Irpc 2013

Pyrophoric Hazard of Catalyst Handling in Refining and
Petrochemical Industry
AB
Phyrophoric Hazard of Catalyst Handling in Refining and Petrochemical Industry
 Scientific Background
 Regulation
 Case History
 Hazard Scenario
 Best practise
AB
AB
 Regulation
 Case History
 Hazard Scenario
 Best practise
AB
Terminology  From ancient Greek
πῦρ  fire
φέρω  bear
Prometheus carrying fire - Jan Cossiers
AB
Scientific Background
Pyrophoric materials are substances that ignite instantly upon simple exposure to oxygen
Definition of pyrophoricity is not restricted to finely divided powders. Pure metals, alloys,
carbides, hydrides, non-metallic materials and even liquids may show a pyrophoric
behaviour.
The focus is on finely divided pyrophoric powders used as catalysts in refining and
petrochemical Industry
AB
Hypergolic
A rocket propellant consisting of mixture of fuel and oxidizer,

other than air, that ignite when come into contact with each
other.
Triethyl aluminum (TEA) is referred as hypergolic
Hypergolic is other than Pyrophoric

Basic Thermodynamics T1
W Q
T2
AB
Basic Thermodynamics
Pyrophoric substance do not require an ignition source. Thus,

they are considered to have zero Minimum Ignition Energy
(CCPS)
AB
Basic Thermodynamics
AB
(CCPS)
W Q
Theory of Metals Combustion

T2
AB
Pyrophoricity
This term has usually been applied to the ignition of very fine
sizes of metal particles
Most metals when exposed to air form an oxide coat tick

around 25 Angstroms.
The ratio of the oxide formed to the metal consumed is

called the Piling and Bedworth number
AB
Pyrophoricity
Pilling and Bedworth Number
n is the number of atoms of metal per one molecule of the oxide
AB
Pyrophoricity
In corrosion chemistry a general rule of thumb exists, based on PB number:

- PB<1  oxide coating layer too thin no protective effect
- PB>2  oxide coating does not provide any protective effect
- 1<PB<2  oxide coating does provide a protective effect
AB
Pyrophoricity
(Source: NACE)
AB
Pyrophoricity
- PB theory is a general law showing that the reaction between metal and
oxygen is promoted or prevented depending on the surface availability
- In metal oxidation, as in all surface based mechanisms, surface/volume ratio

is a governing factor
AB
Pyrophoricity
Glassman’ theory of metal combustion
- The protective oxide coat must be destroyed and the temperature
must be sufficient to vaporize the exposed surface of the nascent metal.
- The metal vapour that reacts with the oxidizer present must reach a
temperature that will retain the vaporization of the metal.
AB
Pyrophoricity
The heat of vaporization–dissociation or decomposition of the metal
oxide formed is greater than the heat available to raise the condensed
state of the oxide above its boiling point.
AB
Pyrophoricity
For a metal to burn as a vapour, the oxide volatilization temperature
must be greater than the temperature of the metal boiling point.
Glassman’s criterion for the vapour-phase combustion of metals
AB
W Q
Theory of Phyrophoricity
T2
AB
Transition (d-block)metals present a general pyrophoric behaviour

AB
(Housecroft and Sharpe)
Pyrophoricity
- The term pyrophoricity pertains to the instantaneous

combustibility of fine metal particles that have no oxide coat.
- Coating prevention is achieved by keeping or being the

particles formed and stored in an inert atmosphere
AB
Pyrophoricity
A metal is considered pyrophoric when in its nascent state (no oxide

coat) it is small enough that the initial oxide coat that forms due to
heterogeneous reaction with air under ambient conditions
generates sufficient heat to vaporize the remaining metal
Metal vapours are extremely reactive and are consumed rapidly.
AB
Pyrophoricity
Critical condition for pyrophoricity
The heat release of the oxide coat formed on a nascent sphere at the
ambient temperature must be sufficient to heat the metal to its
vaporization point and supply enough heat to vaporize the
remaining metal
Energy necessary to raise the metal from the ambient temperature to the
vaporization temperature is a determining factor
AB
Pyrophoricity
d
d= oxide layer thickness
r = metal particle radius
AB
Pyrophoricity
Terms of critical heat balance for pyrophoricity
- ( Δ H °298 )ox = standard state heat of formation of the oxide at 298 K

