Accident Hazards

Attachment No. B.
9
(extract from Safety Report prepared under SI 476 of 2000)

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0
Dynea Ireland Limited Standard Operating Procedure
Control of Major Accident Hazards Involving Dangerous Substances Regulations
Safety Report
Document Revision: Issue Date:
Number:1.0.3 3 111 2/05
Section 5 =Identification
8i
Analysis of Accidental Risks
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1
dunea
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~~ ~ ~
1 Identification & Analysis of Accidental Risks
1.1.1 Introduction
A major hazard as defined in Regulation S.1476 of 2000 is
"The intrinsic property of a dangerous substance or physical situation, with a potential for creating
damage to human health and/or the environment"
The purpose of the Hazard Identification and Risk Assessment process is to identify all potential major
accident Hazards in each area of the site where dangerous substances are held processed or stored.
The assessment is carried out to determine the likelihood, severity and consequences of major
accident scenarios. The methodology used is based on Preliminary Hazard Analysis, which involves a
systematic assessment of the risk levels of all operations in order that effective management of the
facility can occur. This method gives a semi quantitative assessment of the overall level of risk
presented in each case.
An assessment of the existing measures in place and recommendations for new measures for each
major accident scenario was carried out. This assessment shows that Dynea is proactive in providing
all necessary measures to protect both man and the environment from the consequences of each
major accident scenario arising from its operations at the facility at Marino point.
This method of Preliminary Hazard Analysis (PHA) is an approved risk assessment technique, which
is approved by Institute of Chemical Engineers (IChemE). In addition to the PHA study which focuses
specifically on major accident scenarios, HazOp studies are being carried out on all plant and
equipment.
1.1.2 2004/2005 HazOp Study
In late 2004 Dynea Ireland reviewed the HazOps completed on the plant in 1995/1996. These
HazOps were shown to be incomplete. It was decided in 2004 that a complete HazOp of the plant
would begin. This process is ongoing. It is hoped that this process will be finished by March 2006. A
summary of the HazOp procedure is given below.
A HazOp (1) study identifies hazards and operability problems. The study involves investigating how
the plant might deviate from the design intent. If, in the process of identifying problems during a
HazOp study, a solution becomes apparent, it is recorded as part of the HazOp result. HazOp is
based on the principle that HazOp team members with different backgrounds can interact and identify
more problems when working together, than when working separately and combining their results.
The HazOp concept is to review the plant in a series of meetings, during which a multidisciplinary
team methodically assesses the plant design, following the structure provided by the guide words.
The process requires that all team members participate. The team focuses on specific points of the
design (called "study nodes"), one at a time. At each of these study nodes, deviations in the process
parameters are examined using the guide words. The guide words are used to ensure that the design
is explored in every conceivable way.
Each guide word is applied to the process variables at the point in the plant (study node) which is
being examined. For example:
1 HAZOP Guide to Best Practice, IChem E (UK), EPSC, CIA, 2000
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. . .. . . . .
Guide Words
NO
MORE
Safety Report
Document Revision: issue Date:
Number:1.0.3 3 1 I1 2/05
Parameter Deviation
FLOW NO FLOW
PRESSURE HIGH PRESSURE
I
dynea
These guide words are applicable to both the more general parameters (e.g., react, transfer) and the
more specific parameters (e.g., pressure, temperature).
With the general parameters, meaningful deviations are usually generated for each guide word. It is
not unusual to have more than one deviation from the application of one guide word.
The results of the discussions are recorded on the standard HazOp report form. This form details
recommended actions for improvements and assigns a member of the team to complete the action. A
summary of HazOp technique is given in appendix 5. The makeup of the HazOp team is detailed in
section 1 .I .5 and contains the same members as PHA team.
0
1.1.3 Risk Assessment
In 2005 Dynea purchased Risk Assessment (RiskSase) software from Crest Solutions who have
developed this new Risk assessment software. This software allows the user to schedule risk
assessment occurrence and to track the implementation of control measures generated. The following
is a summary of how the risk assessment software works. Risk questions are developed, and
downloaded to a pocket PC. The Pocket PC prompts the user to answer risk questions and resulting
from answers given, will be required to enter control measures to reduce the risk. When the
assessment is complete the user will upload the assessment and sign off the risk assessment. The
actions generated during the assessment will be placed on an actions database and assigned to
individuals with a time frame for completion. People who are assigned actions will be automatically
given reminders by email as to status of the action. When the action is completed the action is
approved by the Health and Safety Manager. Reports can then be created of actions completed,
actions not completed and number of assessment completed on time etc. A complete guide to the
system is detailed in Appendix 15.
1.7.4 2003 PHA Study
A review of the safety report took place at end 2003 and it was decided that the previously used
methodology might not be sufficiently detailed to include all possible scenarios. Dynea Ireland, to
comply with the requirements of SI 476 of 2000, requested that a Preliminary Hazard Analysis study
(i.e. PHA) be conducted on their Marino Point facility to assist in the formal identification of the major
hazard scenarios associated with their manufacturing and storage facility. Another outside consultant
was engaged and a Preliminary Hazard Analysis was carried out with the involvement of key Dynea
personnel. Preliminary Hazard Analysis is typically used to identify site major hazards and as a
precursor to further detailed analysis of the hazards identified.
The technique of Preliminary Hazard Analysis2,3 is typically used to identify the major hazards
associated with a production or storage facility and is a precursor to a more detailed analysis of major
hazards using the technique of Quantified Risk Assessment.
A PHA study typically has the following steps:
2 Institution of Chemical Engineers, Hazard Identification and Risk Assessment, Geoff Wells, 1996
3 Loss Prevention in the Process Industries; 1996; Volume 1.
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Safetv ReDort
Doci ment Revision: Issue Date:
Number:1.0.3 3 111 2105
0 The plant is divided into study sections or nodes.
0 A PHA study team is assembled for the section or node under study.
0 Guide-words appropriate to PHA are applied to the section of plant under study to help
identify scenarios with major hazard potential.
The guidewords address major hazards such as:
0 Fire and explosion.
0 Chemical.
0 Environmental.
0 Thermodynamic (pressure and temperature)
0 Domino Effects.
For each major hazard scenario identified a Severity Ranking is assigned as follows.
Severity 5: Catastrophic Consequences
0
Severity 4: Severe Consequences
Severity 3: Major Consequences
Severity 2: Appreciable Consequences
Severity 1: Minor Consequences
A frequency at which it is judged that this scenario is likely to occur is assigned.
A priority rating for the scenario is assigned for further study using the risk ranking matrix as shown in
Table 1.
Based on Table 1, a formal mechanism to allow the major hazard scenarios to be ranked and
prioritised for further study is provided. The purpose of this prioritisation and selection process is to
allow for a representative set of scenarios for further study to be compiled from the initial list of major
hazard scenarios that has been generated by the PHA process. Many of the scenarios identified from
a PHA study have similar severity ratings and similar consequences. J udgement is therefore applied
to ensure that the set of scenarios selected for further study is representative of the cross range of
major hazards presented by a facility.
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Risk Ranking Matrix
Risk =L+S
Lower Value of Lower Risk Equal Greater
\ L l -2
Severity (S)
I -I I o I o
Risk =loglo l oL +loglo I O s
= L + S
The Risk is only acceptable when its value is equal to or less than zero.
A
B
C
None
=High priority for further study (risk considered to be high)
=Further study probably required (risk considered to be medium)
=Further study may be unnecessary (risk considered to be low)
=No further study (risk considered to be well within acceptable limit)
Table 1 Risk ranking matrix
Dynea conducted the PHA exercise at Marino Point in late 2003, early 2004. A further review of the
study took place in the third quarter of 2005.
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Preliminary Work
An inventory of all materials stored, used or produced at Dynea was drawn up. All the substances
covered by SI 476 of 2000 were identified, with the inventories and risk phrases assigned and storage
locations identified. The inventory included by-products and intermediates, which are produced from
planned and unplanned operations at Dynea. This process ensured that all dangerous substances
under SI476 of 2000 and their influence on major accidents were considered in the assessment
process. Within the Dynea group a HSE database is used to record all accident and near misses that
have occurred in its plants worldwide. This information was gathered prior to the PHA study and used
to aid the identification of Major accident scenarios. Information from past incidents at the plant at
Dynea was also used. This information was recorded on the PHA pro forma.
7.7.5 PHA / HazOp Study Team
Q
-
The PHA team was selected on the basis of their experience and knowledge and expertise to ensure
that all major accident scenarios were identified and each of the associated risks assessed. The team
members have had appropriate training in hazard identification and risk assessment and have
knowledge of all operations at the plant. The study team also included an outside consultant who
facilitated the whole process.
The members of the team are as follows:
James OCallaghan - Production Manager
21 years experience in the food and bulk chemical industry, primarily at a supervisory level.
Previously employed by Wheat Industries/Cerestar in Ringaskiddy and FMC in Little Island.
Completed City and Guilds 275 Instrumentation
Has worked for Dynea since before start-up in 1996, initially in a shift leader (production supervisor)
role and since November 2000 as the Production Manager with overall responsibility for all
manufacturing activities on site.
Dermot OCallaghan - Laboratory Analyst/ HSE Chemist
BSc. Industrial Chemistry from University of Limerick 1997. Has completed a Diploma in Safety Health
and Welfare at Work in 2004. Has attended Risk Assessment courses provided by outside consultants
through Dynea.
@
Has worked for Dynea since 1997 as a laboratory analyst with primary responsibility for air and water
environmental sampling as well as all raw material and finished product testing. Has, since Q1 2003,
assisted in HSE duties and, since Q1 2004 has been on full-time HSE duties.
Peter ORegan - HSEITechnical Services Manager
BSc Industrial Chemistry from the University of Limerick in 1991. MSC in Environmental Analytical
Chemistry from UCC in 1993. HDip in Management and Marketing from UCC in 1998. Cert. in Health
Safety and Welfare at Work from UCD in 2001.
Previously worked for SmithKline Beecham (now Glaxo SmithKline) in Dungarvan. First as a lab
analyst, then as a LlMS (laboratory information management systems) co-ordinator responsible for
creation and validation of new protocols and finally as technical services co-ordinator for
packaginghableting - commissioning and validating equipment.
Has worked for Dynea (previously Dynochem) since start-up in 1997 - first as lab
supervisor/environmental chemist; then as quality, safety and environmental manager/plant chemist;
and since Q1 2003 as HSEiTech Services Manager.
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.J
Member of:
The Institute of Chemistry of Ireland
The Emergency Planning Society (Ireland Branch)
Denis Curtin -Consultant, MSc. (Eng.), M.I.E.I., M.I.Chem.E., M.I.0.S.H
Denis Curtin is a qualified chemical engineer with a post-graduate degree in process safety. He has
18 years experience working within the pharmaceutical, fine chemical and gas processing industry,
including employment as safety manager for a major hazard process, storage and distribution
installation.
Over the past 7 years he has worked as a consultant to the pharmaceutical and chemical industry in
process safety. He specialises in quantified risk assessment techniques for major hazard sites, and
process safety management evaluation and development.
Denis Curtin graduated from the Cork Institute of Technology in 1986 with a Degree in Chemical
Engineering and graduated with Distinction from the University of Sheffield in 1995 with a Masters
Engineering Degree in Process Safety and Loss Prevention.
(D
Denis Curtin set up a consultancy practice in process safety to provide support and assistance to the
chemical and allied industry in accident and incident prevention.
Member of:
The Institution of Chemical Engineers.
The Institution of Engineers of Ireland.
The Institution of Occupational Safety and Health.
7.7.6 Areas Assessed
For the purposes of the risk assessment, the overall plant was broken down into areas. All areas of
the site were assessed. Areas in which there was no likelihood of a dangerous substance being
present were identified but were eliminated from the study.
The locations assessed include:
1. Methanol ship offloading at jetty
0 2. Pipelines
3. Methanol Tank T401
4. Methanol Road tanker loading/Offloading area
5. Formox process
6. By - products / Intermediates
7. Formalin Tanks (50% formaldehyde)
8. Reactors
9. Chemical Storage
IO. LPG Storage
1 1. Diesel storage
I
The study covers all areas where dangerous substances are stored used or produced.
7.1.7 PHA Procedure
Maior Accident Scenarios
The PHA team assessed each of the above areas in detail. The contracted consultant produced a
PHA pro- forma which is detailed in Appendix 15. The process involved determining the Major
0
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Accident Scenario (MAS) for each area. Each area was assessed and an assessment made of the
consequences.
Site Major Accident Scenarios (MAS) generally fall into the following categories:
Explosions
Fires
Toxic Gas Releases
Environmental Impact
Assianina Severity Rating
Each event was assigned a Severity Rating between 1 and 5 in accordance with PHA methodology,
bv assessing the realistic potential consequence. Severity ratings are assigned on the basis of health
ai d safetv and environmental impacts. For any incident which would incur significant costs, the
severity rating may be increasedi.e. property damage, environmental cleanup etc. The tables used
for assigning severity ratings are given in Table 2.
Q
Severity Rating Consequences Consequence detail
5 Catastrophic
4
3
2
Severe
Major
Appreciable
1 Minor
Catastrophic damage and severe clean-up costs.
