Inherent Safety - Scientific Update

Transcription

Hazardous Chemistry or Hazardous Process :
Where is the Hazard ?
2nd International Conference on Hazardous Chemistry
For Streamlined Large Scale Synthesis
4-5 November 2013 – Cologne
1
… What about chemistry without conscience ?
François Rabelais alias Alcofribas Nasier (Priest, Physician and Writer of the 16th century)
2
Yves Robin 4-5 November 2013 – Cologne
Summary
 Introduction
 Clarification
 Hazard
 Accident
 Risk management
 Inherent safety
 Principle - Definition
 Case studies
 Process & plant lifecycle
 Safety principles
 Case studies
 Business and company impact
 Conclusion
3
Introduction
What do we want to prevent ?
4
Clarifications
Hazardous Chemistry or Hazardous Process : Where is the Hazard ?
Hazardous chemistry or Hazardous process :
is there any official definition or classification ?
Hazardous chemicals :
there is an international classification system : GHS *
Hazardous systems :
is there any official definition or classification ?
* GHS : Globally Harmonized System of Classification and Labelling and Packaging
5
Clarifications
Hazard
A hazard is a condition or practice that has the potential to cause harm,
including human injury, damage to property, damage to the environment, or
some combination of these*
*Sutton, I. S., 2010 . Process Risk and Reliability Management Operational Integrity Management, 1st ed
William Andrew Publishing, Oxford UK/Burlington, MA, pp. viii, 850 p. ill. 825 cm
6
Clarifications
Accident
Oxford Dictionary : an unfortunate incident that happens unexpectedly and
unintentionally, typically resulting in damage or injury
An accident comes from 3 factors*
One or more
Events
Inherent
Hazard
Damage
Injury
Undesired
Outcome
(uncontrolled toxic release, fire, explosion…)
(internal/external that instantiate a failure mode)
(in the technology for converting RM to products)
*Sutton, I. S., 2010 . Process Risk and Reliability Management Operational Integrity Management, 1st ed
William Andrew Publishing, Oxford UK/Burlington, MA, pp. viii, 850 p. ill. 825 cm
7
Clarifications
Accident
Undesired outcome
Material release
Explosion
… and
combination
of several
Fire
Energy release
(heat or
pressure)
8
Clarifications
Risk
Risk is the probability that an exposure to hazard would lead to an outcome
Risk management is the collective efforts to manage risks
in order to prevent accident
.. but what kind of collective efforts ?
*Srinivasan R. , Natarajan S. , 2012 , Process Saf. Environ. Prot. 90, 389-403
9
Clarifications
Hazard to Accident : summary
Minimized risk
of accident
Accident
Collective
efforts
Undesired
outcome(s)
Event(s)
Hazard(s)
10
Collective
efforts
Inherent Safety
Inherent safety
11
Inherent safety
A bit of history
Concept of Inherent
Safer Chemical
Processes and Plants
December 14, 1977
Trevor Kletz lecture*
June 1, 1974
Flixborough disaster
* “What You Don’t Have, Can’t Leak” , Trevor Kletz, 1977 Annual Jubilee Lecture to the Society of Chemical
Industry in Widnes (England)
*Srinivasan R. , Natarajan S. , 2012, Process Saf. Environ. Prot. 90, 389-403
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Inherent Safety
Inherent Safety Principle
Change or alter the process to either eliminate the hazard completely or
sufficiently reduce its magnitude or likelihood of occurrence, rather than
controlling them
Inherent hazard
Likelyhood
* “What You Don’t Have, Can’t Leak” , Trevor Kletz, 1997 Annual Jubilee Lecture to the Society of Chemical
Industry in Widnes (England)
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Inherent Safety
Inherent hazard
Materials used
Chemistry of the
process
Operation
regimes
Where does it
come from ?
Unit operation
design
Storage and
transportation
Flowsheet and
layout design
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Inherent Safety
Likelihood
Process control
& safety system
of what kind
of event ?
