ABSTRACT

This report explores the various risks and hazards present in the design of an acrylic and
acetic production plant within Trinidad. This was accomplished by consequence modelling of the
expected damages for four differing hypothetical hazardous incidents. The various scenarios were
developed with the intention of thoroughly covering and identifying the potential damages caused
by a toxic gas release, pool fire, BLEVE and explosion while keeping the chain of events as
plausible to the industrial setting as possible.
Applying suitable discharge, source and effect models to the various scenarios
demonstrating the hazards of fire, explosion and toxic release, a quantitative consequence analysis
based on these events were determined. With respect to the Pool Fire scenario, the probability of
having such an event as explained was the most likely of the other scenarios in comparison, coming
in at 3.80% within the 15 year span. The safe distance from this fire was also determined to be
50m.
The fire followed by the explosion of the reactor was caused by a power outage which
decreased the flow of the cooling water to the reactor. This caused an increase in temperature
which led to a fire. The continuous increase in the reactor cause a direct relation to the pressure
increase and this caused the explosion of the reactor. This caused injuries to workers on the
facility and they suffered from fatalities such as eardrum rupture, lung haemorrhage and there
was also structural damage of the reactor.

For the toxic acrylic gas release from the reactor, results showed that acrylic acid gas was
released at 14,524 kg/s from the reactor. The acid concentration released was at its highest at 40
m away from the source at 25,481,793.08ppm which could cause immediate death. The
concentration decreased as the distance from the source increased and was found to reach
concentrations lower than 100 ppm at a distance of alarmingly 70,000,000 m which would cause
only discomfort and slight irritation. Such a likelihood of the scenario discussed was found to be
very unlikely.

Finally, with respect to the explosion scenario, calculations revealed that persons in the
range of 22.5m will experience ear drum rupture and structural damage. Persons in the range of
6m would be affected with lung haemorrhage and since there was only two fragments, the
probability of persons being injured by the explosion would be small.

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Table of Contents
ABSTRACT .................................................................................................................................... 2

1.0 INTRODUCTION .................................................................................................................... 9

2.0 DESIGN INTENT .................................................................................................................. 10

3.0 PROCESS DESCRIPTION .................................................................................................... 11

3.1 Propylene Oxidation Process .............................................................................................. 11

3.2 Separation ........................................................................................................................... 14

3.3 Hazards and Material Identification.................................................................................... 15

3.4 Maintenance and Emergency Procedures ........................................................................... 16

3.5 Environmental Considerations ............................................................................................ 16

4.0 PLANT LOCATION AND SITE SELECTION .................................................................... 18

4.1 Site Layout .......................................................................................................................... 22

4.2 PLANT LAYOUT .............................................................................................................. 23

5.0 HAZOP ANALYSIS .............................................................................................................. 24

5.1 Introduction ......................................................................................................................... 24

6.0 EMERGENCY RESPONSES ................................................................................................ 27

6.1 Emergency Plan .................................................................................................................. 27

6.2 Levels of response action ................................................................................................... 27

6.3 Emergency Response Plan .................................................................................................. 28

6.4 Emergency Response Service Training ............................................................................. 29

6.5 Emergency Response Service Organization ....................................................................... 30

6.6 Making the Plan Work ........................................................................................................ 31

7.0 HAZARD SCENARIOS......................................................................................................... 33

7.1 Pool Fire .............................................................................................................................. 33

Scenario................................................................................................................................. 33

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 Results ................................................................................................................................... 34

Discussion ............................................................................................................................. 35

Conclusion ............................................................................................................................ 44

Recommendations ................................................................................................................. 44

LOPA .................................................................................................................................... 44

HAZOP ..................................................................................................................................... 46

7.2 Boiling Liquid Expanding Vapour Explosion (BLEVE) .................................................... 52

Scenario................................................................................................................................. 52

Results ................................................................................................................................... 52

Discussion ............................................................................................................................. 54

LOPA .................................................................................................................................... 56

HAZOP ..................................................................................................................................... 61

Mitigation Methods ............................................................................................................... 65

Conclusion ................................................................................................................................ 65

7.3 Toxic Gas Release............................................................................................................... 66

Introduction ........................................................................................................................... 66

Scenario................................................................................................................................. 68

Results ................................................................................................................................... 70

Discussion ............................................................................................................................. 76

Conclusion ............................................................................................................................ 79

Recommendations ................................................................................................................. 80

LOPA .................................................................................................................................... 81

HAZOP ................................................................................................................................. 84

7.4 Explosion ............................................................................................................................ 92

Scenario................................................................................................................................. 92

