit: Example (3)
Stage 3: Process Design Optimization
INSET Toolkit: Example (4)
Stage 4: Process Plant Design
Indexing Tools for Process Selection (1)

Available tools for process selection:

1. Prototype Index for Inherent Safety (PIIS)
• Developed by Edwards and Lawrence (1993) [6]
• It considers raw materials used and reaction steps (reaction routes)
• Chemical score: inventory, flammability, explosiveness, and toxicity
• Process score: temperature, pressure, and yield
• Information is taken from literature and MSDS
2. Inherent Safety Index (ISI)
• Developed by Heikkilä (1999) [4]
• It considers reaction routes and separation sections
• Chemical index: chemical reactivity, flammability, explosiveness, toxicity,
and corrosiveness
• Process index: inventory, temperature, pressure, equipment, and process
structure
• Information is taken from literature and MSDS, and process selection
Indexing Tools for Process Selection (2)

Available tools for process selection:

3. i-Safe index
• Developed by Palaniappan (2002) [7]
• Using sub-index values from ISI and PIIS, plus NFPA reactivity rating
• Individual (overall) chemical index: flammability, toxicity, explosiveness,
NFPA reactivity
• Individual (overall) reaction index: temperature, pressure, yield, heat of
reaction
Indexing Tools for Flowsheet Development

Available tools for flowsheet developments:

1. Inherent Safety Index (ISI)
• Developed by Heikkilä (1999) [4]
• It considers reaction routes and separation sections
• Chemical index: chemical reactivity, flammability, explosiveness, toxicity,
and corrosiveness
• Process index: inventory, temperature, pressure, equipment, and process
structure
• Information is taken from literature and MSDS, and process selection
2. i-Safe index
• Developed by Palaniappan (2002) [7]
• Flowsheets are ranked based on scoring scheme proposed in ISI [3]
Indexing Tools for Process and Equipment
Design
Available tools for process and equipment design:
1. Integrating Dow’s fire and explosion index (F&EI) into process design [2]
• Dow’s F&EI is used as a function of material inventory and operating
pressure
• This function is used as a safety constraint in the process optimization
framework
Indexing Tools for Planning and Scheduling

Available tools for planning and scheduling:

1. Integrating Dow’s F&EI in inherently safer design and process scheduling [8]
• Alternative designs and expected scheduling options are evaluated based
on their technical constraints
• Economical values for each options are evaluated
• Safety indices are calculated for each option
• Pareto curve is developed demonstrating a trade-off between the inherently
safer design and various production and operation scheduling
Case Studies of Index Calculation Tools
for Inherently Safer Process Design
 Case Study for Process Selection (1)

Comparison of Methyl Methacrylate (MMA) process routes [9]:

6 process routes are identified to produce MMA, namely:
1. Acetone cyanohydrin (ACH) route
2. Ethylene route via propionaldehyde (C2/PA)
3. Ethylene route via methyl propionate (C2/MP)
4. Propylene route (C3)
5. Isobutylene route (i-C4)
6. Tertiary butyl alcohol (TBA) route
Case Study for Process Selection (2)
Case Study for Process Selection (3)
 Case Study for Process Selection (4)

• ISI approach is more in agreement with expert (from industries and universities
including professors Kletz, Lees, and Duxbury [9]) evaluations. It is however more
laborious.

• PIIS is very reaction-step oriented and does not consider separation sections, lacks
of inventory evaluation. Straightforward and fast to use with relatively good results.
• i-Safe is also reaction oriented, easy to use, wider range of subindices than PIIS.
Also does not consider separation sections, lacks of inventory, equipment and
process subindices.
Case Study for Flowsheet Development (1)

ISI index is used for calculating the safety index while developing the flowsheet [10].

Flowsheet is developed in iCON (a process simulation software, similar to Aspen

HYSYS) while the ISI index is calculated in MS Excel.

This allows various design alternatives to be evaluated simultaneously with the

safety aspect.
Case Study for Flowsheet Development (2)

Connecting process simulation software and safety index [10]

Case Study for Flowsheet Development (3)

Process flow diagram in iCON connected with ISI index in MS Excel [10]
Safety can be evaluated simultaneously during flowsheet development
Case Study for Process and Equipment
Design (1)
Case study is taken from Suardin et. al., 2007 [2]:
Simple Reactor + Distillation units
A B (gas phase)
Reactant A = hazardous chemical
Reactor pressure range = 2 – 8 atm
Feasible conversion = 40% - 70%
Distillation pressure range = 10 -16 atm
Case Study for Process and Equipment
Design (2)
Feasible range of conversion without taking into account the inherently safer limit
Case Study for Process and Equipment
Design (3)
AIChE (1994) recommends that F&EI < 128
This additional safety constraint is included into the optimization

Conversion limit for

ensuring safer design
Case Study for Process Scheduling (1)

A refinery case study for gasoline and diesel productions with NOx emission as the
environmental issue.
Variations of demands for gasoline and diesel during the year.
Unit operations involved: Fluidized Catalytic Cracker (FCC) for fuels productions and
Selective Catalytic Reduction (SCR) unit for reducing NOx emission.
Different crude properties and different operation mode yield different NOx
emissons.
Case Study for Process Scheduling (2)
Pareto curves are constructed to show trade-offs (each dot represents a certain design
and production schedule):

As production increases (productions are scheduled more often), profit increases,