Human factor
& Management
systems
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Inherent Safety
Risk management techniques
Decrease
the
likelihood
Minimize
severity
Damage
Injury
Minimize
the Hazard
One or more
Events
Undesired
Outcome
Inherent
Hazard
*Srinivasan R. , Natarajan S. , Process Saf. Environ. Prot. 90, 2012 389-403
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Inherent Safety
Avoiding
incorrect
assembly**
Inherent safer process
Limitation
of effects*
Making
status
clear**
Simplify*
Moderate*
Substitute*
Minimize*
Key principles for anyone
who contributes to the
design of a new
chemical process
Inherent Safer Process
*Kletz, T.A. Inherently safer plants ., 1985 , Plants Oper. Prog. 4 ,164-167
**Kletz, T. A. , 1998. Process Plants : A Handbook for inherently Safer Process Design. Taylor & Francis,
Philadelphia, PA
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Inherent Safety
Inherent safer process
Let’s have a look to practical examples in relation
with Inherent Safer Process Principle
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Inherent Safety
Case studies 1* : Hydrogenation - dehalogenation reaction
H2 - Pd/C
Base
Base,HCl
What is the thermal analysis of this reaction?
*Isochem 2006 unpublished data
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Inherent Safety
Reaction classification for thermal risk
Class :
Tproc :
MTSR :
1
2
Process temperature
Tproc + ΔTadia
3
4
Tdec :
Teb :
5
Temperature of decomposition (thermal runaway)
Boiling Point of the reaction mixture
* F. Stoessel, 1993 , Chem. Eng. Progr. 89(10) , 68-75
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Inherent Safety
Case studies 1 : Standard process
H2 - Pd/C
Base
ΔHdec -1350J/g
ONSET : 280°C
Base,HCl
ΔHreact 201J/g
ΔTadia 41°C
Reaction temperature
MTSR
Solvant Eb @ process pressure :
Tdec : (280 -100°C)
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Lower ΔHdec
More stable
80°C
121°C
151°C
180°C
Class 1
Inherent Safety
Case studies 1 : Half catalyst load compared to standard process
H2 - Pd/C
Base
ΔHdec -1350J/g
ONSET : 280°C
Base,HCl
ΔHreact 201J/g
ΔTadia 41 -> 70°C
MTSR
Reaction not completed
Solvant Eb @ process pressure :
Tdec : (280 -100)
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60-65°C
106 -> 134°C
????
151°C
180°C
Lower ΔHdec
More stable
Class ?
Inherent Safety
DSC of the reaction mixture when the reaction stops
E2=227J/g
E1=186J/g
146°C
230°C
Presence of large quantity of low stability and high
energy decomposition species
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Inherent Safety
Further studies led to determine the TMRad at 134°C
After 3h a runaway start is observed :
E1 : ΔTadia = 84°C
Temperature
E1+ E2 : ΔTadia = 151°C
Desired reaction
Decomposition
Tfinale = 285°C
Ebullition = 151°C
MTSR = 134°C
TMRad = 3h
Tp = 60°C
Deviation = 100% of accumulation
Uncontrolled reaction can switch to Class 5 risk !
Process parameter and catalyst quantity (and quality) are critical
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Inherent Safety
Process parameters and thermal scenario are clearly identified
Considering “an event” can once impact the reaction (eg catalyst
poisoning …)
Monitoring temperature profile and hydrogen absorption kinetic
An emergency procedure has been defined to “quench the reaction”
if standard reaction kinetic is not observed (heat and hydrogen flow)
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Inherent Safety
Case study 2 : Nitration*
HNO3 - H2SO4
Semi batch process : introduction of the acetamide derivative on sulfonitric acid
Quality rely on a maximum temperature of
-5 to 0°C
0°C
How to control the temperature range during powder feeding ?
How long will it take at 275 Kg scale ?
26
Inherent Safety
Case study 2 : Nitration
ΔHreact 155J/g ΔTadia 77°C
Class 2
Quality rely on a maximum temperature of
-5 to 0°C
0°C
Powder introduced per 10Kg units
maximum ΔT per load : 4°C
Simulation for
Glass-lined reactor 4000 L
Feed time (H)
EG -7°C
EG -10°C
EG-25°C
Half batch size
15,2
9,4
4,1
Full batch size
20,6
12,6
5,5
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Inherent Safety
Case study 2 : Nitration
Scale-up to 275 Kg : Successful in time and quality
Reaction time
Full batch
EG -10°C
Calc.
EG -15/-20°C
4000L
EG-25°C
Calc.