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 Results ................................................................................................................................... 93

Discussion ............................................................................................................................. 94

Conclusions ........................................................................................................................... 97

Recommendations ................................................................................................................. 97

LOPA .................................................................................................................................... 97

HAZOP ............................................................................................................................... 100

8.0 REFERENCES ..................................................................................................................... 103

9.0 APPENDIX ........................................................................................................................... 104

9.1 Pool Fire Scenario ............................................................................................................. 104

Evaporation Model.............................................................................................................. 106

Dispersion model ................................................................................................................ 108

Pool Fire Model .................................................................................................................. 109

Thermal Effect Model ......................................................................................................... 112

9.2 BLEVE SCENARIO ......................................................................................................... 113

BLEVE Thermal Flux ......................................................................................................... 113

Blast fragments from a BLEVE .......................................................................................... 116

Fatalities Due to Thermal Flux from A BLEVE Fireball ................................................... 120

Overpressure from A Combustion in a Vessel ................................................................... 121

9.3 Toxic Gas Release Scenario.............................................................................................. 123

Discharge rate model .......................................................................................................... 123

Dispersion Model ................................................................................................................ 126

The Probability of Death ..................................................................................................... 129

9.4 Explosion Scenario ........................................................................................................... 130

Baker’s Method for Overpressure of a Ruptured Vessel: (24) .......................................... 130

Velocity of Fragments from a Vessel Rupture ................................................................... 133

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 Range of a Fragment in Air ................................................................................................ 134

BLEVE Thermal Flux ......................................................................................................... 136

Fatality ................................................................................................................................ 138

TABLE OF TABLES
Table 1: Probability of Fatalities for a Pool Fire .......................................................................... 34
Table 2: Estimated likelihood of each event occurring ................................................................ 41
Table 3: Showing Layer of Protection Analysis ........................................................................... 46
Table 4:HAZOP Study for Pool Fire ............................................................................................ 46
Table 5: Showing the Percentage Of Fatalities (%) Occurred With Varying Distance for The
Thermal Radiation Probit Model .................................................................................................. 52
Table 6:Results Were Calculated Using Formulas To Determine The Following Data............... 53
Table 7: Results Obtained For the Percentage Fatalities for Each Probit Equation ..................... 53
Table 8: Showing The Layer Of Protection Analysis ................................................................... 58
Table 9: Shows The Data Required To Calculate The Gas Release Rate. ................................... 70
Table 10:Shows The Results Obtained From The Discharge Rate Model ................................... 71
Table 11: Shows The Release Concentration (Ppm) Over A Range Of Downwind Distances For
Stability Class F At A Wind Speed Of 2 m/s................................................................................ 71
Table 12: Shows The Concentrations Required To Cause Different % Fatalities For Different
Exposure Time .............................................................................................................................. 75
Table 13: Shows The Effects Of Certain Concentrations Of Acrylic Acid .................................. 75
Table 14 :Layer of Protection Analysis for the Scenario .............................................................. 82
Table 15: HAZOP For The Reactants Feed Stream To Reactor ................................................... 85
Table 16: HAZOP For Cooling Stream To Reactor ..................................................................... 88
Table 17: HAZOP For Crude Product Stream From Reactor ....................................................... 89
Table 18:Percentage Of Fatalities For The Distance Of The Range Of The Fragments. ............. 93
Table 19: Percentage Of Fatalities For The Distance Of The Fragments. .................................... 93
Table 20: Layer of Protection Analysis for the Explosion Scenario ............................................ 98
Table 21: Shows The Design Specifications And Capacity Of Tank , T-108 ........................... 104
Table 22: Showing The Input Information For The Pool Fire Scenario ..................................... 106

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Table 23: Meteorological And Gas Release Data For Ignition Of Vapour Cloud...................... 108
Table 24: Showing Values Used In The Calculation Of The Pool Fire Model .......................... 109
Table 25: Input data for BLEVE thermal flux ............................................................................ 113
Table 26: Design Specifications When Calculating The Blast Fragments From A BLEVE...... 116
Table 27: Data Used for Overpressure Calculations................................................................... 121
Table 28: Data Used To Calculate Rate of Gas Release Through Hole ..................................... 123
Table 29: Data for Overpressure Calculations ............................................................................ 130
Table 30: Ln (R) and Ln(P) Values from Overpressure curves .................................................. 131
Table 31: Ln (R) and Ln (I) values from Impulse Curves .......................................................... 132
Table 32: Data Used For Velocity of Fragments form a Vessel Rupture ................................... 133
Table 33: Results obtained for Dimensionless Velocity of Fragments....................................... 134
Table 34: Data Used to Calculate Range of Fragments in Air ................................................... 134
Table 35: Interpolated Values From Figure For Various Lift To Drag Ratios ........................... 135
Table 36: Data Used to Calculate BLEVE Thermal Flux........................................................... 136