On-site: Loss of normal occupancy >3 months.
Off-site: Loss of normal occupancy >1 month.
Severe national pressure to shutdown.
Three or more fatalities of plant personnel.
Fatality of member of the public or at least five injuries.
Damage to historic building.
Severe environmental damage involving permanent or long
term damage to a significant
Severe damage and major clean-up.
Major effect on business with loss of occupancy up to
3months.
Possible damage to public property.
Single fatality or injuries to more than five plant personnel.
One in ten chance of a public fatality.
Short-term environmental damage over a significant area.
Severe media reaction.
Major damage and minor clean-up.
Minor effect on business but no loss of building occupancy.
Injuries to less than five plant personnel with one in ten
chance of fatality.
Some hospitalisation of public.
Short term environmental damage to water, land, flora, or
fauna.
Considerable media reaction.
Appreciable damage to plant.
No effect on business.
Reportable near miss incident under EC Directive - Seveso
It.
Injury to plant personnel.
Minor annoyance to public.
Near-miss incident with significant quantity released.
Minor damage to plant.
No effect on business.
Possible injury to plant personnel.
No effect on public, possible smell
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Table 2 Major Accident Scenario Severity Ratings
The severity ratings used in the Dynea PHA study ensures that all notifiable incidents as defined
under schedule 7 and 8 of S.1 476 of 2000 of the regulations are captured as shown in Table 3 .
SI 476 of 2000 Dynea Severity Ratings
Schedule 7
Any fire, explosion or accidental discharge involving at least 5%
Of the qualifying quantity laid down in Annex 1 of the Seveso 11
Directive, i.e.
-1 0 tonnes of Formalin
-250 tonnes of Methanol
- a death,
- six persons injured within the establishment and hospitalized
- one person outside the establishment hospitalized for at least
- dwelling(s) outside the establishment damaged and unusable
- the evacuation or confinement of persons for more than 2
-the interruption of drinking water, electricity, gas or telephone
for at least 24 hours
24 hours,
as a result of the accident,
hours (persons x hours): the value is at least 500,
services for more than 2 hours (persons x hours): the value
is at least 1 000.
e
permanent or long-term damage to terrestrial habitats:
- 0,5 ha or more of a habitat of environmental or conservation
- 10 or more hectares of more widespread habitat, including
- significant or long-term damage to freshwater and marine
importance protected by legislation,
agricultural land,
habitats
Significant or long term damage to terrestrial habitats
10 km or more of river or canal,
0
- 1 ha or more of a lake or pond,
- 2 ha or more of delta,
.- 2 ha or more of a coastline or open sea,
Significant damage to an aquifer or underground water
>I ha
Damage to property
- damage to property in the establishment at least ECU 2
million,
- damage to property outside the establishment; at least ECU
0,5 million -
Cross- border damage
Schedule 8
The explosion, collapse or bursting of any closed vessel,
including a boiler or boiler tube, in which the internal pressure
was above or below atmospheric pressure.
An explosion or fire occurring in any installation or place which
Q)
2-5
2-5
4
4
4
4
2
2
4-5
4-5
4-5
5
3-4
3-4
3-4
4-5
4-5
4-5
Not applicable
3
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resulted in the stoppage of any part of the installation or
suspension of normal work in that place for more than 24 hours,
where such explosion or fire was due to the ignition of process
materials, their by-products (including waste) or finished
products.
The uncontrolled or accidental release or the escape of any
dangerous substance from any apparatus, equipment, pipe
work, pipe-line, process plant, storage vessel, tank or in works
conveyance tanker, which, having regard to the nature of the
substance and the extent and location of the release or escape,
might have been liable to cause serious injury to any person or
serious damage to the environment.
3
2-3
Any unintentional ignition or explosion of explosives
containing a dangerous substance:-
(a) the bursting, explosion or collapse of a pipe-line or any part
thereof;
( b) the unintentional ignition of anything in a pipe-line or of
anything which immediately before it was ignited was in a
pipeline.
Table 3 Notifiable incidents as defined under schedule 7 and 8 of S.1476 of 2000
Not applicable
Depending on severity of pipeline
damage
Either of the following incidents in relation to a pipe-line 1-5
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Identification of initiafinq events
After assigning the severity rating the team completes the PHA pro forma. A structured approach was
used by the PHA facilitator to identify the initiating events which could lead to a major accident.
Which include mechanical failure, human error, control equipment failure, external events etc. This
detail is recorded on the PHA pro forma as detailed in Appendix 15.
Assiuninn frequency rating
A PHA will not give an accurate assessment of the frequency of any incident nor the measures used
to control or avoid the release. With this technique it is particularly important to identify the worst
accident which might occur such as the greatest fire, explosion, toxic gas release, or incident with a
major environmental impact.
For a PHA study, it is also not necessary with this step of an analysis to determine exact frequencies
-a
of events. The acceptable frequency ratings are detailed below foreach of the severity classes
Severity Description Acceptable frequency(occurrence per year)
5 Catastrophic 10-5
4 Major 10-4
3 Severe 10-3
2 Appreciable 10-2
1 Minor 10-1
Identifying all the site major hazards is, however, essential, as a hazard omitted is a hazard not
analyzed. The frequency ratings were assigned using the following information available.
The methodology involved in conducting a PHA study is detailed in Appendix 15.
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With the assistance of the risk-ranking matrix outlined in Table 1 above, Table 8 summarises the
major hazard scenarios that are representative of the Dynea Ireland site, and where further detailed
analysis is required.
Physical Inspections
Physical inspections were carried out at the site to ensure that measures discussed at the PHA
meeting were in fact present and to identify other existing measures that should be accounted for.
1.1.7.1
After the PHA study was completed a study group was formed to examine the hazard scenarios and
to assess the adequacy of the control measures in place. The criteria used to determine the adequacy
of the risk control measures is based the ALARP (As Low As Reasonably Practicable) principle. The
assessment involved assessing the control measures for each Major Accident Scenario and
determining whether the control measures reduce the risk to an acceptable level (as low as
reasonably practicable). Control measures which did not satisfy the ALARP criteria were subject to
further analysis. A standard pro forma was developed, this pro forma and the detail of assessments is
detailed in Appendix 15. The team carrying out this assessment was made up of HSE Technical
Services Manager and Production Manager, Quality Manager and Health and Safety Officer. These
discussions involved assessing all accidents regardless of severity. Accidents with severity 3, 4 or 5
were categorised as major accident scenarios. Incidents with low severity but high frequency were
assessed to determine whether by virtue of their high frequency, they would be classified as major
accident scenarios.
PHA Assessment of Maj or Accident Scenarios
,@
1.1.8 Consequence Modelling
1.1.8.1 Quantified Risk Analysis
In a QRA both the frequencies of events and their consequences are quantified, using appropriate
techniques. Typically, QRA will consist of the following steps:
1. Identification of the hazards.
2.
3.
4.
Summarising the findings of the hazard identification study as a set of scenarios to be
modelled.
Estimation of the rates and duration of releases, and the quantities of material involved.
Estimation of the consequences of each release in terms of an area inside which, for a given
wind speed /weather stability combination, a specified level of harm (toxic load, explosion
overpressure, thermal radiation flux) will be met or exceeded.
Consideration of the effects of mitigation (for instance by people going or staying indoors).
Translation of the release, by way of a model of human impact, into a measure of
harm (e.g. injury or fatality) to the specified individual or population.
Estimation of the frequencies with which events (usually releases of hazardous material
from their containment) are expected to occur.
Combination of various probabilities and frequencies to calculate numerical estimates of
risk.
a
5.
6.
7.
8.
Steps 1 to 3 results in a set of scenarios for modelling, together with the necessary data to
compute frequencies and consequences. It should be conducted by an experienced
analyst or team of analysts. Step 4, on the other hand, usually involves some form of modelling
of gas dispersion, fire or explosion effects. This is carried out by use of computerised models which
will be discussed in the next section.
It is possible to produce different types of numerical risk estimate at step 8, depending on the
purpose of the QRA study. Broadly speaking, numerical risk estimates are one or both of:
- Individual risk estimates; and
Societal (or group) risk estimates.
Q -
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Individual risk has been defined as follows (HSE 1995):
Individual risk is the risk of some speciJied event or agent harming a statistical (or
hypothetical) person assumed to have representative characteristics. I
The individual referred to will be defined in accordance with the requirements of the QRA to
be undertaken. It may, for example, be a member of a certain group of workers on a facility with
defined characteristics in terms of their working pattern. Alternatively, the individual may be
defined so as to be representative of a member of the public, such as the hypothetical house
resident .The specified event or agent may be defined as fatality, injury, or exposure to a defined
level
of blast overpressure, thermal radiation or dose of toxic material.
Quantitative risk assessment (QRA) involves obtaining a numerical estimate of the risk from a
quantitative consideration of event probabilities and consequences.
@ 1.1.8.2 Modelling
The objective of consequence modelling is to predict the impacts of accident scenarios involving fires,
explosions and toxic release on the site. The quantitative data resulting from the consequence
modelling was used as an aid for assigning severity rating in the PHA study, for the development of
the specified area around the Dynea site and as an aid in emergency planning.
The consequences of the scenarios were modelled using the DNV Technica computer packages
PHASTMicro and WHAZAN, and the US EPA-approved air dispersion model lSCST3.
PHAST examines the progress of a chemical process incident from initial release through formation of
a cloud or pool to final dispersion - calculating concentration, fire radiation, toxicity and explosion
overpressure. Due to its reliability and outstanding technical superiority, PHAST is used by over 300
organisations world-wide.
PHAST is a comprehensive hazard analysis package, applicable to all stages of design and operation
across a range of process and chemical industry sectors. It is used to identify situations which present
potential hazards to life, property or the environment. Such scenarios may be removed by re-design of
the process or plant, or modification to existing operational procedures. Scenarios which remain may
be submitted to further analysis such as rigorous risk assessment, where necessary, using more
sophi st i cat ed QRA t ool s such as SAFETI.
The Unified Dispersion Model (UDM) used in PHAST has been extensively verified and has been
validated against a large number of field experiments. These include continuous, elevated two phase
and vapour releases, ground level liquid spills and unpressurised instantaneous releases. A subset of
these experiments were used in the EC funded SMEDIS project. The SMEDIS project is an
independent review of both the theory and the performance of many dispersion models. The UDM has
excelled in both aspects of the review
The Industrial Source Complex Short Term (ISCST3) model is the US Peas current regulatory model
for many New Source Review (NSR) and other air permitting applications. The ISCST3 model is
based on a steady-state Gaussian plume algorithm, and is applicable for estimating ambient impacts
from point, area, and volume sources out to a distance of about 50 kilometres. ISCST3 includes
algorithms for addressing building downwash influences, dry and wet deposition algorithms, and also
incorporates the complex terrain screening algorithms from the COMPLEX1 model.
Extensive in-house modelling was carried out on ALOHA - the dispersion modelling software
developed jointly by the US Environmental Protection Agency (EPA) and US National Oceanic and
Atmospheric Administration (NOAA). ALOHA has a number of limitations which are mentioned below.
@
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@ Number:l.O.3 3 111 2105
Condition Pasquill Atmospheric
Stability Category
PHASTMicro is a package consisting of a series of linked models that predict the consequences of
releases of hazardous materials, whether flammable, toxic or both.
WHAZAN is an older and simpler package consisting of a series of stand-alone models that perform
essentially the same function as PHASTMicro.
Wind Speed
(mW
ISCST3 is a suite of models that are used to predict the ambient air quality from industrial source
complex terms. A previous version of the model was used to predict the impact of normal or licensed
emissions from the plant. The model was used to predict abnormal emissions for this study.
Extensive in-house modelling was carried out on ALOHA - the dispersion modelling software
developed jointly by the US Environmental Protection Agency (EPA) and US National Oceanic and
Atmospheric Administration (NOAA). ALOHA has a number of limitations which are mentioned below.
ALOHA'S results can be unreliable when the following conditions exist:
(a) Very low wind speeds
e
(b) Very stable atmospheric conditions
(c) Wind shifts and terrain steering effects
(d) Concentration patchiness, particularly near the source
ALOHA doesn't account for the effects of:
(a) Fires or chemical reactions
(b) Particulates
(c) Solutions and mixtures
(d) Terrain - ALOHA expects the ground below a leaking tank or puddle to be flat, so that the liquid
spreads out evenly in all directions. It does not account for pooling within depressions or the flow of
liquid across sloping ground. The raw data required for the modelling is detailed below.
Material Properties
The model was used with the standard properties of methanol and formaldehyde.
For modelling of formalin, a new material was defined as a 50% aqueous solution of formaldehyde.
The vapour pressure of formaldehyde over an aqueous solution of this strength at various
temperatures was taken from published material, and a correlation fitted to the data. The correlation
was inserted into the data file. Other physical properties of 50% aqueous were also inserted into the
data file.
s)
Meteorological Conditions
Two standard meteorological conditions were used and these meteorological conditions are
representative of the majority of the conditions experienced at Cork Airport.
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Concentration Limits .
For methanol and formaldehyde, the model was used to predict the dispersion distances to the
various concentration limits, i.e. ERPGI, ERPG2, ERPG3. An explanation of these terms is detailed in
Table 5.