12,6
8-10
5,5
Safe process and right quality are often closely linked
Thermal safety evaluation helps to prepare a scale-up
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Inherent Safety
Case study 3 : Powder handling
ONSET 376°C
ΔHdec -228J/g
ONSET 237°C
Powder
mp 140°C
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ΔHdec -245J/g
Inherent Safety
Case study 3: Powder handling
Dry powder
Explosion and flammability risks
Minimum Ignition Energy (MIE)
Explosive Concentration limits:
Ability to generate charges
Volumetric Resistivity
30
5mJ
500 < EC < 2000 g/m3
2900 pc/g
6,8 10+11 Ωm
!
Worse
scenario
Inherent Safety
Case study 3: Powder handling
Powder
Explosion of flammability risks
MIE and EC limits are unpredictable
MIE and EC of one powder depends on particle size and moisture
Ability to generate charges and resistivity are additional key parameters
Wet or dry powder handling requires attention, and
electrostatic discharge is a frequent source of ignition
Powder handling units and packaging have to comply with the
best standards to prevent electrostatic discharges
Regular controls are necessary
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Inherent Safety
Case study 4: “Lack of knowledge = Hidden risk”
Use of Triphosgene … and wastes*:
!
Beside the fact you have phosgene in your equipment,
remaining triphosgene can be found in mother liquors
Solvent recycling :
!
Recovered Chloroform after > 3 months storage :
Detection of Phosgene
Decontamination :
!
Oxalyle chloride hydrolysis with water
generates carbon monoxyde
*Isochem Int. Conf. on Hazardous Chemistry For Streamlined Large Scale Synthesis, 2011 Cologne
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Inherent Safety
Inherent Safety and process innovation
Chemical &
Process options
Inherent safety
Principle
Innovation
activity
Safer
solution
Chemical and Process R&D for safer chemistry
33
Safer
Process
Inherent Safety
Conclusion
Inherent safety principles, methodologies, metrics make the backbone of risk
management system for chemical processes
Inherently Safer Process is the root of safer Fine Chemical Processes
Inherently Safer Process is even more critical for multipurpose plants , the process
being designed for a predefined equipment/unit
34
Process & Plant Lifecycle
Process and Plant Lifecycle
35
Safety principles and lifecycle
Process
development
Research
Operations
Detailed design
Maintenance and
Modifications
Decommissioning
Lifecycle of a process for a multipurpose plant or a dedicated plant is a long run !
*CCPS, 2009, Inherently Safer Chemical Processes : A Life Cycle Approach, 2nd ed. John Wiley and Sons
Ltd, New York, NY
36
Safety principles and lifecycle : Risk management
Research
Process development
Operations
Detailed design
Maintenance and
Modifications
Decommissioning
Risk management up to mid 20th century
… too late to change process technologies bringing most of the inherent hazards
- Materials used
- Chemistry of the process
- Unit operation design
37
Safety principles and lifecycle : Risk management
Process
development
Research
Operations
Detailed design
Maintenance and
Modifications
Decommissioning
Risk management nowadays
… Integration of risk management at early stages
Minimize Substitute
Moderate Simplify
38
Safety principles and life cycle : Risk reduction
Effectiveness of risk reduction
Hazard elimination
or reduction
Early stage integration is critical
Safety
systems
Production
Research
Process
development
Detailed
Design
Operations
maintenance and
modifications
39
Case study 4: Cumene Hydroperoxyde pilot run
A detonation occurred
Circumstances
and destroyed the plant
A catalytic process is developed
Laboratory and Kilo-lab studies has been successful
Running a scale-up in an existing 400 L pilot plant reactor
Events
Rapid temperature increase
Rapid pressure increase
*Langerman N. 2008 Org. Process Res. & Dev. ,12 , 1305-106
40
Case study 4: Cumene Hydroperoxyde pilot run
Facts
Use of a new catalyst
Reactor cooling capacity and venting was inadequately sized
The pilot plant operator did not understand the implication of the rapid pressuretemperature increase
Changes (management of)
New catalyst
New reaction in an existing equipment
Operator familiar with the unit but not with the process
Risk management has to carefully consider process
development activities & scale-up studies
41
Case study 5: Process using POCl3
Circumstances
Pilot Plant
Process with POCl3 feeding
Corrosion of the unit
Minor inhalation
injuries of the operator
Events
1- Slow POCl3 leakage 2m away from the operator
2- Worker has left without hitting Emergency Stop or alarm controls
3- Delayed response to stop the leakage
4- What else then ? Fortunately nothing
*Langerman N. 2008 Org. Process Res. & Dev. , 12,1305-106
42
Case study 5: Process using POCl3
Training of operators
A gasket has failed
(mechanical integrity & material compatibility
The technician has not received sufficient training
no adequate supervision - lack of experience
Experience and Training of employees are often critical to
react properly to the first level event
43
Conclusion
The three steps of a safe process and plant life cycle
Process Research and Development set up the “nature and magnitude” of most o f
the hazards , Inherent safety principle is the key driver at this stage
Detailed process design prepare robust and production operations but does not
change the main hazards
Operation and maintenance implement and manage the permanence low likelihood
of events and risk, and the reduction of severity of a potential undesired outcome
44
Business and company consideration
Business and company impact
… on safety management
45
Safety management system robustness
Are there specific points to pay attention in custom manufacturing activity ?