- Ho =the standard state enthalpy at temperature T ,
- “ bpt ” specifies the metal vaporization temperature
- m and ox refer to the metal and oxide
AB
Pyrophoricity
Critical Condition
Heat available = Heat needed to vaporize the metal +Heat needed to heat the oxide coat
AB
Pyrophoricity
(Glassman, Papas, Brezinsky)
The smaller the value of ( δ / r ), the greater the pyrophoric tendency of the metal
AB
Pyrophoricity
The general size of particles that are pyrophoric is of the
order 0.01 μm (Glassman, Papas, Brezinsky)
All of metals that have values of ( δ / r ) less than 0.2 meet

Glassman’s criterion for vapour-phase combustion of metals
regardless of size
Only those metals that have a (δ/r) value less than 0.2 are
prone to dust type explosion
AB
(Glassman)
Pyrophoricity
-Development and sustainment of pyrophoric

phenomena can be macroscopically understood
comparing reaction heat versus heat removal
- Semenov, Frank-Kamenetskii, and Thomas approaches

are effective in modelling (f.i Bradley)
(Glassman)
AB
Pyrophoricity
DIFFUSIONAL KINETICS
Rate limiting step – kinetics vs oxygen diffusion – is

difficult to establish due to lack of knowledge of
reaction temperature
(Glassman)
AB
Pyrophoricity Scenarios
AB
Goetzel pyrophoric substances classification includes:
- Pure metals
- Alloys
- Compounds
- Composite and coated powders
AB
(CCPS)
AB
Carbon-supported dry powder catalysts can undergo dust

explosions in the same manner as carbon itself
AB
Catalyst may contain adsorbed hydrogen, which can be released
and ignited
AB
Iron may form iron sulphide (pyrite) in presence of H2S
Fe2O3 +3H2S2FeS + 3H2O + 3S

Pyrite has the same ancient Greek root
AB πῦρ  fire
Pyrite oxidation produces heat
4FeS +3O22Fe2O3 + 4S + Heatreact
4FeS +7O22Fe2O3 + 4SO2 + Heatreact

AB
Spent catalyst carbonaceous coating may enhance or show a

pyrophoric behaviour
AB
Organometallic compounds like Li(CH3), Zn(CH3)2, B(CH3) 3, and

Al2(CH3) 6 are spontaneously flammable in air (pyrophoric)
AB
 Regulation
 Case History
 Hazard Scenario
 Best practise
AB
European CLP Regulation
REGULATION (EC) No 1272/2008 OF THE EUROPEAN PARLIAMENT AND OF THE

COUNCIL of 16 December 2008 on classification, labelling and packaging of substances
and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and
amending Regulation (EC) No 1907/2006
AB
Regulation
Pyrophoric solids
Definition
Pyrophoric solid means a solid substance or mixture which, even in small quantities, is
liable to ignite within five minutes after coming into contact with air.
AB
Regulation
Pyrophoric solids
Classification criteria
A pyrophoric solid shall be classified in a single category for this class using test N.2 in Part
III, subsection 33.3.1.4 of the UN Recommendations on the Transport of Dangerous Goods,
Manual of Tests and Criteria in accordance with Table 2.10.1:
AB
Regulation
Pyrophoric solids
AB
Regulation
Pyrophoric materiala like catalysts are categorised by the following Risk Phrase:
R 17 - Spontaneously flammable in air
AB
Regulation
OSHA - APPENDIX B TO §1910.1200 – PHYSICAL HAZARD CRITERIA
Pyrophoric solids
A pyrophoric solid shall be classified in a single category for this class using test
N.2 in Part III, sub-section 33.3.1.4 of the UN ST/SG/AC.10 (incorporated by
reference; See §1910.6), in accordance with Table B.10.1:
AB
Regulation
OSHA - APPENDIX B TO §1910.1200 – PHYSICAL HAZARD CRITERIA
Pyrophoric solids
B.10.3 Additional classification considerations
The classification procedure for pyrophoric solids need not be applied when
experience in production or handling shows that the chemical does not ignite
spontaneously on coming into contact with air at normal temperatures (i.e., the
chemical is known to be stable at room temperature for prolonged periods of
time (days)).
AB
Regulation
European Agreement concerning the International Carriage of Dangerous Goods by Road