Q
ERPG
ERPG- 1
ERPG- 2
Basis
Effects other than
mild transient adverse
health effects or
perception of a clearly
defined objectionable
odour
Irreversible or other
serious health effects
or symptoms that
could impair an
individual's ability to
take protective action.
Life threatening
health effects
Table 5 Toxic Harm Criteria
The ultimate concentration of interest for formaldehyde was specified as 10 ppm (ERPG- 2). The
ultimate concentration of interest for methanol was specified as 250 ppm (OEL-STEL).
These concentration limits is a time-weighted average, and are based on specified time periods. The
model calculates the dispersion distances for time-averaged concentrations. As the time over which
the concentration is averaged increases, the average concentration for that time decreases.
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Safetv ReDort
- Doci ment Revision: Issue Date:
@ Number:1.0.3 3 1/12/05
7.7.9 All Necessary Measures
Dynea is committed to putting in place all necessary measures to prevent major accidents occurring
at the plant and to limit the consequences of any such major accidents to man and the environment.
During the PHA process and the HazOp study, the systems in place at Dynea are assessed to ensure
that the risk to man and the environment is as low as is reasonably practicable (ALARP). If the
systems in place are not adequate an analysis will be carried out to determine the necessary
measures required to reduce the risk to as low as reasonably practicable.
The assessment was carried out as set out below.
Staae 1 - PHA Team Meetinas
During the PHA study, each scenario was described and assigned a risk rating based on the
likelihood of occurrence and severity of impact. The relevant risk reduction and consequence
mitigation measures in place for each scenario were recorded by the PHA team. Additional measures
highlighted during the study were included in an implementation programme. These measures will
further reduce the risk of major accident scenarios.
Staqe 2- Review of PHA findinqs.
After the scenarios were identified a process began whereby a review of the PHA findings was
undertaken. This involved determining appropriate actions to reduce higher levels of risk to as low as
is reasonably practicable. Actions generated during the study were assigned to individuals to
complete. These actions are tracked by the HSE Technical Services Manager. Actions that are not
closed out are tracked at the HSE monthly meetings and further resources will be made available to
close these actions out.
7. 7. 70 Review
The hazard identification process will be reviewed every 5 years as part of the Safety Report review
which is required under SI476 of 2000. The process will also be carried out once there has been a
significant increase in inventory of Seveso 2 substances at the Dynea facility, and where installation of
new plant and equipment is taking place at the site. This review will be triggered by the control of
change procedure.
The review process will ensure that the hazard identification processes reflects all changes in installed
plant, operational procedures etc. and will ensure maximum protection for both man and the
environment at all times.
ab
1
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1.2 Major Accident Hazards Excluded
1.2.1.1 Aircraft Impact
In a recent report the Department of Transport and the Department of the Environment and Local
Government commissioned ERM (Environmental Resource Management) consultants to carry out an
investigation of the Public Safety Zones (PSZs) at lrelands 3 principle airports Dublin, Shannon and
Cork. The purpose of the report was to prevent inappropriate use of land during the planning process,
where the risk from aircraft crashes in a populated area is the greatest. This study involved using risk
modelling techniques to quantify the risks to the public from aircraft crashes. The proposed PSZ for
Cork Airport is shown in Figure 1.
Figure 1 Public Safety Zones (Source ERM Ireland)
The areas of highest risk of airplane crashes are in the vicinity of the airport due to the amount of air
traffic in the area. This area is highlighted in yellow on the map. The area outside the outer zone
shows that the individual risk from an aircraft crashing is (UK HSE6 guidance proposes an
individual risk of death of per annum as the threshold between the broadly acceptable and
tolerable risk to the general public.) Any location in this area will not be restricted from development
5 Public Safety Zones: Cork, Dublin and Shannon Airports, ERM, J une 2003(Draft) on behalf of
Department of Transport and Department of Environment & local Government.
6 Reducing Risks, Protecting People: HSEs decision- making process. Health and safety Executive,
2001
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on the basis of the Public Safety Zones. The plant at Dynea is well outside these zones in Cobh and
based on this probability, an aircraft crash is not likely to result in a Major Accident Scenario
1.2.1.2 Earthquakes
The School of Cosmic Physics (part of the Dublin Institute of Advanced Studies) has been monitoring
earthquake activity in Ireland since 1978. They have concluded that Ireland is seismically very stable
and that this is unlikely to change in the future. The US geological Survey (have recorded the number
of earthquakes across Europe between 1975 and 1995.
Figure 2 Earthquake Incidents in Europe
From the diagram in Figure 27, it can be seen that there was scarcely any earthquakes in Ireland in
that period. Any recorded activity in Ireland was confined to the Southeast and Northwest of the
country. There are no figures on the map to quantify the risk; the map does show that there were
7 US Geological Survey
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Maximum Daily Value
Maximum Hourly Value
Maximum Monthlv Value
dynea
85mm/day
23.7mm/hr
220.5mm/month
- - -. . . -. . .
Number:1.0.3 3 1/12/05
scarcely any earthquakes in Ireland during the period from 1975 to 1995. Based on this information a
Major Accident resulting from an earthquake at Dynea was eliminated from the study.
1.2.1.3 Floods
Rise in Sea Level
Flooding from estuaries or the sea is generated from sea levels (a combination of astronomical tides,
atmospheric surges, wind set-up and waves) exceeding the level of, and hence spilling onto, the
neighbouring l and.
The tidal levels at Ringaskiddy are given in Table 6.
Table 6 Tidal Levels at Ringaskiddy Table 6 Tidal Levels at Ringaskiddy
The average mean sea levels in Southwest Ireland are rising at a rate of 1 mm per annum'.
The maximum height recorded at Ringaskiddy is 4.3m. The harbour is at its widest point at the Dynea
site, which means that it can retain a substantial amount of water before an increase in water height
would be noticed. The plant at Marino point has no history of flooding. The Dynea site is
approximately 6 m above the datum line. From historical data recorded at the J etty and from an
examination of the records at Port of Cork shows that since 1980 the highest tide(inc1uding waves)
has been 5.2 m with 5.0m being reached three times. From this data we can conclude that the
probability of flooding at the Dynea site is very low and is thus not considered as a major accident
scenario.
Storm water
All storm water at the site flows into the main collection point at Basin 1. Bunded areas at the site are
closed systems and storm water will collect there. This storm water is drained to Basin 1 by opening
valves at the bunds. After heavy rainfall operators check the bunds and drain the water to Basin 1.
In order that a tank would float the water level in the bund would have to rise to a sufficient level. This
is unlikely to happen in the resin tank farm as the bund wall is only half a meter. The rainfall recorded
at Roche's Point is given in Table 7.
@
I I Rainfall I
Table 7 Average and Worst Case Rainfall
In order to float the methanol tank (empty) a water depth of approximately 2 meters in the bund would
be required. This would mean that it would need to rain for approximately 9 months at the maximum
monthly value to float the tank (this would mean that the bund would never have been emptied of
rainwater for those 9 months). Based on the above information, a major accident involving storm
water flooding at the plant has been eliminated on the grounds that the probability is too low.
1.2.1.4 Subsidence
The Dynea site is a partly reclaimed site located at Marino Point. A full Geotechnical Survey including
@ 8 OPW Publication "Report of the Flood Policy Review Group "
9 ENFO publication BS27, ' Sea Level Changes and Ireland'.
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boreholes and trial holes was carried out in 1995. The most Northerly end of the site is recently
reclaimed, with levels raised by importing stone prior to construction of the new plant.
All the main structures on the north end of the site are piled, these are:
0 Urea Store
0 Resin Building
Formalin Building
Control Building
0 The Former Spray Dryer
The Former Packaging Building
In addition, because of the very high loading, the concrete slab directly beneath the Methanol Tank is
piled. The remainder of the Methanol bund is not piled, due to its large surface area. The Waste
Water Treatment Plant contract was originally let as a design and build contract to EPS, with specific
mention that the foundations were to be piled. During the end of 2003 it was noticed that the aeration
tank were subsiding. In 2004 engineers were contracted to carry out an assessment of the tanks in
the waster water treatment plant. As a result of this assessment the tank was dismantled and piling
began in the summer of 2005. The tank has been reassembled and at time of writing and is
undergoing leak tests.
The resin tank farm is not piled but is instead designed as a raft slab. The overall loading on the slab
relative to the area of the slab is not excessive. Also the location of the tank farm is away from the
Northern end of the site, where the very poor ground conditions are located.
Based on the above information, a major accident resulting from subsidence at the plant has been
eliminated on the grounds that the probability is too low.
I .3 Major Accident Scenarios
The list of major accident scenarios compiled during the PHA study is detailed in Appendix 15. From
this list a subset was identified as detailed in Table 8. A number of follow up action items were raised
during the PHA study meetings where further information or investigation is required to ensure that
the severity of the scenario assigned is correct and clearly understood. Actions generated during the
study were assigned to individuals to complete. These actions are tracked by the HSE Technical
Services Manager. Actions that are tracked at the HSE monthly meetings and further resources will
be made available to close these actions out. On-going reviews of these action items will be
conducted by Dynea Ireland until all of these issues have been addressed. The HSE manager is
responsible for ensuring that actions generated for reducing the likelihood of major accidents are
closed out.
The findings of the PHA major hazard scenarios identified through the PHA study are detailed in
Appendix 15. The scenarios are ranked according to the degree of severity (and priority for further
analysis) as assigned by the PHA study group and in accordance with the criteria set out for
conducting Preliminary Hazard Analysis.
63 scenarios were identified and assessed for the site, broken down as follows:
0
Five scenarios were ranked as potentially having catastrophic consequences i.e. Severity 5.
0 One scenario was ranked as severe i.e. Severity 4.
0
Thirteen scenarios were ranked as major i.e. Severity 3.
0 The remaining scenarios were ranked as having appreciable consequences i.e. Severity 2 or
lower.
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The potential consequences of the scenarios identified are various e.g. thermal radiation effects from
a Methanol fire, overpressure effects from a reactor explosion, toxic vapour exposure from a
Formaldehyde release, and environmental impacts to the harbour from a Methanol spill.
With the assistance of a risk ranking matrix as outlined in Table 1, a total of 15 scenarios are selected
as representative of the major hazard scenarios associated with the Dynea Ireland site. The
Scenarios are listed in Table 8 below.
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0
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No.
01
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07
-
10
Severity
5
5
5
Priority
A
A
A
Scenario Description
Ship off loading methanol -
loading arm leaks or fractures -
solvent ignites resulting in a
large scale fire on the jetty
potentially engulfing the ship and
resulting in a large scale
explosion on the ship.
Methanol storage tank TK401
fails instantaneously - resulting
in a large release of Methanol
which overtops the bund wall -
and ignites encompassing a
large area.
Similar to Scenario 06 - solvent
fire in bund - a prolonged fire
causes the tank to overheat and
rupture resulting in an
overpressure effect locally.
Potential escalation of Scenario
10 -where a rupture of the
storage tank potentially impacts
on the Methanol road tanker
loading/offloading bay and other
production/storage areas.
Methanol road tanker
rupture/explosion.
Flammable air/Methanol mixture
within a reactor - mixture ignites
- potential overpressure and
rupture of reactor causing a blast
effect.
Similar to Scenario 07 no ignition
occurs - dispersion of toxic
vapours over local area.
Similar to Scenario 01 -the ship
off loading arm leaks or fractures
- resulting in a spill of solvent
causing a local environmental
impact on the harbour area.
Similar to Scenario 01 -where a
Methanol pipeline leak/fracture
xcurs on the line leading to the
storage tank - causing local
:ontamination of the soil.
Methanol storage tank TK401 -
eak into the bund - solvent
gnites - potential radiation
2ffects from a large scale fire.
Hazard Effects
Thermal radiation
effects
Explosion
overpressure effects
~~
Thermal Radiation
Overpressure/blast
effect
Overpressure/blast
effect
Ove rp ressu re/b last
effect
Overpressure/blast
effect
Toxic effects
Thermal radiation
effects
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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
B
Safety Report
0 Number:1.0.3 3 1/12/05
Similar to Scenario 07 no ignition
occurs - potential environmental
impact of a spill on the local
Environmental impact
-
No.
09
-
-
B
B
24
-
29
-
53
-
61,
62
-
'able
Formaldehyde vapours -
potential impact on personnel.
Formalin Tank instantaneous Toxic effects
rupture - Formaldehyde toxic
gas vapours disperse and
potential impact on personnel.
WWTP tank rupture due to
subsidence causes a short term
environmental impact.
Severity
C
3
Fire water retention pond leaks
or overfills - potential
environmental impact.