TABLE OF FIGURES

Figure 2: Process Flow Diagram Part 1 ........................................................................................ 13

Figure 3: Process Flow Diagram Part 2-Focusing on Separation ................................................. 14
Figure 4: Location of the Union Industrial Estate, La Brea (Javeed, 2008) ................................. 18
Figure 5:Illustrating the proposed location for the plant in Union Industrial Estate, La Brea
(AIChE 1999)................................................................................................................................ 21
Figure 6: Illustrating the Plant Layout for the Process ................................................................. 23
Figure 7: Procedure for Developing HAZOP Report ................................................................... 26
Figure 8: Emittance Radiation vs Receiver at 60s exposure......................................................... 42
Figure 9: Percentage fatality vs Er (W/m2) fatality at different exposure time (s) ...................... 42
Figure 10: Receiver distance (m) vs Percentage Fatality at different exposure time (s) .............. 43
Figure 11: Position of Acetic Tank in Plant Design ..................................................................... 51
Figure 12: Results showing the % fatalities for each probit equation used .................................. 56
Figure 13: Hazop for the BLEVE Scenario .................................................................................. 64
Figure 14: Acrylic Acid Dose-Effect Relationship ....................................................................... 68

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Figure 15: Shows The Following Graph Illustrates The Concentration Profile Of Acrylic Acid
Gas With Respect To Downwind Distance. ................................................................................. 72
Figure 16: Shows The Isopleth For The Plume ............................................................................ 74
Figure 17: Shows The Change In Percentage Fatality With Increasing Exposure Times For Given
Concentrations Of Acrylic Acid. .................................................................................................. 74
Figure 18: Schematic of Reactor, R-100....................................................................................... 84
Figure 19: Showing The Mass Flow Rate At Different Heat Capacity Ratio ............................ 125

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 1.0 INTRODUCTION
Safety is one of the most important aspects for the operation of a chemical plant. In
ensuring a high level of safety within the plant, hazard analysis studies are performed during the
implementation of the plant. Plant safety can be considered under several layers, namely hazard
identification and assessment, hazard control, process control which comprises of good operation
practises, control systems and proper management. Hazard analyses are performed on materials,
intermediates, and products prior to the plant implementation. Hazard studies are also performed
in the design stages of plant in addition to hazard studies during the operation of the plant. The
hazard studies performed also considers the probability of incidents occurring and the effects of
the incidents on the plant equipment, structures and people on the plant.

A hazard is a situation in the workplace that has the potential to harm the health and safety
of people or to damage plant and equipment. The situation could involve a task, chemical or
equipment (SafeWork SA – definitions of hazard). Loss prevention can be defined as a systematic
approach which is aimed at prevention of accident or minimization of inevitable effects. Safety
issues and some financial losses are usually associated with loss prevention. Risk can be definied
as the likelihood of an undesirable event which have occurred within a stated period or simply,
under circumstances. It may be further described as a particular frequency, that is, a number of
particular events occurring per unit time or simply a probability. Risk comprises of individual risk
which is the frequency at which it is expected that a person may sustain a particular level of harm
from certain hazards coming to pass (Crawlry 2014)

The purpose of this report was to evaluate the risks and hazards present within an industrial
scale acrylic acid production plant. This was accomplished by estimating and assessing the
expected damage for three differing hypothetical hazardous incidents. The various scenarios were
developed with the intention of thoroughly covering and identifying the potential damages caused
by a toxic gas release, fire and explosion while keeping the chain of events as plausible to the
industrial setting as possible. Additionally, measures of alleviating will be undertaken and
explored.

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 2.0 DESIGN INTENT
The intention of the Acrylic acid facility was to provide a cheap, marketable source of high
purity acrylic and acetic acid to meet global demands. As a consequence, the main intent was
centred on designing a plant which would only be able to compete against and surpass these global
production plants. In pursuing this goal, the primary processes involved were all based on the
utilization of process water, propylene and air, which are available in substantial quantity within
Trinidad.

