Process Safety in the Laboratory

Maria J Sanderson
Content

Background

Overview of the Sour Laboratory

What is process safety and why this is applicable

Process Hazard Review - scope of study

Explanation of key concepts - ALARP, LOPA,

What we learned

Benefits and outcomes

Sour laboratory
Properties of H2S Gas

Very toxic by inhalation

May cause damaging effects to central nervous system, metabolism
and gastrointestinal tract.
Prolonged exposure to small concentrations may result in pulmonary
oedema.
Workplace Exposure Limit
Exposure limit value:
Long-term exposure limit Short-term exposure limit
Substance CAS number (8-hour TWA reference (15 minute reference
perid) period)

ppm mg.m-3 ppm mg.m-3

Hydrogen Sulphide 7783-06-4 5 7 10 14

Extremely flammable
Exposure to fire may cause containers to rupture/explode.
If involved in a fire sulphur dioxide (toxic and/or corrosive) fumes may
be produced by thermal decomposition
What is Pipeline / Linepipe?

Pipe operating under pressure for the purpose of

transporting quantities of fluid (liquid and / or gas) over
relatively large distances, from a few km to thousands of km
Major European Gas Trunklines
Examples of other types of tube and pipe

Blackpool Rollercoaster
Structural

Wembley
Stadium

Ascot racecourse
Examples of other types of tube and pipe

Process plant

Picture courtesy of Alan Clements

Critical Pipe Properties

Strength
Yield stress
Tensile strength Special Properties

Toughness Sour Gas Resistance

CTOD Tests
Battelle Drop Weight Tear Test
Charpy V-notch impact energy
Test temperature
Composition
Low CEV for weldability
Linepipe corrosion

Terminology
Sweet Corrosion
Carbon dioxide and water present produce carbonic acid
predictably reduces the pipe wall thickness

Sour Corrosion
Hydrogen sulphide gas and water present result in
absorption of atomic hydrogen
embrittlement leading to catastrophic failure
Mechanism of HIC

Hydrogen Induced Cracking

Hydrogen diffuses to inclusions / segregation
Hydrogen diffuses to hard regions
Cracking occurs when pressure exceeds local threshold
Mechanism of Hydrogen Induced Cracking, HIC

Need hydrogen sulphide gas and water present in pipeline fluid

H2S + H2O HS- + H3O+

HS- + H2O S2- + H3O+

2H3O+ + 2e 2H2O + 2H
Cathodic Reaction

2+
Fe Fe + 2e
Anodic Reaction

H2O
Fe + H2S FeS + 2H
Overall Reaction
Consequence of HIC

Macro-scale

Micro-scale
Sulphide Stress Corrosion Cracking - SSCC

Need an external stress

Pits form due to corrosion
H diffuses to high tensile stress regions
Local embrittlement takes place
Crack extends by increments
Generally occurs in higher strength
grades
Highly sensitive to microstructure
Importance of Pipeline Toughness

Propagating brittle fracture

Importance of Pipeline Toughness

Non propagating gas line event

August 19th, 2000, Pecos river, New Mexico

Natural gas line ruptured, 12 people killed

Pipeline fracture self arrested- but why did it initially rupture ?

Corrosion by exposure to Sour Environment
Process Safety
Process Safety - background

PROCESS HAZARD
REVIEW (PHR)
PHR methodology

Team-based hazard ID and risk evaluation methodology

Specialist and independent facilitator
Team comprising experienced operators, engineers and technical staff
Uses checklists and guide diagrams to:
Identify credible losses of containment (or energy releases)
Understand the consequences
Assess need for remedial measures
Key issues are identified more quickly
Risk-based improvement plan
PHR re-validation
Sour Lab PHR steps

Team introduction
Scope meeting
Structured hazard identification exercise
Qualitative risk assessment for each hazardous event considered
 Consequence ranking

Categoty Title Description

Off-site fatality
Multiple (5 or more) on-site fatalities
5 Catastrophic
Very serious contamination of ground or water course, long-term loss of aquatic life
Prohibition notice
One or few major injuries off-site
Few (less than 4) on-site fatalities
4 Extremely serious High levels of carcinogen exposure
MATTE (DETR definition)
Severe fine
One of few off-site medical treatment cases
One or few major injuries on-site
3 Major Distressing exposure, irreversible effects
Disturbing visual evidence, fish killed
Prosecution
Distress to off-site population
One or few serious injuries on-site
Release 2-5 times OEL
2 Serious
Sustained or repeated nuisance, noise, unpleasant smell, dust fall-out, flaring or venting
Exceed liquid effluent consent
Warning from CA
Nuisance off-site
One or few on-site medical treatment cases
Release above OEL, unpleasant conditions
1 Minor
Short duration nuisance, noise, offensive smell, flaring or venting
Small amount released to watercourses
Release notifiable to the CA
Frequency ranking

Category Title Description

Has occurred in the
Probable Greater than 1 per year
A lifetime of the plant
2 Could occur during the
1 in 10 years to once remaining lifetime of the
Possible
B per year plant
4 2 Incidents in industry on
Unlikely 1 in 10 to 1 in 10 years
C similar technology
Foreseeable event but
chance of occurring is
6 4
Very unlikely 1 in 10 to 1 in 10 years very low, requires the
failure of a number of
D layers of protection
Equivalent to the risk of
7 6
Extremely unlikely 1 in 10 to 1 in 10 years being killed by a
E lightening strike
PHR output qualitative risk evaluation

A full list of major accident hazards for the plant

All major accident hazard events positioned on the risk matrix
PHR output safety integrity level (SIL) determination

LOPA principal steps :

1. Identify the specific hazardous event and its severity.
2. Identify the initiating causes of the hazardous event.
3. Determine the target frequency.
4. Identify independent layers of protection.
5. Completion of LOPA Spreadsheet
PHR output safety integrity level (SIL) determination

LOPA principal steps :

1. Identify the specific hazardous event and its severity.
2. Identify the initiating causes of the hazardous event.
3. Determine the target frequency.
4. Identify independent layers of protection.
5. Completion of LOPA Spreadsheet
PHR output safety integrity level (SIL) determination

LOPA principal steps :

1. Identify the specific hazardous event and its severity.
2. Identify the initiating causes of the hazardous event.
3. Determine the target frequency.
4. Identify independent layers of protection.
5. Completion of LOPA Spreadsheet
Summary what we learned

PHR review
Recommendations for improvement
Intolerable risks
Tolerable if ALARP
SIL Determination
Assessed using LOPA technique
Achieved SIL assessment demonstrated that weekly functional testing
achieves target PFDavg
Action plan and closure review PHR in the event of change / 5 years
Summary benefits

Prevents major accidents with the potential to harm

Part of the Risk Management toolkit
Assurance that any possible risks are reduced to ALARP

Questions?