3
3
Priority I Scenario Description I Hazard Effects
I I
1 harbour area:
B I Formox Process - leak of 1 Toxic effects
b: Summary of Dynea Ireland site Major Hazard Scenarios
The PHA did not identify any significant new hazards which required modelling so the originally
identified set was used for this purpose. The following major accident scenarios were identified in the
original Major Accident Scenario assessment for the Dynea site:
Fire
Methanol Tank Fire
0 Methanol Bund Fire
Formalin Plant Fire
Ignition of methanol
0 Ignition of Dowtherm
0 Ignition of Stabilizer
0 Methanol Ship Fire
Methanol Tanker Loading Bay Fire
Q) 0 Ignition of formaldehyde
Explosions
Reactor Head Space Explosion
0 Methanol Tank Explosion
Gas Explosion
t
Loss of Containment
0 Formaldehyde Gas Cloud Release
0 Formalin Tank Rupture
0 Formox Process Rupture
0 Methanol Release
Methanol Tank Rupture
0
Methanol Ship Spillage to water
Page 22 of 65
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Number:1.0.3 3 111 2/05
Radiant Heat
( kW/m2)
dynea
Effect
0 Methanol Tanker Loading Spill
Domino Effects
0 Domino Effects IF1
Transport of Hazardous Materials (Road Transport Regulations)
0 Methanol
0 Formalin
Major-Accident Scenarios with Environmental Impact
Major-accident scenarios with environmental impact comprise all of the above. In particular, the
following accidents are considered:
Loss of containment of methanol - pollution of Cork Harbour may affect aquatic flora and
fauna
Loss of containment of formaldehyde - pollution of Cork Harbour and air pollution may
affect flora and land-based fauna
Fire involving methanol, resin or formaldehyde - products of combustion may affect flora
and land-based fauna
0
0
0
@
1.3.1 Fires
Three thermal radiation levels are chosen to cover a range of effects of fire:
4 I Not fatal, but will prevent escape I
12.5 I Can be fatal I
37.5 I Can cause damage to equipment I
Table 9: Effects of Fire (Thermal radiation)
1.3.1.1 Methanol Tank Fire
Methanol is stored in a bunded bulk tank. The tank diameter is 20 m and the capacity 3,805, tonnes.
It is assumed that the quantity of methanol contained in the tank is 3,600 tonnes, i.e. 3.6 x 10 kg.
In this scenario, both the fixed and floating roofs of the methanol storage tank collapse. This could be
caused by an external event or by mechanical failure. Catastrophic tank failure will result in the
complete loss of contents of the tank to the bund. The HSEIO have carried out studies to show that a
failure frequency of 2 x IO- per tank per year for large thin walled, non-pressurized tanks used for
liquid storage. The actual failure frequency is a lot less than the figure quoted by the HSE as this
calculated figure does not account for recent development in tank maintenance and inspection
procedures.
Following collapse of the roof of the tank, the contents of the tank (methanol) vapourise and disperse
with the wind.
10 Bund overtopping- the consequences following catastrophic failure of large volume Liquid storage
vessels, A. Wilkinson, SRD/ HSE R530
I
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Safety Report
Weather Conditions
Vaporisation Rate
kgls
Number:1.0.3 3 1 I1 2/05
F2
D5
Fire
If the vapours catch fire almost immediately (early ignition), the flame burns back to the tank and the
methanol burns as a pool fire, the diameter being the diameter of the tank. The hazard is thermal
radiation on the surroundings. The flames tilt with the wind.
0.3
0.45
It is assumed that 3,600 tonnes are available to burn.
Radiant Heat
(kWlm*)
The rate of vaporisation of methanol depends primarily on the wind speed. The predicted initial
vaporisation rates are:
Distance from source centre (m)
F2 D5
4
12.5
37.5
54 47
35 33
23 25
q) Flash Fi re
The furthest extent of a flash fire was calculated to be:
Table 12: Furthest Extent of a Flash Fire from
Methanol
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%, Number:i.0.3 3 1/12/05
1.3.1.1.1 Human Consequences
The human consequences resulting from a methanol tank fire were determined using data readily
available that illustrates the human effects of been exposed to heat energy. From the harm criteria
data detailed in Appendix 15 it estimates that there would be a 1 % fatality level after 30 seconds at
35m from the source. This area would include all of the methanol bund and it would reach outside the
bund wall. There is restricted access to the methanol bund at all times and the frequency of entry to
the area is very low. The effects of the fire would reach the loading bay. In the vicinity of the loading
bay there is 1 person with the load while it is loading. The loading procedure lasts for approximately
30 minutes and the operator would be in the area approximately 10 times in any one week. The bund
wall would offer some shelter from the fire, giving the person in the methanol loading area time to
leave the area.
The Canvey Report
0
0
assumes the following times to take cover from thermal radiation.
20 seconds for person outdoors to take cover from heat flux in the range of 6.5-12.6kW/m2.
Less than 1 minute for a person outdoors to take cover from heat flux in the range 4-6.5kw/m2
@
People located in regions outside this zone will have varying degrees of burns during a methanol tank
pool fire. The three types of burns are as follows.
0
0
0
Superficial Burn: This burn involves only the outermost layer of skin. Superficial burns are
characterized by redness swelling and tenderness
Partial- thickness burn: This affects the epidermis, and the skin becomes red and raw. Blisters
form over the skin due to fluid released from the damaged tissues.
Full-thickness Burn. With this type of burn, all the layers of the skin are affected; there may be
some damage to nerves, fat tissue, muscles, and blood vessels.
The vast majority of employees are indoors in the administration building each day, which is
approximately 100m from the source of the fire. Incident heat flux in the administration building would
be less than 4kW/m2.
1.3.1.1.2 Environmental Consequences
The majority of the methanol will be contained within the bund wall with minimal overtopping. During
the fire, foam units will be turned on and this will reduce the heat effects from the fire. There will be
minimal amounts of smoke as methanol is a low molecular mass molecule with only one carbon
constituent. When the fire has been controlled there will be methanol/ foam mixture to be adequately
dealt with. Since the foam will float on top of the methanol, the uncontaminated methanol underneath
can be used in the process. The contaminated portion left will be sent away for incineration. At
present there are studies taking place at Dynea to determine the feasibility of solvent recovery at the
plant at Cork. This study is at the early stages but if it is implemented this would provide a safe way to
recover the methanol. The effects of environmental impact resulting from bund failure are discussed in
the loss of containment section of the report.
@
1.3.1.1.3 Risk Reduction Measures
The original layout of the plant was designed such that the methanol storage facility had adequate
separation form other areas at the site to minimise the spread of fire to other process areas and plant
buildings. There are no permanent ignition sources in the vicinity of the tanks. The tanks including the
methanol tank at the site were built in accordance with specific standards (see section 4). Non
destructive testing is carried out on the methanol tank every 5 years. The maintenance policy as
discussed in following sections of the safety report sets out the way in which Dynea Ireland preserve
0
11 Canvey, A Second Report. A review of potential hazards from operations in the Canvey Island/
Thurrock area three years after publication of the Canvey Report, HSE 1981.
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@ Number:1.0.3 3 111 2105
the integrity of plant and equipment to specific standards such that there will be no loss of
containment or mechanical failures leading to major accident scenarios. It is planned that methanol
vapour and flame detection system will be put in place at the methanol tank bund. At time of writing of
this report Argos fire have visited site and are presently preparing a proposal to implement this
initiative. This project is due for completion in the third quarter of 2006.
1.3.1.1.4 Mitigation Measures
The mitigation measures for reducing the effects of a major fire are outlined in section 5 of the report
(Emergency Response). The above scenario would involve opening valves to the foam unit by the
cooling towers. The foam unit contains 10001trs of foam which is checked monthly to ensure
availability. When operational it will feed the foam pourers in the methanol bund. This will have the
effect of cooling the fire, and reducing the supply of oxygen to the flame and reducing vapour
pressure. During normal office hours there are more people available to carry out site tasks during an
emergency. The above operation would involve 2 trained personnel, with full PPE opening the valves
on the foam tank (if it is safe to do). This operation will take approximately 20 minutes. Outside normal
office hours there will only be three personnel available. The shift leader in this case will take
responsibility until Emergency Crew Leader arrives on site. The people resources at his disposal will
be limited. He will contact the fire brigade and other competent authorities and interested parties and
will then survey the situation. If it is safe to send two operators over to the foam tank to turn it on he
will do that, if it is safe to do so.
@
1.3.1.2 Methanol Tank Bund Fire
In this scenario, the contents of the methanol storage tank are lost to the bund. This could be caused
by an external event or by mechanical failure. The contents of the tank (methanol) vaporise and
disperse with the wind.
The bund floor area, net of the cross-sectional area of the tank, is 1,591 m2. The diameter of a circle
of this area is 45.01 m.
This scenario envisages a loss of containment of the bulk tank, so that the entire bund is flooded.
This could be caused by a tank rupture, pipe rupture, pump leak, etc.
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Number:1.0.3 3 1 I1 2/05
.-
Radiant Heat
( kWlm2)
Pool Fire
The thermal radiation levels from a pool fire were calculated to be as follows:
F2 D5
4
12.5
37.5
104 96
67 66
43 49
dl
I 42 I 56 I
Methanol Bund
1.3. I. 2.1 Human Consequences
The worst case scenario would be a pool fire, which would extend 66m under D5 weather conditions.
This fire would extend to the car park and would cover the area of the methanol loading area. From
the data outlined on Appendix 15, there would be a 1 % fatality level at 67m from the source after 30
seconds. There is restricted access to the methanol bund at all times and the frequency of entry to the
area is very low. In the vicinity of the loading bay there is 1 person with the load while it is loading as
discussed previously. The bund wall would offer some shelter from the fire, giving the person in the
methanol loading area time to leave the area. At present the car park is situated in front of Basin 1.
The majority of employees work in the administration building each day. Incident heat flux in the
administration building would be less than 4kW/m2 and is not expected to present a major hazard.
e
As in section 1.3.1.1.2
As in section 1.3.1.1.3. As part of the budget in 2006 the car parking area will be moved to the eastern
side of the plant, well away from the dangerous substance storage facilities.
I. 3.1.2.4 Mitigation Measures
As in section 1.3.1.1.4
1.3.1.3 Methanol Tanker Loading Bay Fire 0
In this scenario, the contents of a road tanker (19.2 tonnes) are lost to the bund. This could be caused
by rupture of a hose or pipe joint. Methanol would spill into the contained area and drain to the
underground sump from which it is automatically pumped to the methanol tank bund. It is assumed
@
\I (
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0 Number:1.0.3 3 1 / I 2/ 05
that the contained area is 200 m2. The diameter of a circle of this area is 15.96m. The contents of
the tank (methanol) vapourise and disperse with the wind.
Pool Fire
The thermal radiation levels were calculated to be as follows:
I 12.5 I 25 I 24 I
I 37.5 I 17 I 18 I
Table 15: Thermal Radiation Levels from Pool Fire in Methanol Tanker
Loading Area
Flash Fire
Table 16: Furthest Extent of a Flash Fire in
Methanol Tanker Loading Area
1.3.1.3. I Human Consequences
The worst case scenario would be a fire, which would extend 24m under D5 weather conditions.
There would be a 1% fatality level at 24m from the source after 30 seconds. This fire would extend
inside the methanol tank bund wall. In the vicinity of the loading bay there is 1 person with the load
while it is loading. This person would be within 25m of the loading bay. The loading procedure lasts
for approximately 30 minutes and the operator would be in the area approximately 10 times in any
one week. This equates to approximately 3% of the working week that this person will be in the
vicinity of the loading bay.
0
, ' I j i
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I
I. 3.1.3.2 Environmental Measures
The environmental consequences of a methanol loading bay fire would be minor, as the volumes that
are involved are relatively small. The bund will contain the majority of the load, however there will be
overtopping. This overtopping will result in methanol spilling on to the gravel area by the methanol
loading area bund wall. This methanol will seep into the soil (The degradation processes etc. of
methanol in soil/ water is discussed in section 1.3.5). There will be foam pumped on the fire from 3
monitors in the loading bay area. When the fire is quenched this foam/methanol mix will be placed in
ex rated IBC's and disposed of as per the regulations.
Safety Report
9 Number:1.0.3 3 1 I1 2/05
1.3.1.3.3 Risk control measures
The loading bay is positioned away from areas of high employee density. All plant personnel involved
in loading and unloading methanol have been trained to do so. All the operators have many years'
experience. During the loading process the operator remains with the load while loading/ unloading
takes place. All tankers on site are inspected by DGSA (Dangerous Goods Safety Advisor) to ensure
they are suitable for the purpose. Certification for tankers must be provided from haulier prior to
loading. There is a tanker earthing system in place, which means that pumps will not start if a correct
earthing connection is not made. A green light is shown on the display when a correct earth
connection has been made. This eliminates the effects of static electricity. The pipe coupling to the
tanker is a "Dry Link" coupling, which ensures liquid tight connection between hose and road tanker
connection. The hose is armoured, thus preventing accidental damage. Footwear of people in the
area is checked regularly to ensure that they are not capable of carrying any charge.
There is signage on entry into the loading area that all sources of ignition (mobile phones etc.) are
prohibited in the area. The only source of ignition within the methanol-loading bay is the truck unit
itself. All trucks must be certified for carrying flammable materials and must provide this evidence. All
truck drivers receive site induction training and must provide evidence that they are Haz Chem.
trained prior to distributing loads of methanol to customers.
Dynea have invested in a Deluge system at the methanol loading area. At present it is a manual
system whereby one person can go over to the fire water valve, opens it from a safe distance. This
will spray the whole loading bay with foam/water. This process takes approximately 20mins. If
resources allow there are mobile foam monitors which can be used at a safe distance.