Acrylic acid, is an unsaturated carboxylic acid with chemical formula CH2CHCO2H and
the compound consists of vinyl group connected to a carboxylic acid. It is a colourless liquid with
an arid smell and is miscible in water, alcohols ethers and chloroforms. Its boiling point is around
140oC and melting point is around 13oC under atmospheric conditions but it is flammable and
reactive. It is has a pH of 3 and they are used for making certain polymers since acrylic acid are
versatile monomers. (Pubchem 2016)

Acetic acid is the main component of vinegar. Its chemical formula is (CH 3COOH) and it
is a colourless liquid with a distinctive sour taste and pungent smell. It has a boiling point of 118oC
and thus is flammable and reactive. It is miscible in water under normal laboratory conditions and
is more acidic than acrylic acid with a pH of 2.4. It is a simple carboxylic acid with a methyl group,
CH3 linked to carboxylic acid group, COOH or the acetyl group CH3CO linked to a hydroxyl
group, OH. (Pubchem 2016).

Trinidad and Tobago’s economy is one known for being an excellent investment site for
multinational businesses. Trinidad’s economy is based solely on the energy sector and is heavily
dependent on oil and natural gas production. In today’s economy, Acrylic and Acetic are one of
the most valuable commodities being produced since its presence is accompanied with a vast array
of uses. The proposal of a 161 970 tonne Acrylic acid and 2610 tonne of Acetic acid production
will aid in diversifying the economy of Trinidad and Tobago. This facility is anticipated to have
little impact on the employees, surrounding communities and environment.

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 Construction of an acrylic and acetic plant in Trinidad and Tobago will be beneficial due
to large consumption and demand of the both acids worldwide. The acetic and acrylic acid plant
takes into consideration the world market demand, environmental and safety aspects and social,
political and economic factors. The acrylic acid plant could possibly become the pathway to
globalization, advanced technology and innovation for future generations by committed
continuous building and improvement in the industrial sector.

3.0 PROCESS DESCRIPTION

The most common chemical pathway to produce acrylic acid is the partial oxidation of
propylene. This mechanism follows a two-step process where propylene is oxidized to form
acrolein and then further oxidized to Acrylic acid. The reaction stoichiometry shown below:

𝐶3 𝐻6 + 𝑂2 → 𝐶3 𝐻4 𝑂 + 𝐻2 𝑂

1
𝐶3 𝐻4 𝑂 + 𝑂2 → 𝐶3 𝐻4 𝑂2
2

This oxidation of reactants to form products results in several side reactions shown below:

7
𝐶3 𝐻4 𝑂 + 𝑂2 → 3𝐶𝑂2 + 2𝐻2 𝑂
2

3
𝐶3 𝐻4 𝑂 + 𝑂2 → 𝐶2 𝐻4 𝑂2 + 𝐶𝑂2
2

9
𝐶3 𝐻6 + 𝑂2 → 3𝐶𝑂2 + 3𝐻2 𝑂
2

3.1 Propylene Oxidation Process

A detailed process will now be outlined:

Firstly, the front end of the plant which comprises of the compressors and tubular fixed
bed reactors. In this process, as seen from the Process Flow Diagram below, air, steam and
propylene are being fed into the plant. Air is generated within the plant while steam (from process
water obtained from W.A.S.A to  steam via boilers within the plant) and propylene, obtained
from Petrotrin. Air and steam is fed in a 1:3 ratio respectively and it can be noted that the propylene

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stream and air and steam stream were all split accordingly and sent to two reactors where
optimizations were done here.

It can be noted that R-101 tubular fixed bed acrylic reactor was optimized to produce
acrylic acid with a 93.7% conversion rate while second reactor R-102, which is also a fixed bed
reactor was optimized to produce acetic acid with an optimum conversion rate of around 12%. It
was ensured that the flammability limits of propylene and oxygen were within the flammability
limit which was below 11% and 5% respectively to prevent any explosions or fires from occurring.
Also these reactors were made in the form of a shell and tube where the catalyst, mixed metal
oxide catalyst molybdenum based catalyst such as Mo12V4.6Cu2.2Cr6W2.4 supported on alumina
and the reason for this construction is to maintain the high temperatures within the reactors which
was around 312-313.5oC in both reactors. Steam was used to cool both reactors which was sent
from shell side while the tube side contains the main components. The reactors’ effluent was sent
to two steam economizers , E-100 and E-101 and then further cooled to around 85oC by passing
two other cooling heat exchangers, E-102 and E-103.