Can a company merge or acquisition impact safety management efficiency ?
46
Business & custom manufacturing
Technical
Transfer
• Accuracy of information
• Data understanding & familiarization
• Communication & information management
Project
Lifecycle
Custom
manufacturing
specificity
Time and cost
pressure
Raw material
47
• Stepwise process development
• Go-no Go
• Change of teams and contacts
• Short lead-time expectation
• Minimizing R&D
• Rapid scale-up
• Sourcing
• Specification set-up
• Change of supplier
Company lifecycle
Policy &
Culture
• Policy sustains efficient risk management
• Culture is easier to loose than to built
Organization
• Clear responsibilities and roles are critical
• Insufficient management of change can
weaken the system
Merge and
Acquisition
Knowledge &
Know-How
System
& SSP
48
• Change of managers or operators
• Staff reduction
• Insufficient training
• Change of SSP
• Control and audits
• Training content
• Metrics
Case study 6 : Plant accident
Circumstances
Production of a polymer
Acrylic polymerization in flammable solvent
Explosion
1 death 14 injured
employees
Facts
Order received 12% over the standard batch size
Decision made to modify the process :
12% more monomer
12% less of low bp solvent and 6% more of high bp solvent
*SYNTHRON (PROTEX),
2006 Morganton NC -USA
49
Case study 6 : Plant accident
Events
1- Higher internal temperature
2- Pressure increase
3- Solvent vapour release by the manhole
4- Ignition source
Consequence of the change of reagents loading
Increase of monomer quantity and concentration => Higher heat flow
Decrease of Boiling point of mixture => Higher pressure increase
Other
Condenser efficacy reduced by 25% due to lack of maintenance (deposits)
Clamps of the manhole not all locked
*SYNTHRON (PROTEX), 2006 Morganton NC -USA
50
Case study 6 : Plant explosion
Staff
3 to 9 months staff seniority at the plant
None of them was experienced in polymerization
Unit
No “on process” safety system, devices and procedures
(no pressure alarm , no inhibitor injection , no burst disk …)
No general alarm, emergency procedure and training
Chemistry and Process knowledge
Unit design and Maintenance
Experience and Training
Management of change
Safety and emergency procedures
Five
fundamental
gaps
51
Conclusion
Business nature like custom manufacturing activity can interfere with a safe
process lifecycle. A CMO must have a robust and suitable risk management
system, fully integrated in the management of the projects
Company lifecycle can weaken the risk management system. The company policy
and the culture as well as the management of employees knowledge are the best
guaranty
52
Conclusion
There are hazardous reactions and chemicals but the process technology,
operation design, operation regimes, can manage the risk
… if the risk management system covers all the topics and all stages of
process lifecycle
There are plenty of “non hazardous reactions” which can lead to “hazardous
production operation”
…if the risk management system is not robust enough
Safe Fine Chemical activity relies on knowledge and expertise, technology,
design, training, management of change, continuous control and culture
… whatever the business and all along the company lifecycle
53
Conclusion
Behind all safety management system of any organization
there are PEOPLE with their CONSCIENCE,
the root of a strong safety culture
54
Acknowledgement
Mikael Paugam (R&D and Process safety manager)
Olivier Dabard (former Process safety manager)
Christian Gaillard, Nicolas Marcault , Eric Vermeulen (HSE managers)
Isochem’s R&D & Production managers
People and former colleagues who share strong values for sustainable chemistry
and promote continuous action toward safer chemistry and processes
55
Q&A
Thank you for your attention !
Contact : Yves Robin
[email protected]
www.isochem.eu
Our People make the difference
56

Inherent Safety - Scientific Update

Transcription

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