1.3.1.4 Methanol Ship Line Fire
(A fire in the ship carrying methanol is outside the scope of the site, and is therefore not included in
this assessment.)
In this scenario, the pipeline carrying methanol from the ship to the bulk tank is ruptured, and pours on
to the ground. In this analysis, it was assumed that the rupture takes place approximately half way
between the jetty and the methanol tank, i.e. on the IF1 site. Over most of its route, the methanol
pipeline is out of reach of vehicle impact - being behind buildings or on high pipe racks. In the areas
where it is most exposed it is one of the middle pipes on the rack with outer pipes protecting it. On the
most exposed side there are two major pipelines outside it, one of these being the fire ring main - a
major impact on this side would, therefore, also take out the ring main and very large quantities of
water would pour onto the spillage, lowering the vapour pressure and all but negating the likelihood of
ignition. On the other side there is a narrow roadway beside the pipeline which would not reasonably
allow a vehicle to turn into the pipe rack with the impact necessary to go through the outer pipe and
into the methanol line.
The assumed pumping rate is 350 m3/hr, i.e. 280 tonneslhr or 77.8 kg/s. It is assumed that this
continues indefinitely. The model does not allow for leaks of limited duration. It is however expected
that the leak would be detected and the pump stopped within 20 minutes based on differentials
between the ship and tank volumes. 20 minute isolation time is based on site personnel having to
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Radiant Heat
(kW/m2)
advise ships captain to stop pumps and that Dynea personnel to close valves at the methanol tank
and from plant experience this time is very conservative.
The liquid methanol continues to spread around the source of the leak until the rate of vaporisation
equals the rate of leakage. That is a steady-state condition. There is no containment.
The contents of the tank (methanol) vaporise and disperse with the wind.
Pool Fi re
The thermal radiation levels were calculated to be as follows:
F2 D5
4
12.5
37.5
378 375
245 259
160 187
Flash Fire
FZ DS
I 96
102
Methanol Ship Line
I . 3. I . 4.1
Presently IF1 is being dismantled and as of yet information as regards the new owners is not known.
The methanol fire resulting from pipe rupture will encapsulate a wide area. The worst case scenario is
that the heat wilhadiate as far as 259m. There would be a 1%fatality level after 30 seconds.
Human Consequences
Due to the fact this is an uncontained spillage there will vast quantities of methanol seepage into the
soil. When released into the soil, methanol is expected to readily biodegrade, based on the results of
a large number of biological screening studies. Further discussion on the environmental
consequences will be discussed in the loss of containment section 1.3.3.
I . 3.1.4.3 Risk Control Measures
The methanol pipe from the jetty is pressure tested every 5 years to ensure pipe integrity. The
methanol line is a continuous welded pipe. As part of the ship unloading procedure prior to the ships
arrival the shift supervisor will walk the line and carry out a visual check on the line every 4 hours.
When the ship arrives the ships captain is given a Dynea radio which allows him communication
between the jetty and Dynea control room which allows for quick action in the case of a major
accident scenario. During the unloading process there are levels taken in the control room which are
compared to ships pumping rates. Any major deviations, the ships pump will be stopped and valves at
%,
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Number:1.0.3 3 111 2/05
Overpressure
(barG)
dynea
Overpressure Effect
(psig)
methanol tank closed and an investigation carried out. Any deviations would be noticed within 20
minutes which would result in approximately 100 cubic meters of methanol available to the fire.
0.3
2
3
Dynea have 2 employees manning the jetty at all times and who are communication with Dynea
control room and the ships captain. During this emergency the shift leader will communicate with
ships captain to stop ships pumps. He will push emergency stop button on the jetty and this will shut
off methanol line valves. The captain will mobilize his crew to remove the ship off the jetty. The shift
leader will then communicate to Dynea control to close valves at the methanol tank. This operation
will take approximately 30mins. The Emergency Crew Leader will notify the relevant authorities and
will mobilize a crew to start foam units to reduce the effects of the fire, if it is safe to so. This
operation will take approximately 30mins.
Safe distance@ (probability 0.95 no
serious damage beyond this value);
projectile limit; some damage to house
ceilings; 10% window glass broken
Partial collapse of walls and roofs of
houses
Heavy machines (3,000 Ib) in
industrial building suffered little
damage; steel frame building distorted
and pulled away from foundations
1.3.2 Explosions
The following three blast overpressure levels are normally chosen to cover a range of effects of
explosion:
@
0.0207
0.14
0.21
Table 19: Effects of
A vapour cloud explosion may be defined as an explosion occurring outdoors, producing a damaging
overpressure. In a vapour cloud explosion, a volatile liquid vaporises, and the cloud of vapour travels
with the wind, dispersing and diluting as it moves.
If ignition does not take place until a large cloud of vapour has been generated overpressure is
developed, with consequent damage to structures and either direct injury or, more likely, indirect injury
to persons caused by projectiles or building (late ignition), a vapour cloud explosion takes place.
The intensity of the explosion depends on the degree of confinement of the explosion. Most releases
of vapour clouds take place in or near buildings and other structures, and so are partially confined.
Further, the cloud will not be of a uniform shape, or at a uniform composition. All of these
uncertainties make it necessary to generalise, and the fraction of the heat of combustion in an
explosion that appears as energy in the shock wave has often been estimated based on observations
of incidents and experiments, particularly stemming from military sources.
This fraction is given by the yield, Q. q is the product of two independent yield factors qC and Q,,,, as
follows:
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~ 8 Number:1.0.3 3 1 / I 2/05
qc is the yield factor due to the non-stoichiometry of a cloud with a continuous development of fuel
concentration in the explosive part of the cloud; qc is approximately 30%.
qm is the mechanical yield of the combustion. Approximate values of qm are as follows:
-
Total confinement: qm . 100%
lsochoric combustion: qm 33%
Isobaric combustion: qm 18%
-
I
The value of qm also depends slightly on the type of gas.
-
Where a gas cloud explosion occurs there is probably some form of confinement, and hence qm 33%,
and t j 10%.
If there is no confinement, then qm 18%, and 6 5%.
In the case of total confinement, qm loo%, but total confinement means no rupture. If there is rupture
of the vessel, then this is similar to a partially confined vapour cloud explosion, and qm 33%.
0
-
Four cases are assessed:
0
0
0
0
Vapour cloud released when roof of Methanol Tank collapses
Vapour cloud released when Methanol Tank leaks to bund
Vapour cloud released when road tanker spills
Vapour cloud released when ship line ruptures
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Weather Conditions F2
Number:1.0.3 3 1 I1 2/05
D5
-
1.3.2.1
In this scenario, both the fixed and floating roofs of the methanol storage tank collapse. This could be
caused by an external event or by mechanical failure. Following collapse of the roof of the tank, the
contents of the tank (methanol) vapourise and disperse with the wind.
Vapour Cl oud Explosion from Vapours released from Methanol Tank
. - I
Overpressure
(barG)
The explosion effects from late ignition were calculated to be:
I
I
I
163,700
I 1049100
Mass of methanol
involved in explosion [ka) I
I 0.0207 I 1,187 I 1,316 I
0.14 I 32 1 I 35 1 I
I 0.21 I 252 I 275 I
Table 20: Explosion Effects from Late Ignition from Vapours Released from
Methanol Tank
The human consequences due to an explosion can be divided into two categories:
0
0
Direct effects: pressure change caused by the blast can cause injury to sensitive human organs,
such as lungs and ears.
Indirect effects: Injury due to impact by fragments and debris originating from the explosion. Injury
may also arise due to persons or objects being thrown by the blast wave.
The worst case scenario would be a blast overpressure of 0.14barG at 351m from the source. The
effects from the blast overpressures would be sufficiently high to cause damage to buildings at the
site. The blast overpressure would not impact on the residences in the locality. The main areas of
employee population density are in the administration building. This building has a precast concrete
frame which would remain intact after explosion which will give some protection to employees.
Employees who are working outside within the radius of the explosion are likely to suffer very serious
injuries from the explosion.
@
The environmental consequences of a vapour explosion will be minor as the explosion will be of short
duration. There will no emission to ground or water thus preventing potential pollution. There is little
vegetation around the plant so scorching is unlikely to occur.
The methanol tank undergoes non-destructive testing once every five years. This process will show
up any defects with the tank. The tank itself is built to a recognised standard, which will be discussed
further in the technical section of the Safety Report. It is planned in the third quarter of 2006 to install
methanol vapour detection in the methanol bund.
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N um ber: 1.0.3 3 1/12/05
0
Weather Conditions F2
I
D5
dynea
. -,
Overpressure
(barG)
1.3.2.2
by an external event or by mechanical failure. The contents of the tank (methanol) vapourise and
Vapour Cloud Explosion from Vapours released to Bund from Methanol Tank
I
I
0.0207
0.14
0.21
368 82
114 51
93 48
Mass of methanol 2,620 4.9
I
involved in exdosion (ka) I
Table 21 : Explosion Effects from Vapours from Methanol Released to Bund
1.3.2.2.1 Human Consequences .
The worst case scenario would be a blast overpressure of 0.14barG at 114m from the source. The
consequences from the blast overpressure would result in personnel injury and building damage. The
effects from the blast overpressures would not be sufficiently high to cause any damage to windows at
any of the residences in the locality. The main areas of employee population density are in the
administration building. This building has a precast concrete frame which would remain intact after
explosion which will give some protection to employees.
@
See section 1.3.1.2.2
I . 3.2.2.3 Risk Reduction Measures
See section 1.3.2.1.3
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1
Weather Conditions
Safety Report
F2 D5
I
I
Mass of methanol
involved in explosion (kg)
dynea
4 43
N urn ber: 1.0.3 3 1112105
Overpressure
(barG)
1.3.2.3 Vapour Cloud Explosion from Vapours released from Road Tanker
I
I
In this scenario, the contents of a road tanker (19.2 tonnes) are lost to the contained area. This could
be caused by rupture of a hose or pipe joint. Methanol would spill into the contained area and drain to
the underground sump from which it is automatically pumped to the methanol tank bund. It is
assumed that the contained area is 200 m2. The diameter of a circle of this area is 15.96 m. The
contents of the tank (methanol) vaporise and disperse with the wind.
0.0207
0.14
0.21
54 99
26 35
23 30
I . 3,2.3. I Human Consequences
The worst case scenario will revolve around a 35m radius of the loading bay area. This area is only
occupied when a tanker is being loaded. This operation lasts approximately a half an hour, and occurs
approximately 10 times a week. While the tanker is loading the operator remains with the load so if
there is an explosion, they will be within the 35m zone. The result of the explosion would be 100%
fatality to operators at the loading bay and some distortion of the loading bay. The galvanized roof on
the loading bay will be blown off. Residents in the locality will not be affected by overpressure. The
administration building at the plant will not be affected by the blast overpressure.
See Section 1.3.1.3.2
All production personnel have been trained on methanol loading. The detail for methanol loading is
contained in the methanol loading procedure (3.5.50 Methanol loading procedure). All equipment in
the loading bay is Ex rated. All methanol pipelines have earthing straps across the flanges to reduce
effect of potential difference arising from a flowing liquid. There is signage on entry to the bay that
ignition sources are forbidden in the bay. The designated Methanol tankers arriving on site are
checked prior to loading for any damage to hatches and connection pieces. All drivers taking
methanol off site are site inducted and must have a HAZ Chem license and provide proof of this, each
time they take methanol from the site. The Dangerous Goods Safety Advisor (DGSA) checks each
new tanker arriving on site and receives its certificate of conformance. The DGSA determines the
maximum/ minimum loading capacities of the tanker using the ADR guidelines.
I . 3.2.3.4 Mitigation
The loading bay is positioned away from areas of high employee density. In the event of an explosion
in the methanol loading the deluge system can be manually operated. The response times etc. are
@
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dynea
-
Number:l.O.3 3 1/12/05
similar to detail described in section 1.3.1.3. This system can be started from a remote location to
reduce any further effects from the explosion. The mobile foam unit can be brought to the area and
connected to the fire hydrants and can then pump foam from a remote location. As part of the budget
in 2006 it is planned to have remote activated deluge system in place at the loading bay. The deluge
system is currently in place; however the wiring to the actuated valve is to be completed. This will be
I
completed in the first quarter of 2006.
I
I
!
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Number:1.0.3 3 1/12/05
Blast Overpressure (mbar) Pressure (bar)
1.3.2.4 Reactor Headspace Explosion
Distance from
source centre (m)
Flammable and explosive vapours are not normally present in the headspace of reaction vessels in
normal operation, because the concentration is below the lower flammable limit, 6%. The vessel is
earthed to prevent accumulation of static electricity.
However, the worst case is an explosion involving 70 kg of methanol/formaldehyde vapour. Assuming
a 50/50 mixture of methanol and formaldehyde, the distances to blast overpressures are as follows:
Damage Level 1 (heavy damage to buildings and
to process equipment)
Damage Level 2 (repairable damage to building
and facade damage to dwellings)
Damage Level 3 (glass damage causing injury)
0.36 14
0.18 26
0.03 71
The design pressure of the vessel is 3 barG. Two bursting disks, rated at 1 barG and 1.5 barG
provide pressure relief.