The effluents were then sent two vertical flash drums , T-100 and T-101 operating at around
2.8 bars and 85oC where the vapour streams, consist of gases such as oxygen, nitrogen, acrylic,
propylene, carbon dioxide, water vapour and small amount of acetic vapour. The liquid streams of
the flash drums, contain acrylic and acetic acid and combined with the liquid outlet stream of the
Absorber, T-102 which contains the dissolved acids in the water. It can be noted that water from
the top absorber inlet stream was required to dissolved the acids alone while the remaining gases
were purged and was within the environmental limit. 15 stages were obtained from the absorber
for this required separation. Propylene can be used as fuel for the process and carbon dioxide can
be sold to the Mitsubishi methanol plant that is being constructed near our plant. All three streams
were then combined, that is, the liquid outlet stream of T-102 and the two streams from T-100 and
T-101 and sent to the separation section.

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Figure 1: Process Flow Diagram Part 1

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3.2 Separation

Figure 2: Process Flow Diagram Part 2-Focusing on Separation

In this section, the inlet stream to the liquid-liquid extractor, T-103 contains three different
azeotropes: Water/acrylic, water/acetic and acrylic and acetic and thus a suitable solvent was
required to remove 99.9% of the water. Around 9408 kmol/hr solvent, isopropyl acetate was
required to remove all of the water and a total of 15 stages were obtained and it was assumed that
all of the solvent was fully recovered via the solvent recovery column with 20 stages and with the
high flow of solvent, it resulted in the largest heat load and heat sink (reboilers and condensers) in
this column, T-104.

The solvent was recycled and it can be considered in a closed loop and the bottom stream
of solvent was sent to the first acid tower, T-105 where 20% of the top stream contain acetic acid
and the bottom stream contain 99.9% acrylic acid and a total of around 22 stages were obtained
for this required separation. Another tower was needed to achieve 99.9% purity of the both acids
and required production rate and a total of around 20 stages were obtained for this separation and

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then sent to two storage tank under and stored under atmospheric conditions for seven days before
shipping.

3.3 Hazards and Material Identification

As with all chemical process plant, hazards and potential for large scale destruction are
everywhere. The acrylic plant is by no means an exception to this. The main objective of a
responsible chemical manufacturing project is to lessen the threat of any harm to people,
property and the environment. Hazard identification is the first step in building a thorough
Emergency plan and are a major part of responsible chemical manufacturing.
There are 4 principal types of hazards; fire, explosion, toxic release and environmental
damage. In synthesising flammable chemicals such as acrylic and acetic acid a large quantity of
propylene is required. It can be noted that the high volatile liquids of acetic and acrylic acids are
volatile was stored in 2 cylindrical tanks of around 1200m3 stainless steel tanks.
Having such a large feed inventory of flammable materials poses a major fire hazard within the
facility. Should a fire erupt in any one of these vessels, it can quickly spread to the other nearby
tanks, quickly becoming uncontrollable.
Within the acrylic and acetic acid production process, high quantity of pressurized oxygen
and propylene is fed to both synthesis reactors. In addition to this gas being flammable, it is also
explosive. The reactor operates at very high temperatures and thus is vital to keep the temperature
controlled. Rupture of this vessel can pose a serious threat of creating a fire, explosion and even a
toxic gas release.
Acetic acid and acrylic acids are the most hazardous chemical present on the facility with
respect to health and the integrity of the equipment it contacts due to its high corrosiveness. Contact
with the skin can cause burns and irritation while a mist of this chemical can lead to choking or
shortness of breath. The acids are also a mutagenic for mammalian somatic cells and can therefore
have potential chronic health impact for a long scale exposure. The corrosiveness of this chemical
can deteriorate the pipelines which transport it. Poor maintenance of these lines may lead to the
formation of holes, leaks or even critical failure where the line ruptures. This chemical can also
harm aquatic life by increasing pH levels if allowed to spill into waterways, sewers and drains.

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3.4 Maintenance and Emergency Procedures
All equipment needs to be properly maintained to prevent any unforeseen stoppages in
production. It can be noted that the plant is expected to run 330 days per year to account for any
routine maintenance. If there is any malfunction of any equipment, the plants profitability will be
decreased while the expenses and labour remain idle. To prevent any such incidents from
occurring, corrective and preventative measures should be undertaken and in addition, condition-
based maintenance procedures should be utilised as illustrated by WIPRO technologies.

The reactors’ walls should be inspected frequently for any signs of corrosion or heat
damage. If the active surface area of the catalyst diminishes, catalyst packing must be inspected
and may be regenerated. It can be estimated that the life of catalyst is around 2-3 years. In
addition, compressors and pumps must be well maintained and frequently monitored for signs of
performance losses or physical damages. All other equipment should be monitored for any signs
of wear and reduced performance.

