catalytic processes process safety requirements · take into account deactivation of catalyst...
TRANSCRIPT
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Catalytic Processes
Process Safety Requirements
Geert VercruysseProf. Process Safety
Catholic University of Leuven
33rd Annual European Seminar
Breda, 17th April 2018
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Contents
1. Introduction
2. Definitions
3. Catalyst Design
I. Ex Situ Activation
II. In Situ Activation
4. Root cause analysis SM/PO incident
5. Potential Risk Catalyst Incident
6. Process Safety Competency of Management
7. Conclusions
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Introduction
▪ Research started following the explosion at an SM/PO
plant which happened in June 2014.
▪ Video « Onderzoeksraad voor Veiligheid »
▪ Review of incident database specific for catalytic
processes.
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Definitions : Introduction to Reactor Design
The reactor/catalyst is the heart of the process:
▪ It may be endothermic or exothermic or have little heat effect.
▪ It determines the separation processes required downstream:
‐ Low conversion means large recycles.
‐ Low selectivity means additional separation units.
▪ Take into account deactivation of catalyst during runtime in design:
‐ Define Start of Run conditions (SOR)
‐ Define End of Run conditions (EOR)
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Catalyst Design : Generic features (1/2)
How is a catalyst prepared (generic) :
▪ Precipitation / impregnation
➢ e.g. Na2CO3 + NiCl2 NiCO3 + 2 NaCl
▪ Washing and drying
➢ Removing solution material + excess of water.
▪ Calcining: Carbonate or nitrate is reformulated to oxide
(e.g. with air)
➢ e.g. Ni(NO3)2 +O2 NiO + (NO + NO2)
➢ e.g. NiCO3 + O2 NiO + CO2
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Catalyst Design : Generic features (2/2)
How is a catalyst prepared (generic) :
▪ Calcining is necessary to obtain a more robust catalyst
for the next step in process.
▪ Rating a “shape” of catalyst: by extrusion and/or
tabletting.
▪ Activation of catalyst.
➢ e.g. NiO + H2 Ni + H2O
Two options : ex situ or in situ activation
Management to decide based on risk assessment.
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Catalyst Design : In situ vs ex situ
Advantages ex situ :
▪ Within control of supplier – Quality certificate.
▪ Final product is “pyrophoric” metal – how to prevent safety
issues at client:
‐ Mild oxidation before unloading into recipient (drum, big bag).
‐ Passivation via a wax layer on top of the catalyst (a coating to
prevent possible oxygen ingress).
‐ If not possible, unloading in reactor under nitrogen conditions is the
only option.
▪ No provisions to be foreseen for in situ activation.
▪ See Process Flow Diagram (PFD).
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Catalyst Design : PFD ex situ activation
H2O
Cooling water in
Cooling water out
Chilled water in
Chilled water out
H2
Reactor HeatExchanger
Condensor 1 Condensor 2
Electrical HeaterCompressor
N2CO2Air
H2O
PC
Vent to Atmosphere
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Catalyst Design : In situ vs ex situ activation
Advantages in situ :
▪ Within control of producer (supplier should be invited to witness).
▪ Safer to handle in loading and precommissioning phase:
‐ Catalyst loading can be done within “normal” circumstances.
‐ Complete load of catalyst can be activated in one action (efficiency gain).
▪ If possible, combine existing infrastructure to execute activation.
▪ See Process Flow Diagram (PFD).
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Catalyst Design : PFD in situ activation
Hydrogen
40 barg
Compressed
air
Nitrogen
Fuel Gas
R1 A/B
Flare
Waste Water
Steam
T R2 A/B
R3 A/B
R4
Furnace Reactor Quench Column
F
Q
T : Temperature sensor
F : Flow sensor
Q : Measurement off gas
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SM/PO Incident : Root cause analysis & conclusion
▪ A non-activated catalyst was introduced in
the reactor.
In situ reduction design was foreseen.
▪ New catalyst was introduced – higher
Cr-oxide content then previous one.
▪ During the heating phase (start of
commissioning),
EB reacted with Cr-oxide initiating the
reduction of
Cu-oxide with EB (*).
‐ Cr - O + C8H10 Cr + H2O +CO2 (g)
‐ Cu - O + C8H10 Cu + H2O +CO2 (g)
▪ Uncontrolled reaction resulting in an explosive
outburst.
(*) Simplified reaction scheme
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Catalyst phases
Procurement
DecommissioningOld catalyst
LoadingNew catalyst
Activation &Commissioning
Plant Operation= deactivation
Regeneration
Quality inspection, transport
Risk for combustion
Contact with dust/dust explosion
Exothermicity activation reaction
Flow distribution
Exothermicity regeneration
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Potential risk of catalyst incident : Cfr Incident database (1/3)
Examples:
▪ During commissioning, catalyst dust in eyes (not expected at this stage of commissioning).
▪ Underestimation of the exothermicity of a new catalyst, start-up procedure is writtenby trial and error.
▪ Heating of the catalyst duringdecommissioning caused by insufficientreduction/deactivation.
Case study with 73 catalyst incidents found in the incident database.
The potential risk levels weren’t always indicated in the incidents. Some of the potential risks are thus a personal judgement call.
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Potential risk of catalyst incident : Cfr Incident database (2/3)
Examples :
▪ Environment : Leakage in sievecontainer where decommissioned catalystwas deposed.
▪ Fire : Hole in suction hose fordecommissioning of pyrophoric catalyst. Through this hole, air was sucked insidethe hose, leading to a fire.
▪ Process : A change in catalyst causingproduction of too many by products.
Case study with 73 catalyst incidents found in the incident database.
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Potential risk of catalyst incident : Cfr Incident database (3/3)
Examples :
▪ Decommissioning : Dust explosion
during suction of catalyst.
▪ In process : Local hotspot around
temperature measurement.
▪ Deactivation : Unknown pressure
increase during deactivation (new
procedure).
Case study with 73 catalyst incidents found in the incident database.
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Process Safety Competency of Management
▪ Increase awareness for process safety risks connected to catalysts.
▪ Checklist for occupational safety regarding the handling of a catalyst.
▪ Always contact vendor prior to start-up!
▪ SHE-review of (de-)commissioning catalyst.
Guidewords: dust, pyrophoric, adsorption energy, SOR-conditions
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Conclusion
▪ No similar procedure where a flammable liquid is used as
cooling medium during the activation phase has been found.
▪ Nevertheless, review of the incident database learns criticality
of handling with catalysts.
▪ Checklist(s) and a good vendor contact should give enough
guidance to prevent catastrophic incidents.
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Thank you … for your attention !
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