A reactor head space explosion would result in serious injury/ death of personnel working around the
reactors and in the control room if the bursting disks were to fail. There would be a maximum of 5
people in this area during day work and 3 during night shifts and weekends. Considerable ongoing
work has been taking place to thoroughly evaluate the risk. Dynea and competitor companies have
been operating the reactors in this fashion for over 50 years. Analysis of the design and build
specifications of the reactor and the DIERS calculations for the bursting disks shows that the system
has been designed to fully vent such an explosion and that an overpressure will not occur.
1.3.2.5 Environmental Consequences
0
If the vessel is not significantly damaged, the contents of the reactor can be reworked. In the worst
case scenario where the reactor vessel ruptures there will be 34tonnes of a formalin/ methanol
mixture to be dealt with. Some of the mixture will be contained within the reactor bund wall which can
be placed in IBCs and reworked. There will be overtopping of the bund wall, and the reactor contents
will end up in the process drains and finally in Basin 1. This substance will be contained in Basin 1
and the Basin will be quarantined. Some of the solution may end up on the grass area by the reactors.
The degradation processes for the formaldehyde in soil/ water are discussed in 1.3.5.
The bursting discs relieve pressure build-up in the reactor and because of this they are classified as
safety critical. These bursting discs are on maintenance schedule and are changed at regular
intervals. The reactors are built to a specific standard (See technical section). The agitator is also on a
maintenance schedule so that seals around the shaft are in good condition reducing the risk of sparks
resulting in an explosion.
During the above scenario, foam canons on the reactor ground floor will be used to reduce the toxic
effects of the spillage. Some of the reactor contents will be contained within the reactor bund wall.
This liquid in the bund can be pumped into IBCs and reworked. Foam will be sprayed into Basin 1 to
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I
I
dynea
,
reduce the toxic effect. Water will also be pumped into the Basin 1 to dilute the mixture. The liquid in
the basin can be reworked by pumping it to the distillate tank, and from there it can be used in the
absorber tower.
@
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q) Number:1.0.3 3 111 2/05
Blast Overpressure (m bar)
1.3.2.6 Methanol Tank Explosion
This scenario envisages that the methanol tank contains no liquid, but is full of methanol vapour, i.e.
the inner roof is at the top of its travel. If concentration of methanol vapour is between the upper and
lower explosive limits, and a source of ignition is introduced, the vapour/air mixture will explode.
The volume of Tank 4500 m3. At the LEL (6%), the volume of methanol vapour is 300 m3. At the UEL
(36.5%), the volume of methanol vapour is 1825 m3.
Pressure (bar) Distance from
source centre (m)
The density of Methanol Vapour at NTP is 2.55 kg/m3. The mass of methanol at the LEL is 765 kg.
The mass of methanol at the UEL is 4,651 kg.
Damage Level 1 (heavy damage to buildings and
to process equipment)
Damage Level 2 (repairable damage to building
and facade damage to dwellings)
Damage Level 3 (glass damage causing injury)
The worst case was taken, i.e. all vapour at the UEL.
0.36 53
0.18 105
0.03 263
If an explosion were to occur, involving the entire tank volume at the upper explosive limit, the
distances to blast overpressures would be as follows:
ID
A methanol tank explosion would result in serious injury/ death within 105 meters of the tank. It would
also cause severe damage to buildings in that area. It would encapsulate the methanol loading area
which may escalate the incident. Access to the methanol bund is on a restricted basis only.
There may be operators in the vicinity of the bund, during the loading of methanol to road tankers at
the methanol loading area. The administration building and occupants would experience level 2
damage (see table above). Residents in the locality may experience damage to windows
@
After an explosion of this magnitude there would be probable damage to the bund wall. Since this
scenario deals with a vapour and an empty methanol tank there will be no environmental damage
There is non destructive testing of the methanol tank every 5 years. The tank itself is built to a
recognised standard. There is a pressure relief valve on top of the tank and a flame arrester. The
pressure rating etc. of this equipment will be discussed in the technical section of the report. This
equipment is on a maintenance schedule and is maintained at regular intervals. There is a constant
feed of Nitrogen to the methanol tank, which will prevent ignition. There are two sources of Nitrogen,
the Nitrogen compressor, and Nitrogen bottles for instances when Nitrogen compressor is being
maintained. It is planned to have vapour detection in place in 2006.
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1.3.3 Loss of Containment
1.3.3.1 Formaldehyde Gas Cloud
A cloud of formaldehyde gas could be released in the event of:
Formalin Tank Rupture
Failure of the Catalytic Converter
Opening of the Pressure Relief Valve and failure of all Absorber pumps
1.3.3.2 Formalin Tank Rupture
Formalin is a solution of formaldehyde in water. At Dynea, formalin is produced as an aqueous
solution of strength 55%, and diluted to 50%. The solution is stored at a temperature of up to 6OoC,
normally about 50C to prevent the formation of polymers, i.e. Para formaldehyde.
The vapour pressure of formaldehyde gas over a 50% aqueous solution at 4OoC is extremely low - 5
mm Hg (0.066 atm). At this pressure, a formalin solution would not give off a vapour whose
concentration of formaldehyde is above the flammable limit.
@
In the event of rupture of a formalin tank, the liquid would be released into the bund and evaporate.
The rate of evaporation depends primarily on the wind velocity, but also on the temperature of the
surface under the pool.
There are two formalin tanks. Each is 8 m in diameter, 6 m high, and has a volume of 300 m3. The
density of the formalin is1 kg/m; i.e. total contents are 151 tonnes of formaldehyde.
The bund dimensions are 56.5 m x 31.4 m. After allowing for the area taken up by the tank and pump
a base, the floor area is 1,160 m2, so the equivalent diameter of the bund is 38 m.
The initial rate of evaporation of formaldehyde from 50% wlw formalin at 30C was calculated to be:
Initial Rate of Evaporation (kg/s) for wind
speed
I 0.012 I 0.030 I
Table 25: Initial Rate of Vaporisation from 50%
Formalin at 30C
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NumberA.O.3 3 111 2/05
The dispersion of formaldehyde gas under various combinations of wind speed and atmospheric
stability was predicted to be as follows:
10
Basis Averaging Distance from source centre
Time to Concentration (m)
F2 D5
(SI
256 I 99 I
US EPA Immediate
Danger Level
NIOSH IDLH I 3,600 I 432 I 148 I
AlHA ERPG-2 3,600 642 203
1,800 691 216
(evacuate)
I 900 I 750 I 231 I
I 10 I 783 I 240 I
Table 26: Dispersion of Formaldehyde under Various Combinations of Wind Speed and
Atmospheric Stability
I . 3.3.2. I Human Consequences
The effects from a formalin spillage (50% Formaldehyde) from a formalin tank (T402, T403) will be
experienced by personnel and members of the general public in the vicinity of the plant. There is an
immediate danger to life and health within 432m of the site. Formaldehyde poisoning is a disorder
brought about by breathing the fumes of formaldehyde. The major symptoms may include eye, nose,
and throat irritation; headaches; and/or skin rashes. Formaldehyde has a distinctive smell and would
be noticed immediately. Dynea personnel would don breathing apparatus.
The tanks are constructed to recognised standards (See technical section of safety report). Both
these tanks undergo non destructive testing to ensure tank integrity. The tank is surrounded by a
bund wall which will contain some of the spill. There are level transmitters on the tank which alarm in
the control room at high and low levels, which will allow for, immediate action in the case of an
emergency. The legislation (SI 476of 2000) requires that information is to be provided to the general
public regarding Seveso 2 sites. An information pack has been developed and has been distributed
to the general public illustrating the actions to be taken in the event of a major formalin leak.
I . 3.3.2.3 Environmental Consequences
Loss of containment of formalin would require:
(a)
(b)
Loss of contents of a formalin tank to bund and leakage from bund
Loss of contents of more than one formalin tank to the bund
In the event of loss of contents of a formalin tank to bund and leakage from bund, formalin solution
would be released to the surrounding area.
If the leak was to the hard standing in the yard, the formalin would enter the drainage system,
which would be discharged to the retention basin.
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0 If the leak was to under the hard standing, or to ground beneath the bund, formalin could
seep into the ground. In this case, formalin would drain to the groundwater.
The EPA Report Measurement and Modelling of Nutrient Dynamics of Two Estuaries in Ireland -
Wexford and Cork Harbours - Synthesis Report (2001) gives the following information on Cork
Harbour:
Characteristic Value
I Estuary area (ha) I 8,585
I Estuary length (km) I 17.72
Maximum width (km) 6.14
Width at mouth (km) 1.65
Main channel width at mouth (km) 1.65
Maximum depth (m) 28
Maximum depth at mouth (m) 28
I Freshwater catchment area (ha) 1 186,000
I Annualised catchment rainfall (mm) I 830
I Annual freshwater inputs (m3/s) I 41
180,000
Volume (m3) 642 x l o6
Ration of prism to volume 0.10
Tabl e 27: EPA Report Information on Cork Harbour
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Number:1.0.3 3 1/ 12/ 05
Figure 4 in the EPA report shows that the main channel is well-defined and narrow, and between 10
and 20 m deep from Marino Point to the mouth of the harbour.
Figures 15, 16, 17 and 18 in the EPA report show the vector plots of current velocities in Cork
Harbour during different stages of spring tides (high water, mid-ebb, low water and mid-flood). These
show that the direction of flow at Marino Point reverses on the flood tide.
If there was an uncontained total loss of containment of a formalin storage tank, the rate of discharge
of formalin to the harbour would be slow, as the liquid would have to seep through the ground and
travel along the saline water surface. Hence, there is no credible risk of water supplies being
contaminated.
In the case of loss of containment of storage tanks, the total quantity is very small in relation to the
total capacity of the Harbour.
0
The BOD load released in the event of loss of containment of a tank of formalin would be
110,000 kg. This is equivalent to over three times the daily assimilative capacity of Cork
Harbour at Marino Point, and one third of the daily assimilative capacity at the Rams Head
Bank
The average concentration in the tidal prism volume would be 1.725 mg/l. This concentration
is well below the toxicity levels for rainbow trout, but comparable to the levels for other aquatic
organisms.
t.dwever, the above is the worst case situation. In reality, some formalin would be retained in the tank
farm, and the portion released would take some time to seep through the ground, or over the surface.
Further, the scouring action of the tide, and the assimilative capacity would reduce the impact.
On the other hand, the concentration would not be uniform throughout the harbour, and local
concentrations would be higher.
The impact would depend on the stage of the tide. One could infer from the vector diagrams that
most of the formalin would be swept out to sea with the main current, although some would spread to
either side of the main channel, where there are larger areas of shallower water.
All of this assumes that the bunding is ineffective, and this is unlikely as integrity testing has been
@ carried out.
I . 3.3.2.4 Mitigation
The pfnd is designed to offer secondary containment during a tank rupture. It has been shown by the
HSE that bunds may not be able to cope with a catastrophic failure of the tank and the sudden
release of a large volume of liquid. The HSE report identifies a number of potential scenarios:
0
0
0
Bund overtopping: The momentum of the liquid causes a proportion of the tank contents to flow
over the top of the bund
Bund collapse: The forces exerted on the wall may cause bund collapse
Collapse of bund following collision with tank debris. There would be a force in the opposite
direction to liquid flow following catastrophic failure of the tank which could propel the tank (much
lighter than contents) towards the bund wall.
The resin bund height is lower than the tank height, so the most likely event is overtopping of the
bund wall. Another study carried out by the HSE illustrates that the amount of overtopping was
largely dependent on height of liquid in the tank and the bund height.
12Effects of secondary containment on source term modelling, WS Atkins Consultants Ltd, Contract
Research Report 324/2001, prepared for the HSE, UK.
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0 Number:1.0.3 3 111 2105
I
dynea
The quantity lost to overtopping can be calculated .The quantity overtopped is calculated to be
approximately 70%.
The means that 70% of the tank will overtop the bund wall equating to 210 cubic meters of formalin
assuming tank is full. (The above calculation is simplistic in that it concludes that a bund capable of
containing 700% of tanks contents needs to be the same height as the tank). This liquid will be
retained in Basin 1 through the rainwater drainage system. 90 cubic meters formaldehyde solution
will be contained within the bund. The formalin that is left in the ruptured tank will be pumped into the
other formalin tank (T402lT403). Operators with full breathing apparatus will spray foam on the
formalin on the road way in front of tank farm to reduce vapours and toxic effects of formalin. The
formalin in the bund can be pumped into IBCS and used in the process. Foam will also be pumped
into Basin 1 to reduce effects of vapour
I
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Component
I
% wl w
dynea
concentration
(PPm)
-
Number:l.O.3 3 1/12/05
Basis Averaging Distance from source centre
Time to Concentration (m)
F2 D5
(SI
I
1.3.3.3 Failure of Catalytic Converter
50
20
10
In the event of failure of the catalytic converter, all the gases would be discharged through the
converter stack for up to one hour.