Moreover, operators must check the integrity of piping to prevent any leaks or blockages
within the system. The system of piping, needs to be flushed with inerts to prevent any blockage
or buildup. In an emergency, the controls valves can be closed to prevent feed flow to the
reactor. A recommendation of constructing a concrete shell over the reactor to ensure operational
activities are safe in the event of a fire or explosion is vital to the safety of the workers on site.

Other maintenances such as ensuring propylene does not leak from reactors’ shell must
be considered because this can form a combustible mixture. The Occupational Safety and Health
Administration recommends using Detector tubes manufactured but AUER/MSA or Drager, so
that is can detect concentrations of higher than 200 ppm in the air. If the reactor is near auto-
ignition temperatures that can be detrimental, the people working must go the reactor
containment unit. Finally, fire extinguishers and other flame retardant materials should be
utilised according to EMA and industrial rules.

3.5 Environmental Considerations

Acrylic Acid and Acetic Acid is miscible with water and not expected to adsorb onto soil
particles or sediments. However, when released in the atmosphere, acrylic acid produces
hydroxyl radicals and thus contributes to ozone degradation. These acids biodegrade in water and

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has residence time in air of less than one month. Since no solid waste is emitted from the process
the plant meets the Federal Hazardous and Solid Waste Amendments (HWSA) under the
Resource Conversation and Recovery Act (RCR). The pollutants that are problematic are CO and
CO2. The EP’s Clean Air Act only regulates CO at a level of 35ppm per hour. However, all CO
is quickly oxidised to CO2 and thus the trace of CO left will within the EP’s Clean Air Act.
Although, there is not a direct standard for CO2 emissions, plants are required to obtain permits
for operational activities and building from the EPA to insure compliance. It can be noted the
CO2 will be regulated in the future. A carbon capture and sequestration process would have to be
utilised if the plant is found to be above the regulatory limits in a future date.

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 4.0 PLANT LOCATION AND SITE SELECTION
When consideration is given to the idea of establishing an Acrylic acid plant, it is viewed
as extremely advantageous. This is because it creates the opportunity of linking the energy industry
with the manufacturing industry in Trinidad and Tobago. It was decided the plant should be placed
in a location close to the desired resources, as far as possible from any local community as well as
close to a port for easy export of products. A region of land within Union Industrial estate was
decided upon located at the co-ordinates [10.222638 , -61.6233271] within the proximity of the
suppliers.

For this particular type of facility, various aspects must be highlighted about the proposed
site for the industry and with each factor, appropriate justifications are made to illustrate the
reasons for choosing that site. At the end, after considering each factor, the favourable location for
the plant was seen to be the Union Industrial Estate, La Brea as depicted:

Figure 3: Location of the Union Industrial Estate, La Brea (Javeed, 2008)

The Union Industrial Estate is a fairly new establishment, placed as an alternative to the
existing and overcrowded Point Lisas Industrial Estate, Point Lisas. This site, found on the south-
western end of Trinidad, is a 600 hectare environment established mainly for the use of heavy and

18 | P a g e
light downstream gas-based industries, which approximately 157 Hectares has been fully
developed. Services at estate include: Aggregate, Bioremediation, oil and gas logistics, pipe
laydown yard and warehousing. In addition, ear to our plant is the country’s first Fabrication Yard
and associated dock for the manufacture of offshore platforms that is found on the estate. One of
the major platforms that have been fabricated at this facility is bpTT’s Juniper topsides which was
loaded out from Berth 2, Port of Brighton in January 2017. It can be noted that the tenants on the
estate and local south-based industries, utilises the Port of Brighton which consist of 3 berths that
is 660m in length.

Additionally, Government agencies such as Customs and Immigration are resent 24 hours
per day. The port is fully equipped with navigational aids and light towers and 150m wide
navigation channel that is dredged to a depth of 12.8m The turning basin has a diameter of 500m.
Found approximately 1km away from the functioning La Brea Industrial Estate (managed by
LABIDCO), this levelled and compacted location is an ideal site for establishing an acrylic acid
production plant simply because the basic amenities required for such production are at hand, such
as the port facility, power, water and storage necessities.