(ADR)
Pyrophoric solids
AB
Regulation
European Agreement concerning the International Carriage of Dangerous Goods by Road

(ADR)
Pyrophoric solids
AB
Regulation
NFPA 400: Hazardous Materials Code
AB
Regulation
NFPA 704: Standard System for the Identification of the Hazards of Materials for
Emergency Response
AB
Regulation
International Building Code
PYROPHORIC. A chemical with an auto-ignition temperature in air,

at or below a temperature of 130°F (54.4°C).
AB
Regulation
 Regulation
 Case History
 Hazard Scenario
 Best practise
AB
1. OVERHEATING OF SPENT CATALYST
AB
Case Hisytory
AB
Case Hisytory
2. CATALYST FIRE
AB
Case Hisytory
Laboratory hydrogenation completed with palladium charcoal catalyst
Catalyst removed by filtration using a nitrogen gas stream
After solvent removal, the dry filter caught on fire
AB
Case Hisytory
Fire from pre=sulphide d new catalyst stored

in large cartons (Source BP)
3. CATALYST FIRE
AB
Case Hisytory
Presulfided new catalyst storage in bags resulted in a fire
AB
Case Hisytory
The deformed section of an overheated reactor

from a runaway reaction (Source BP)
Hreac A
Non return point
B Hrem
AB
4. Thermal Runaway Due to Bad Catalyst Loading
Case History
Thermal runaway was not due to pyrophoric catalyst behaviour
Erroneous catalyst distribution may result in local overheating
Loss of contain may carry catalyst to contact with atmosphere
Catalyst pyrophoric fire can ignite flammable clouds or liquid pools
AB
Case History
AB
5. Vessel Flash Fire
Case Hisytory
A worker rinsing the interior of a pressure vessel was engulfed by

a flash fire suffering severe upper body burns
OSHA presumes residual pyrophoric catalyst was the ignition

source for the fire, along with lack of further gas free
AB
Case Hisytory
6. Burns from pyrophoric catalyst

AB
Case History
A person was working in a vessel where a pyrophoric spent

catalyst dust was assumed to present
Consequently, he was working in inert atmosphere under nitrogen
On one shoulder the inert atmosphere is assumed to have been lost
The worker suffered serious burns
AB
Case History
 Regulation
 Case History
 Hazard Scenario
 Best practise
AB
ATEX FRA QRA Process Licensor Side reactions Storage &
HAZOP Inventory control
design Advise Handling
HAZARD
Different assessments ASSESSMENT
RANKING
Design Input
Shut
Start up Reactive hazards
down
Combustion with air the expected
only intended chemistry?
Design Input
START
Yes Yes Yes Yes Yes Yes Yes Yes Yes
Incompatible
Intentional Any spontaneously
Any substances Any heat Peroxides Water Any Any self materials
chemistry? ignitable?
mixing? generated? forming? reactive? oxidizer? reactive? coming into
No Yes No No No No No No contact?
No
Any other physical

Design Input processing? Yes
HAZARD IDENTIFICATION PROCESS
No
Storage/handle of
any potentially Yes MSDS NFPA CLP NIOSH/NPG
reactive
substances? Lesson Lrnt C.History Regulation
STOP
No
Reactivity hazards
unlikely
Hazard Scenario
Reactive Hazard Assessment
Hazard Scenario of Pyrophoric Catalyst Handling
Inherent
Pyrophoricity
Process
configuration
Operational
Configuration
Off-Set
Unplanned
Events
AB Maintenance
Shut down
Start Up
Hazard Scenario Transient Phases
Inherent Catalyst chemistry characterisation / identification