US EPA Immediate 3,600 6.4 8.1
Danger Level
NIOSH IDLH 3,600 20 13
AlHA ERPG-2 3,600 28 17
1,800 29 18
900 30 20
10 31 22
(evacuate)
Following modifications to the absorber tower carried out as part of the emissions reduciion
programme in 2001, the concentration of formaldehyde has been reduced from 1,25Omg/m to
240mg/m3. With a gas flow rate of 8,000 m3/hr, this is equivalent to a discharge of 1.920 kglh;
(0.00053 kg/s). However, in an attempt to model worst case scenarios, the older figure of 1,25Omg/m
was use as an input to the modelling software.
The gas has the following composition:
I Nitrogen I 89 I
I Oxygen I 6 I
I Watervapour I 5 I
1 Formaldehyde I 0.1 I
Table 28: Composition of Exit Gas from Catalytic
Converter
The diameter of the stack is 400 mm, and therefore the efflux velocity is 17.68 m/s.
This scenario was modelled using PHASTMicro and ISCST3.
With PHASTMicro, the dispersion of formaldehyde gas under various combinations of wind speed
and atmospheric stability was predicted to be as follows:
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@ Number:l.O.3 3 Ill 2105
Conditions of Wind Speed and Atmospheric Stability
e
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@ Number:1.0.3 3 1 / I 2/ 05
Weather Maximum
Condition Concentration of
Formaldehyde (ppm)
With ISCST3, the following results are obtained:
Using 1989 Roches Point meteorological data, the highest I-hour average ground level concentration
(GLC) predicted was 973 pg/m3 (0.8 ppm) at receptor 77800, 69500, a distance of 440 m from the
stack.
Distance downwind
of Source (m)
The maximum concentrations reached, and the distance from the source for weather conditions D5
and F2 were predicted to be as follows:
I D5 I 0.015 I 150 I
r-7 I 0.26 I 150 I
~
Table 30: Maximum Formaldeyde Concentrations and Distance from
Source for Conditions D5 and F2 after Catalytic Converter Release
ISCST3 is more optimistic than PHASTMicro, and predicts lower concentrations of formaldehyde.
The modelling predicts that effects from the above scenario will not affect the residents in the locality.
The ILDH value occurs at 20 meters from the source. Due to the smell of the gas all employees
outside will have time to enter the main building and use the breathing apparatus provided. The
normal wind direction is south-westerly, which would mean the plume of formaldehyde gas would be
directed away from the plant and away from immediate locality.
The environment at risk from such a release includes:
0 Flora
0 Fauna
Formaldehyde gas could lead to distress among birds flying into the plume, but the plume is relatively
narrow, short-lived in duration and disperses to low concentrations quite quickly. The risk to birds is
further reduced as birds can much take evasive action more easily than humans, as they can move in
three directions, whereas humans can only move in two directions. High level formaldehyde could
affect high vegetation, i.e. tall trees.
Formaldehyde gas at low elevation, i.e. when the plume descends to ground level, could cause
distress among earth-bound fauna and low level vegetation. The only incident that could give rise to
high ground level concentrations is a spill of formalin to the bund. This has been discussed earlier in
this report.
The plant equipment is built to recognized standards. The location of the equipment is at the northern
end of the site where employee traffic in this area is quite low. As part of Dynea IPC License there are
continuous air emissions analysers in place and air sampling is carried out twice monthly, both of
these systems will show up any issues with regard to functioning of the catalytic converter.
Page 48 of 65
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Number:l.O.3 3 111 2/ 05
Component
dynea
kglhr
1.3.3.4 Opening of the Pressure Relief Valve and failure of all Absorber pumps
In the event of opening of the Pressure Relief Valve on the Absorber outlet, and coincident failure of
all Absorber pumps, it is estimated that 1 tonne of formaldehyde could be discharged over half an
hour.
I
1
t
The gas stream has the following composition:
I Nitrogen I 30,316 I
r- ~ Oxygen I 2,687 I
I
~~
T W a t e r Vapour 1 2,773
I 43 I
~~
r Methanol
I 552 I
Formic Acid
Dimethylether
Formaldehyde 2,891
Table 31: Absorber Gas Stream Concentration
The concentration of formaldehyde is 7.33%.
The diameter of the PRV discharge vent is 450 mm, and the density of the gas is 0.78 kg/m3
(temperature 16OoC) and therefore the efflux velocity is 88 m/s.
This scenario was modelled using PHASTMicro and ISCST3.
With PHASTMicro, the dispersion of formaldehyde gas under various combinations of wind speed
and atmospheric stability was predicted to be as follows:
l j
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Concentration Basis Averaging
Time
(SI
(PPm)
Document
Number:l.O.3
Distance from source centre
to Concentration (m)
F2 D5
Revision: Issue Date:
3 111 2/05
US EPA Immediate
Danger Level
NIOSH IDLH
3,600 2.0 2.5
3,600 8 11
~~ ~
AlHA ERPG-2
(evacuate)
3,600 23 29
1,800 23 29
900 23 29
10 23 29
Table 32: Dispersion of Formaldehyde Gas from Absorber under Various Conditions of
Wind Speed and Atmospheric Stability
Weather Maximum
Condition Concentration of
Formaldehyde (ppm)
With ISCST3, the following results are obtained:
Distance downwind
of Source (m)
Using 1989 Roche's Point meteorological data, the highest 1 -hour average ground level concentration
(GLC) predicted was 26,564 pg/m3 (22 ppm) at receptor 77750, 69450, a distance of 440 m from the
stack.
05
F2
The maximum concentrations reached, and the distance from -the source for weather conditions D5
and F2 were predicted to be as follows:
4.7 350
1.5 2,000
Table 33: Table 39: Maximum Formaldehyde Concentrations and
Distance from Source for Conditions D5 and F2 after Absorber
Release
ISCST3 is more optimistic than PHASTMicro, and predicts lower concentrations of formaldehyde.
Both modes predict that unsafe concentrations will not occur outside the site.
The consequences human and environmental are similar to 0.
1.3.3.5 Methanol Vapour Cloud
A methanol vapour cloud could be generated from a pool of methanol liquid:
0 Methanol tank rupture
0
0
Methanol road tanker loading spill
Methanol ship offloading - spillage to land
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Number:1.0.3 3 1/12/05
1.36
1.3.3.6 Methanol Tank Rupture
by an external event or by mechanical failure. The contents of the tank (methanol) vaporise and
I
2.03
The initial rate of evaporation of methanol was calculated as follows:
Averaging Time
Concentration (ppm) (SI
Rate of Evaporation (kgls)
Distance from source centre to
Concentration (m)
F2 D5
25,000 (IDLH)
250 (OEL-STEL)
The dispersion of methanol vapour under various combinations of wind speed and atmospheric
3600 97 78
900 260 102
There is an immediate danger to life and health within 97m of the vapour source. There will be
production personnel working near the methanol loading area and the urea store which are within the
97m of the methanol source. People in the vicinity of methanol vapour will experience intoxicating
effects as Methanol is an alcohol. Methanol will be quickly absorbed through the skin and by
inhalation. The liver will metabolise the methanol to formaldehyde and formic acid which will be
removed from the body. Methanol is a hydrophilic compound and will locate itself to areas of high
water concentration usually the eyes. This can result in eye damage. Methanol has the characteristic
smell of alcohol which will alert people outdoors to move indoors. This incident will have no impact on
local residents.
The environmental consequences from a large spill in the methanol bund will be contained within the
bund. Adding foam to the bund will reduce the vapour pressure of the liquid and reduce toxic effects.
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The bulk storage tank holds 3,600 tonnes of methanol, and is totally bunded to 110% of the tank
capacity. It is only in the event of tank rupture, and at the same time leakage from the bund, or
rupture of the bund, that liquid methanol would be released to the environment.
In the event of leakage or rupture of the bund, methanol would be released to the surrounding area,
and would seep into the ground, or overflow to Cork Harbour. Methanol seeping into the ground
would rapidly reach the water table, and then slowly seep into Cork Harbour.
0
The BOD load released in the event of loss of containment of the methanol bulk tank would
be 4,104T. This is many times the daily assimilative capacity of Cork Harbour at Marino
Point.
0
The average concentration in the tidal prism volume would be 36 mg/l. This concentration is
well below the toxicity levels shown.
However, the above is the worst case situation. In reality, some methanol would be retained in the
tank and tank bund, and the portion released would take some time to seep through the ground, or
over the surface. Further, the scouring action of the tide, and the assimilative capacity would reduce
the impact.
On the other hand, the concentration would not be uniform throughout the harbour, and local
concentrations would be higher.
As discussed earlier (formalin spill), if there was an uncontained total loss of containment of the
methanol storage tank, the impact would depend on the stage of the tide. Most of the methanol would
be swept out to sea with the main current, although some would spread to either side of the main
channel, where there are larger areas of shallower water.
This assumes that the bunding is ineffective, and this is unlikely as integrity testing has been carried
out.
Methanol vapours would be released to the atmosphere from any spill. The dispersion of methanol
vapours from a spill of formalin to the bund has been examined elsewhere in this report with regard to
toxicity to humans.
The quantity of methanol vapours from a leak from an overflowing bund would be somewhat greater
than if the leak were contained within the bund. However, the concentration of methanol vapours
from a leak of methanol to groundwater and thence to Cork Harbour would be very small, as it would
take some time for the methanol to seep through the ground. The slow discharge rate would give rise
to a low Concentration. It is not considered that any tangible risk would be posed to the environment
by methanol vapours from this incident.
1.3.3.6.3 Risk Con fro/ Measures
There are access restrictions to the methanol bund. The methanol tank is constructed to a recognised
standard and non destructive tests are carried out on the tank every 5 years. There has been integrity
tests carried out on the bund. As part of the budget for 2006 vapour detection will be put in place.
The bund is designed to offer secondary containment during a tank rupture. It has been shown by the
HSE 10that bunds may not be able to cope with a catastrophic failure of the tank and the sudden
release of a large volume of liquid. The HSE report identifies a number of potential scenarios:
0
Bund overtopping: The momentum of the liquid causes a proportion of the tank contents to flow
over the top of the bund
Bund collapse: The forces exerted on the wall may cause bund collapse
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Number: 1.0.3 3 1112/05
0 Collapse of bund following collision with tank debris. There would be a force in the opposite
direction to liquid flow following catastrophic failure of the tank which could propel the tank (much
lighter than contents) towards the bund wall.
The resin bund height is lower than the tank height, so the most likely event is overtopping of the
bund wall. Another study carried out by the HSE13 illustrates that the amount of overtopping was
largely dependent on height of liquid in the tank and the bund height. The quantity overtopped is
calculated to be between 30 and 40%.
As discussed earlier the calculation used in the research paper carried out by HSE for bund
overtopping is simplistic and does not reflect the actual degree of containment accurately. Further
mitigation measures involve employees with full breathing gear starting the bladder tank and pouring
foam into the bund to prevent escalation of the incident. Other foam units from around the site will be
used if required.
13'Effects of secondary containment on source term modelling', WS Atkins Consultants Ltd, Contract
Research Report 324/2001, prepared for the HSE, UK.
Page 53 of 65
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Number:l.O.3 3 1112105
Averaging Time
Concentration (ppm) (SI
I 1.3.3.7 Methanol Road Tanker Loading Spill
In this scenario, the contents of a road tanker (19.2 tonnes) are lost to the bund. This could be caused
by rupture of a hose or pipe joint. Methanol would spill into the contained area and drain to the
underground sump from which itjs automatically pumped to the methanol tank bund. It is assumed
that the contained area is 200 m . The diameter of a circle of this area is 15.96m. The contents of
the tank (methanol) vaporise and disperse with the wind.
Distance from source centre to
Concentration (m)
F2 D5
The rate of evaporation depends primarily on the wind velocity, but also on the temperature of the
surface under the pool.
25,000 (IDLH)
250 (OEL-STEL)
The initial rate of evaporation of methanol was calculated as follows:
3600 28 27
900 162 70
Initial Rate of Evaporation (kgls)
~1
See section 1.3.2.3.3 for detail
! ?
I 0.13 I 0.17 I
Page 54 of 65
~ i i
Table 36: Initial Rate of Evaporation of Methanol
Following Methanol Road Tanker Loading Spill
1.3.3.7. I Human Consequences
From the modelling of this scenario, the effects from this MAS will be contained within the site.
Residents in the locality will not be in danger from the effects. A person working in the area will have
time to move indoors. As mentioned before in this section, an operator will only be in this area 10
times a week for a half an hour.
Methanol could be spilled and released to the environment from the road tanker loading area.
However, the maximum volume is very small, 20 m3. While the nature of ecological damage would be
the same as for the bulk tank, the potential scale would be much less.
1.3.3.7.3 Risk reduction Measures

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25,000 (IDLH)
250 (OEL-STEL)
dynea
3600 96 102
900 2200 367
Safety Report
Number:1.0.3 3 1/ 12/ 05
1.3.3.7.4 Mitigation
See section 1.3.1.3.4 for detail
1.3.3.8
(A spill to sea from the ship carrying methanol is outside the scope of the site, and is therefore not
included in this assessment.)
Methanol Ship Offloading - Spillage to Land
In this scenario, the pipeline carrying methanol from the ship to the bulk tank is ruptured, and
methanol pours on to the ground. In this analysis, it was assumed that the rupture takes place
approximately half way between the jety and the methanol tank.