Some of the key services and areas found in this estate include: Logistics such Port of
Brighton’s proximity to oil and gas marine fields where the main site for logistics services support
the offshore petroleum activities in the area, leasing where approximately fifty eight tenantable
parcels, fifty four which are leased lots and the existing tenant profile which includes offshore
support services such as Lee’s Contracting, Ad Gas Co Ltd and much more. Some other facilities
and infrastructure that is found within the estate and nearby to our plant are Laydown yards where
NGC uses 60 acres for storage of its 36 and 56 inches diameter pipe and bioremediation where
Kaizen International is the provide of biorememdiation treatment services at LABIDCO’s
bioremediation cells at La Brea and Oil Mop Environmental Services and Tiger Tanks. Finally,
the fabrication yard where A&A Mechanical and Damus/Gulf Island Fabricators Joint Venture
which are located here. Therefore, all necessary resources are readily available for plant start-up

In addition to this, the proposed location is a very recent development in the energy sector
so as to house more energy and hence further downstream manufacturing industries and there is

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still much land available. Therefore, a 50 acre land requirement should not be troublesome to
obtain at this location. Though it is located on the southern end of the country, the Union Industrial
Estate has become, over the years, easily accessible due to improved roadways and additional
routes.
Some of the factors that were considered in choosing this location for the desired industrial facility
included:

1. Easy Access to Raw Materials

2. Proximity to Potential Markets
3. Readily Available Utilities
4. Access to Industry
5. Selection of land
6. Availability of labour
7. Geographical Considerations
8. Climate Considerations
9. Environmental Impact and Effluent Disposal
10. Emergency Services
11. Possibility of Natural disasters

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 Figure 4:Illustrating the proposed location for the plant in Union Industrial Estate, La Brea (AIChE 1999)

(Google. “Google Maps”. 2017)

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4.1 Site Layout
A number of factors determine the plant layout and these include:
• The closeness of certain equipment and materials so time and cost can be minimized
• Limitations of the geographical aspect
• Interaction with roadways, proper drainage and utilities that are already existing
• Interacting with other nearby plants;
• Proper operational and maintenance needs
• Locating hazardous materials as far as possible from people living nearby as well the
facilities itself
• Flammable substances should be confined incase of any release
• Accessibility to emergency services and escape routes
• Proper working conditions for labourers

In determining a plant layout, the main factors that were considered include.
• Safety
• Fire
• Explosions
• Toxic gas release
• Proximity of equipment

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4.2 PLANT LAYOUT

Figure 5: Illustrating the Plant Layout for the Process

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 5.0 HAZOP ANALYSIS
5.1 Introduction
By definition, a HAZOP is an abbreviation for Hazard and Operability Study that is based
on the fact that many personnel discuss a particular hazard and analyze the situation to identify the
problems as well as possible solutions. They concentrate on identifying not only the hazards of the
plant but the operability problems that exist. This has its many benefits because it allows the
notification of more hazards within the process if a group of people communicate versus if
individuals work separately and then combine their final results.

The HAZOP involves examining the particular process under consideration and directing
full attention to a specific portion called nodes. Nodes can be identified from the Piping and
Instrumentation diagram (P&ID) and when a process parameter is chosen, an intention is created
for this node under consideration. The process of HAZOPS usually makes use of guide words that
describe the process parameter and how it affects the entire system.

In order for a HAZOP to be truly successful, deviations are created from ideal operation and
the guide words are placed with the parameters. It creates a situation where the process may
completely take the wrong direction and should this happen during operation, a solution is at hand
to circumvent any implications. Some of the guide words that are often used are:

 No
 More
 Less
 As Well As
 Reverse
 Other Than

Examples of parameters that may be discussed include:

 Flow
 Temperature
 Pressure
 Level

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  Phase
 Composition

The main procedure followed when conducting HAZOPS involves the steps:

1. The system under consideration is first split in several sections and deviations are created
for each situation.
2. The cause of the deviation is then highlighted, followed by the evaluation of the
consequences.
3. In order to reduce the occurrence of such deviations, safeguards are then planned and
discussed to mitigate these problems.
4. Actions are then recommended that may fully eliminate the deviation completelty.
5. The information is then recorded and tabulated.
6. The procedure is repeated for accuracy.

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Figure 6: Procedure for Developing HAZOP Report

(Zhang, 2007)

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 6.0 EMERGENCY RESPONSES
6.1 Emergency Plan
Planning is essential for the success of any operation, especially an emergency one. A
carefully planned emergency plan is vital for any plant which handles hazardous chemicals. Most
emergencies are relatively small and can be dealt with onsite. Although the principles of
emergency planning are applicable to all installations, each plant should have a comprehensive
emergency plan relevant to its particular circumstances. The aim of an emergency plan should be
to contain or minimize the effects of an incident in a swift and effective manner. The plan should
therefore be simple and easy to use and remember. It must be valid and flexible enough to be
applicable to any emergency which may arise and must be known and understood by everyone
involved.