Pyrophoricity
Physical properties, size, porosity, adsorbing capacity
Regulatory classification and labelling
Pyrophoricity co-factors (ie.g. water, …)
AB
Pyrophoricity limits and extension
Hazard Scenario
Process Pirophoric and non Phyrophoric Catalyst coating

Configuration
Hydrogen adsorption
Hazard from loss of containment (thermal runaway)
Pyrite formation
AB
Pyrophoricity induced by overheating
Hazard Scenario
Operational Storage, loading, unloading, transportation

Configuration
Spent catalyst characterisation
Operational errors
Control
AB
Sequences/Procedures
Hazard Scenario
OFF-Set Unplanned replacement

Unplanned
Process change / Inadequate mixing
Change in process chemistry
Omitted procedure / MSDS measures
AB
OFF-SPEC catalyst, size change, performance change
Hazard Scenario
Maintenance Licensor/manufacturer’s specifications

Shut down
Start Up Licensor/manufacturer’s replacement procedure
Transient Phases
Temporary storage
Inerting
AB
PPE
Hazard Scenario
 Regulation
 Case History
 Hazard Scenario
 Best practise
AB
HAZARD IDENTIFICATION
AB
Best Practise
AB
Best Practise
ATEX FRA QRA Process Licensor Side reactions Storage &
HAZOP Inventory control
design Advise Handling
HAZARD
Different assessments ASSESSMENT
RANKING
Design Input
Shut
Start up Reactive hazards
down
Combustion with air the expected
only intended chemistry?
Design Input
START
Yes Yes Yes Yes Yes Yes Yes Yes Yes
Incompatible
Intentional Any spontaneously
Any substances Any heat Peroxides Water Any Any self materials
chemistry? ignitable?
mixing? generated? forming? reactive? oxidizer? reactive? coming into
No Yes No No No No No No contact?
No
Any other physical

Design Input processing? Yes
HAZARD IDENTIFICATION PROCESS
No
Storage/handle of
any potentially Yes MSDS NFPA CLP NIOSH/NPG
reactive
substances? Lesson Lrnt C.History Regulation
STOP
No
Reactivity hazards
unlikely
Hazard Scenario
Regulation
Regulation on classification and labelling (CLP, OSHA, NIOSH, NFPA,
ADR, IBC ) can provide immediate information on pyrophoricity
AB
Best Practise
MSDS
Material Safety Data Sheets are not in general a reliable source for
assuming information about reactive pirophoricity. MSDS drawn
according to ECHA requirements (European Chemical Agency) within the
REACH regulation have probably passed more specific tests.
AB
Best Practise
Safety Studies
PHA, HAZID AND HAZOP skip very frequently to
highlight the occurrence and the consistency of the
hazard.
AB
Best Practise
HAZID Catalyst chemical identification
Spent catalyst characterisation
Coatings with flammable/combustible substances
Presence of pyrite
AB
Synergic water reactivity
Best Practise
HAZOP Normal operation hazards
Maintenance and pre/commissioning hazards
Operational upset
Replacement operational procedures
AB
Waste management
Best Practise
Hazardous area classification

Pyrophoric substances don’t need in general any
ignition source to ignite
AB
Best Practise
Licensor/Manufacturer’s advice
Site safety plan
EPC contractor/Owner shall provide any necessary

information to identify chemistry and inherent hazards
Subcontractor/Outsourcing
Best Practise
Site safety plan
Subcontractor/Outsourcing Specific hazard assessment
Consequence analysis
Technology definition for Best Practise
removal/storage/disposal Mitigation measures
STORAGE
AB
Best Practise
International Building Code

provides requirements for
STORAGE segregation, maximum allowable
quantity for storage, additional
technical specifications (power,
HVAC,…)
AB
Best Practise
STORAGE
(IBC)
AB
Best Practise
STORAGE
Segregation/Separation
Other Chemicals Specific locations Specific Buildings
AB
Best Practise
STORAGE Corrosion protection
Containment Inert environment
Sealed containers Weather protection