The assumed pumping rate is 350 m /hr, i.e. 280 tonnes/hr or 77.8 kg/s. It is assumed that this
continues indefinitely. The model does not allow for leaks of limited duration. It is however expected
that the leak would be detected and the pump stopped within 5 minutes.
The liquid methanol continues to spread around the source of the leak until the rate of vaporisation
equals the rate of leakage. That is a steady-state condition. However, as the duration of the leak is
only 5 minutes, it is unlikely that steady state conditions will be reached. There is no containment.
The contents of the tank (methanol) vaporise and disperse with the wind.
The rate of evaporation of methanol was calculated as follows:
Table 38: The Rate of Evaporation from a
Methanol Ship Line Loading Spill
stabilitywas predicted to be as follows:
e
Environmental Risk
The volume of methanol that could be spilled and released to the environment from a rupture of the
jetty pipeline would be much less than from the bulk tank. While the nature of ecological damage
would be the same as for the bulk tank, the potential scale would be much less. The degradation
processes of methanol in soil and water has been discussed in previous sections.
@
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1.3.4 Domino Effects
Dynea and IF1 are neighbouring plants. The IF1 plant is being dismantled at the time of writing the
report. The report will be reviewed once knowledge of the new occupier of the IF1 site is known and
what work will be carried out at the site. Domino effects are considered with reference to:
0 Dynea site
0 IF1 site
1.3.4.1 Dynea Site
Major accidents at the Dynea site that could have an effect on the adjoining IF1 site include:
0
Loss of containment of the methanol tank into the bund
Rupture of pipe downstream of Formox reactor
Loss of containment of a formalin tank into the bund
1.3.4.1.1
In the event of loss of containment of the methanol tank into its bund, the OEL-STEL could be
exceeded under certain weather conditions within the IF1 site. However, assuming that mitigating
action was taken by Dynea to cover the pool of liquid, the impact would be transitory. The IDLH value
would not be exceeded off the Dynea site.
Loss of Containment of the Methanol Tank into the Bund
1.3.4.1.2
In the event of failure of the incinerator or lifting of the pressure relief valve (with failure of Absorber
pumps, a plume of gas containing formaldehyde would be emitted. If the wind were blowing towards
IF1 it is unlikely that unsafe concentrations would be generated off-site, but the plume might lead to
respiratory difficulties on the IF1 site
Failure of the catalytic or Lifting of Pressure Relief Valve
1.3.4.1.3
In the event of loss of containment of a formalin tank into its bund, a plume of formaldehyde vapour
would be emitted. If the wind were blowing towards IF1 the plume could lead to respiratory difficulties
on the IF1 site.
Loss of Containment of a Formalin Tank into the Bund
@
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1.3.4.2 IF1 Site
At present the IF1 plant is being dismantled and the only scenario which could have an impact at
Dynea is:
0
Rupture of methanol pipeline during ship offloading as a result of decommissioning work
on the IF1 facility
1.3.4.2.1
In the event of rupture of the methanol pipeline while ship offloading was in progress, a major spillage
of methanol would result at the jetty. Concentrations of methanol vapour could exceed the OEL-STEL
within the IF1 site:
0
0
Rupture of Methanol Pipeline during Ship Offloading
In adverse weather conditions, and
In particular if the wind is blowing towards IF1
Further, there is a substantial risk of ignition of the methanol, which could result in a pool fire, a jet fire,
a flash fire or a vapour cloud explosion.
1.3.4.2.2 Transport of Hazardous Materials
The transport of methanol and formalin by road is not considered to fall within the scope of the SI 476
of 2000, and the consequences of a release are not assessed here.
Dynea ensures that it complies with all statutory requirements in relation to road transport of these
materials.
Page 57 of 65
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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . -. . . . . . . . . . -. . - - - . . . - . . . -. . . . . . . . . -
Safety Report
Number1.0.3 3 111 2/05
1.3.5 Major Accident Scenarios with Environmental Impact
Major-accident scenarios with environmental impact comprise all of the above. The descriptions of
the consequences of loss of containment above include environmental impact.
The half-life of a substance is the time required for 50% reduction in the mass released or present.
The half-life depends on numerous factors including: the nature of the release, quantity of the release,
and physical, chemical and microbiological characteristics of the impacted media.
1.3.5.1 Methanol
Methanol occurs naturally in the environment as a result of various biological processes in vegetation,
micro-organisms, and other living species. A large release of concentrated methanol to ground water,
surface water, or soil has the potential to adversely impact the affected environment.
The half-life of methanol in soil, in surface water and in groundwater is 1-7 days. The half-life in the
@ air is 3-30 days.
When released into the soil, methanol is expected to readily biodegrade, based on the results of a
large number of biological screening studies, which include soil microcosm studies, and to leach into
groundwater. Its miscibility in water and log kW (-0.77) suggest high mobility in soil. Based on a
vapour pressure of 92 mm Hg at 20C, rapid evaporation from dry surfaces can be expected to occur.
The biodegradation of methanol can occur under both aerobic (oxygen present) and anaerobic
(oxygen absent) conditions.
~
I
The important environmental fate process for methanol in water is biodegradation. A large number of
screening studies have found methanol to be significantly biodegradable. Aquatic hydrolysis,
oxidation, photolysis, adsorption to sediment, and bioconcentration are not significant.
Methanol is significantly less toxic to marine life than crude oil or gasoline, and many of the
effects of short term exposure are temporary and reversible. The Office of Pollution
Prevention and Toxics indicated that methanol is essentially non-toxic to the four aquatic fish
species that were tested. A large methanol spill into surface water would have some
immediate impacts to the biota in the direct vicinity of the spill. However, because of its
properties (i.e., methanol readily mixes with water and evaporates quickly in the atmosphere)
methanol would rapidly dissipate into the environment, and within fairly short distances from
the spill would reach levels where biodegradation would rapidly oc~ur.~
When released into the air, methanol is expected to be readily degraded by reaction with
photochemically produced hydroxyl radicals and to be readily removed from the atmosphere by wet
deposition. Atmospheric methanol can also react with nitrogen dioxide in polluted air to yield methyl
nitrite. Because of methanols water solubility, rain would be expected to physically remove some from
the air; the detection of methanol in a thunderstorms water tends to confirm this supposition.
1.3.5.2 Formaldehyde
Aqueous solutions of Formaldehyde are expected to be slightly toxic to aquatic life. The LC5,J 96-hour
values for fish are between 10 and 100 mg/l. The methanol portion is expected to be slightly toxic to
aquatic life. The LC5d96-hour values for fish are between 10 and 100 mg/l.
Evaluation of the Fate and Transport of Methanol in the Environment, Drepared for the
14
American Methanol Institute bv Malcolm Pirnie, Inc, J anuarv 1999, Ref 3522-002
I
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When released into the soil, formaldehyde material is expected to leach into groundwater. While
formaldehyde is biodegradable under both aerobic and anaerobic conditions, its fate in soil is
unknown.
When released into water, formaldehyde will biodegrade to low levels in a few days. Little adsorption
to sediment would be expected to occur. In nutrient-enriched seawater there is a long lag period
(approximately 40 hr) prior to measurable loss of added formaldehyde by presumably biological
processes. Formaldehyde is slightly persistent in water, with a half-life of 2-20 days15. Its fate in
groundwater is unknown. This material is not expected to significantly bioaccumulate. About 99% of
formaldehyde will eventually end up in air; the rest will end up in the water.
As well as being directly emitted to the atmosphere, formaldehyde is formed as a result of
photochemical reactions between other chemicals in already polluted air. These reactions may
account for most of the formaldehyde in the air in some areas. This input is counterbalanced by
several important removal paths. It both photolyzes and reacts rapidly with reactive free radicals,
principally hydroxyl radicals, which are formed in the sunlight-irradiated atmosphere. The half-life in
the sunlit troposphere is a few hours. Reaction with nitrate radicals, insignificant during the day, may
be an important removal mechanism at night. The initial oxidation product, formic acid, is a
component of acid rain. Because of its high solubility there will be efficient transfer into rain and
surface water which may be an important sink. One model predicts dry deposition and wet removal
half-lives of 19 and 50 hr, respectively. Although formaldehyde is found in remote areas, it is probably
not transported there, but rather a result of the local generation of formaldehyde from longer-lived
precursors which have been transported there.
l5 State of Knowledae Report: Air Toxics and Indoor Air Quality in Australia 2001
Environment Australia 2001
0
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Ref. Incident Type of
No. Incident
Safety Report
Number:l.O.3 3 1/12/05
Fatal Effects
Distance (m)
1.4 Summary of Consequences of Major-Accident Scenarios
The consequences of major accidents are summarised in the following table.
Table 40: Distance to Fatal Effects from Major Accident Scenarios
VCE =Vapour Cloud Explosion
Note: all scenarios have some potential for impact other than on human beings.
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Range
1.4.1 Likelihood of Major Accidents
A
B
7.4.7.7 Hazard Ranking
The effects of major accident scenarios were classified as low, medium and high, as follows:
<50 m
50-250 m
Radiation
Ranking
Low I 4 I 0.3
rabl e 41: Basis for Hazard Ranking
In Table 41, the shaded cells are those distances or effect levels at or above which fatalities could
occur. The distances are those for a 1% fatality level. Locations closer to the plant than these
distances will have a higher fatality level, and those further away will have a lower fatality level, i.e.
virtually zero. As concentrations of formaldehyde and methanol'that will give a 100% fatality level are
not known, it is not possible to predict these distances.
The scenarios were ranked in order of decreasing distance to the onset of fatal effects, and classified
as follows:
Table 42: Hazard Ranges
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Event Incident Distance to
1% fatality
level (m)
I
Risk of fatality
yr -I
duma
5
6
Q)
1.4.1.2 Risk Estimation
The effects of explosions and fires are almost entirely independent of direction. However, the effects
of releases of toxic gases and vapours depend on the direction of the wind and atmospheric stability.
The effects of incidents 5 and 6 in Table 43 are not direction-specific, and the risk to an individual
continuously present at the maximum effect distance (distance to 1% fatality) is as follows:
Prolonged Fire in Methanol Tank Bund 67 6 x
Methanol to Bund
Vapour Cloud Explosion from Release of 35 1 1.9 x
The effects of incidents 1, 2, 3, 4 and 7 are direction specific. The risk to an individual depends on the
location of that individual. The risk data used for risk estimation are form reputable scientific sources
and are consistant with the data available at the time. The engineering consultant Don Menzie &
Associates carried out this analysis and all information regarding data used and source can be got
through his office on request.
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dynea
1.4.1.3 Tolerable Risk Criteria
I. 4.1.3.1 Individual Risk
The UK HSE in its publication Risk criteria for land-use planning in the vicinity of major industrial
hazards states that the HSE will use the figure of 1 in a million per year for the lower bound for a
typical pattern of user behaviour in a development.
As a cross-section of the population contains a proportion of highly vulnerable people for whom a
'dangerous' dose would likely result in death, this criterion equates to about 1 in a million per year
chance of death for such people.
For the majority of the population, assessments done by HSE suggest that this corresponds to a
risk of about 1/3 in a million per year of death, since this is the risk of receiving a somewhat
higher dose which would be expected to result in the death of 50% of the population.
HSE suggests that a level of 1/3 in a million per year of a 'dangerous' dose or worse would be
trivial even for such cases as homes for the elderly, caring institutions, long-stay hospitals etc.
Q
For hazards which are involuntary and with little immediate benefit to the people at risk, HSE will
use an upper limit of 10 in a million per year of a dangerous dose or worse, for all development
cases above a certain size. This implies that the more vulnerable members of the population are
at a risk of death of about 10 in a million per year.
In using these criteria, HSE would automatically indicate 'negligible risk' for proposals below the
lower bound for developments such as housing where a particular person might well be present
most of the time.
HSE would similarly automatically indicate 'substantial risk' for proposals with a substantial
number of people (25 or more people) above the upper limit since there would probably be one or
more highly susceptible people in such a number.
For proposals where the risks lie between these values, HSE would consider whether there are
features of detail which tend to justify more or less stringent advice.
For the Dynea site, most major incidents assessed will not give rise to effects outside of the
DyneaAFI site. For those that do give rise to a risk of fatality outside of the DyneaIlFI site, the
highest risk is from a large spill of formalin to the tank farm bund. This is 1.3 x and is in a
SSE direction from the centre of the tank farm bund. The off-site effect only occurs during
atmospheric stability conditions F. During atmospheric stability conditions D, the effect is confined
to the site. The risk of 1.3 x has been calculated on assumption that no mitigation takes
place, e.g. covering the spill with foam.
e
When the directional effect of toxic releases is taken into account, very few of the major accident
scenarios assessed lead to an individual risk exceeding that recommended by the UK HSE.
Appendix 18 shows the risk contours fro the site.
1.4.1.3.2 Societal Risk
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dunea
The HSE states that there is at present no clear consensus on criteria for societal risk, and it is
not even clear how best to describe such risk. The FIN curve is a difficult concept, and it is not
apparent how to compare two FIN curves for two different situations.
In view of the absence of residential populations and very low industrial population levels within
the off-site areas affected, F/N curves have not been prepared.
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