HOWEVER, the need for NOx removal increases, more chemicals (NH3 and ethanol)
used for removing NOx, and hazardous level increases.
These curves show trade-offs of economic, environmental, and safety objectives of the
company
 Case Study for Inherently Safer Existing
Plants (1)
Several examples of inherently safer approaches for existing plants [11]:
Plants and Situations
Insecticide production from MIC.
At the time of Bhopal incident, DuPont
was purchasing MIC from a supplier and
transporting it by railcar to a plant located
near a major metropolitan area over a
thousand miles away. The facility stored
several million pounds of MIC at site. MIC
was used to make profitable insecticide.
Approaches
In response to Bhopal incident, DuPont’s
R&D developed:
- an alternative route of a raw material
significantly less hazardous than MIC.
- employed an alternative reactor
technology, converting the new raw
material into MIC in situ and immediately
consume the MIC.
Results: eliminate risk of transporting and
storing MIC
 Case Study for Inherently Safer Existing
Plants (2)
Plants and Situations Approaches

Ethylene Oxide production. To eliminate contact between pure EO

and hot surfaces of the reboiler, two
columns are combined. Eliminating the
potential EO decomposition and providing
dilute mixture in the reboiler. (US Patent:
5,529,667).

EO is very hazardous (flammability range

from 3% - 100% due to its own oxygent,
decomposes, and polymerizes, through
highly exothermic reactions. Explosions
occurred in the 2nd column where pure EO
is reboiled (BP in Antwerp, 1987 and UC in
TX, 1991)
 Case Study for Inherently Safer Existing
Plants (3)
Hydrochloric Acid Regeneration at Hoogovens Steel Strip mill Products (HSSP) [12]:
Conclusion
 Conclusion

1. Inherently safer process design strategy is a pro-active approach to ensure a safer process design

2. Guidelines in the INSET toolkit [3] can be used to generate alternatives. It can be used throughout
the process life-cycle. This is relevant for my activities.

3. Quantifying safety aspect of process design options via index calculation tools is useful for
benchmarking and for decision making tool. Several index calculation tools are available for use
and proven to be reliable (agree with experts’ opinions). Relevant index calculation tools for me
could be Inherent Safety Index (ISI) [4] and Integration of Dow F&EI [2] because:
a. ISI is applicable for both route selection and flowsheet development (which are relevant
tasks)
b. ISI parameters to be evaluated are already available in the conceptual design phase (phase
where relevant tasks are present)
c. Integration of Dow F&EI can be used for equipment design, which is also a relevant task for
me

4. Depending on the projects, it could be beneficial to have these tools as toolkits

Future Works
 Future Works

Future works on inherently safer process design:

1. Develop index calculation toolkits (ISI [4] and Dow F&EI [2]) in MS Excel as toolkits

2. Develop a procedure to link Aspen Plus process simulation with the above index
calculation toolkits by utilizing Aspen Worksheet

3. Create a case study to verify the usefulness of the toolkits by:

a. developing several options by utilizing INSET toolkit together with process and
technical constraints,
b. quantifying their safety indices using index calculation toolkits, and
c. comparing their indices to choose which one is the inherently safer one.
 References (1)

[1] Hendershot, D. C., 1997, Inherently safer chemical process design, Journal of Loss
Prevention in the Process Industries, Vol. 10, No. 3, pp. 151-157.
[2] Suardin, J., Mannan, M. S. and El-Halwagi, M., 2007, The integration of Dow’s fire
and explosion index (F&EI) into process design and optimization to achieve inherently
safer design, Journal of Loss Prevention in the Process Industries, pp. 79-90.
[3] INSIDE Project (2001). The INSET toolkit
[4] Heikkila, A, M., 1999, Inherent safety in process plant design: an index based
approach, PhD dissertation, Technical Research Center of Finland, VTT, Espoo:
Finland.
[5] Kletz, T., 1999, What Went Wrong? Case Histories of Process Plant Disasters 4th Ed.,
Gulf Publishing Company, Houston, TX, USA.
[6]. Edwards, D. W. & Lawrence, D., 1993, Assessing the inherent safety of chemical
process routes: Is there a relation between plant costs and inherent safety?,
Chemical Engineering Research & Design, 71 (Part B), pp. 252-258.
 References (2)

[7]. Palaniappan, C., 2002, Expert system for design of inherently safer chemical
processes, MEng thesis, National University of Singapore.
[8]. Al-Mutairi, E. M., Suardin, J. A., Mannan, M. S. & El-Halwagi, M. M., 2008, An
optimization aproach to the integration of inherently safer design and process
scheduling, Journal of Loss Prevention in the Process Industries, pp. 543-549.
[9]. Rahman, M., Heikkilä, A. M. and Hurme, M., 2005, Comparison of inherent safety
indices in process concept evaluation, Journal of Loss Prevention in the Process
Industries, pp. 327 – 334.
[10]. Takriff, M. S. and Bahnuddin, N. N., 2010, Integration of inherent safety assessment
into process simulation, 4th International Conference on Safety and Environment in
Process Industry, http://www.aidic.it/CISAP4/webpapers/108Takriff.pdf
[11]. Edwards, V. H. and Chosnek, J., 2012, Make Your Existing Plant Inherently Safer, Chemical
Engineering Progress, AIChE, January 2012, pp. 48 – 52.
[12]. Zwetsloot, G. I. J. M. and Ashford, N. A., 2003, The Feasibility of Encouraging Inherently Safer
Production in Industrial Firms, Safety Science, 41: 219 – 240.