Water, oil, nitrogen
Liquid or gaseous maintained also once

AB Metallic
the container has been opened
Best Practise
STORAGE
Containment Never in bags
Best Practise
Unloading
(Source: BP)
AB
Best Practise
As and more than flammable dusts

Unloading free falling will dramatically increase
oxygen transfer and surface to
volume ratio
AB
Best Practise
Thank you!
AB

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Pyrophoric Hazard of Catalyst Handling in Refining and

Terminology  From ancient Greek

A rocket propellant consisting of mixture of fuel and oxidizer,

Hypergolic is other than Pyrophoric

Pyrophoric substance do not require an ignition source. Thus,

Theory of Metals Combustion

Most metals when exposed to air form an oxide coat tick

The ratio of the oxide formed to the metal consumed is

n is the number of atoms of metal per one molecule of the oxide

In corrosion chemistry a general rule of thumb exists, based on PB number:

- PB>2  oxide coating does not provide any protective effect

- 1<PB<2  oxide coating does provide a protective effect

- In metal oxidation, as in all surface based mechanisms, surface/volume ratio

Glassman’s criterion for the vapour-phase combustion of metals

Transition (d-block)metals present a general pyrophoric behaviour

- The term pyrophoricity pertains to the instantaneous

- Coating prevention is achieved by keeping or being the

A metal is considered pyrophoric when in its nascent state (no oxide

Metal vapours are extremely reactive and are consumed rapidly.

Critical condition for pyrophoricity

d= oxide layer thickness

r = metal particle radius

- ( Δ H °298 )ox = standard state heat of formation of the oxide at 298 K

(Glassman, Papas, Brezinsky)

All of metals that have values of ( δ / r ) less than 0.2 meet

-Development and sustainment of pyrophoric

- Semenov, Frank-Kamenetskii, and Thomas approaches

Rate limiting step – kinetics vs oxygen diffusion – is

Carbon-supported dry powder catalysts can undergo dust

Fe2O3 +3H2S2FeS + 3H2O + 3S

AB πῦρ  fire

4FeS +3O22Fe2O3 + 4S + Heatreact

4FeS +7O22Fe2O3 + 4SO2 + Heatreact

Spent catalyst carbonaceous coating may enhance or show a

Organometallic compounds like Li(CH3), Zn(CH3)2, B(CH3) 3, and

European CLP Regulation

REGULATION (EC) No 1272/2008 OF THE EUROPEAN PARLIAMENT AND OF THE

European CLP Regulation

European CLP Regulation

European CLP Regulation

European CLP Regulation

R 17 - Spontaneously flammable in air

OSHA - APPENDIX B TO §1910.1200 – PHYSICAL HAZARD CRITERIA

OSHA - APPENDIX B TO §1910.1200 – PHYSICAL HAZARD CRITERIA

B.10.3 Additional classification considerations

European Agreement concerning the International Carriage of Dangerous Goods by Road

European Agreement concerning the International Carriage of Dangerous Goods by Road

NFPA 400: Hazardous Materials Code

International Building Code

PYROPHORIC. A chemical with an auto-ignition temperature in air,

1. OVERHEATING OF SPENT CATALYST

Laboratory hydrogenation completed with palladium charcoal catalyst

Catalyst removed by filtration using a nitrogen gas stream

After solvent removal, the dry filter caught on fire

Fire from pre=sulphide d new catalyst stored

Presulfided new catalyst storage in bags resulted in a fire

The deformed section of an overheated reactor

Thermal runaway was not due to pyrophoric catalyst behaviour

Erroneous catalyst distribution may result in local overheating

Loss of contain may carry catalyst to contact with atmosphere

Catalyst pyrophoric fire can ignite flammable clouds or liquid pools

A worker rinsing the interior of a pressure vessel was engulfed by

OSHA presumes residual pyrophoric catalyst was the ignition