The starting point for all emergency planning is the identification of the hazards present on the
site. It is necessary to establish what may go where, and where, together with the likelihood and
consequences of these problems. Four main hazards which are always considered includes fires,
explosions, toxic releases and environmental damage although consideration must be given to
natural events such as floods, storms, earthquakes etc. Another important aspect of emergency
planning involves the assessment of counter measures which are required to deal with the
emergencies which may arise. The following areas should be considered:

 Cut off and isolation systems

 Fire fighting
 First aid and handling of casualties
 Staff protection
 Reduction of the impact on the environment
 Organization of an emergency response

6.2 Levels of response action

In the case of an emergency, three different levels of response action may be considered. These
include a level I, level II and level III response:

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 A level I response is used for hazards such as minor leaks or spills where no injury or disruption
is caused to operation. The appropriate response action for this is to alert the shift supervisor,
evacuate the area if necessary, monitor the perimeter and clean up or control the release.
 A level II response is used for a significant leak or spill which may lead to some injury or
disruption to operation. The recommended response action for this type of hazard is to alert
the shift supervisor, evacuate the area, implement the emergency response plan, contact
security to bar entry to the facility, monitor plant boundaries and control and clean the release.
 A level III response is classified by a major accident such as a jet fire, bleve, plume, pool fire
or explosion. In this type of hazard, serious injury is incurred and the operation may be halted.
For a level III hazard the response action involves alerting the incident controller and site main
controller, evacuate the area, bar the entrance to the facility, monitor the plant boundaries,
control the release and contact the media to communicate to the public.

6.3 Emergency Response Plan

Emergency preparation in a plant may lead to the difference between minor incidents and
large scale accidents. For the design of an effective response plan, the three elements which are
required are recourses, organization and people. For a plant, two main types of emergency
responses may exist which includes the onsite and offsite plans. If only the plant is being affected
by the incident, the on site plan is used. For the onsite plan, minor incidents such as small spills
and leaks are usually dealt with by the shift supervisor or the operator. As mentioned above, for
major incidents, such as those which require a level III response three sets of personnel are
required; the incident controller, site main controller and other response personnel. The people
who fulfill these roles should be identified, together with their substitutes in the event of non-
availability, and the details given of how they may be contacted.
The incident controller is mainly responsible for the three following responsibilities:
 Direction of plant operations at the Incident
 Liaison with emergency services at the Incident
 Communication of developments to the Site Main Controller.
In addition to these tasks, they must ensure the evacuation of the area and assembly at muster
points and make sure that the emergency services are contacted quickly and briefly on the situation.
The main responsibilities of the site main controller are as follows:
 Overall coordination of onsite activity

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  Mobilization of additional onsite and offsite resources
 Notification and liaison with senior management, civil authorities and emergency services.
Depending on the size of the plant, and type of incident, there may be various plant personnel
who act as first responders. These include security staff, switchboard staff, administrative backup,
engineering staff and personal staff.

6.4 Emergency Response Service Training

The emergency services play a central role in the response to emergencies with offsite effects.
Each particular service will have its own particular responsibility and information needs. The
process of consultation should ensure that these are taken into account when an emergency
response is formulated. As such the following training must be undertaken:

 Interior structural, storage tank, process unit and marine firefighting response.
 Hazardous materials response (HAZMAT)
 Emergency medical provision
 Undertaking of high angle, confined space and trench rescue

Although not front line responders, a hospital must be involved in the event of an incident
which involves casualties. They must be informed of the type and implications of the potential
incidents and of the properties of the materials handled in the plant. The success of a response to
an emergency with offsite effects depends first and foremost on consultation and
communication. Ambulance services must also be made aware of the likely types of incidents
and their implementations on the plant. Links should be established with onsite first aid
personnel to coordinate actions.

Industrial fire-fighters must be trained to simulate specific hazards that may occur in a given
facility. These may include fire attack scenarios, offensive and defensive firefighting strategies
and flammable liquid fires. First responders, and technicians must be trained on how to
appropriately respond to a release of a hazardous material, preferentially by use of real life
scenarios, which will involve surveying and estimation of the potential harm posed by the
hazardous materials from a safe distance, consideration of options such as appropriate personal

29 | P a g e
protective equipment selection, and the safe halting of the release of a hazardous substance via
plugging, patching or other means, for pipelines, process systems, containers and other potential
emissive sources.

Warehouses, structures and buildings may be subject to exterior and interior fire attacks,
which require consideration of ladder operations, apparatus placement, overhaul operations, and
ventilation operations, with even more rigorous training such as “Rapid Intervention” (RIT)
training being necessary. Response team individuals must be trained in rigging and hauling
system building techniques, patient access, equipment identification, extrication techniques as
well, as rescuer responsibilities and safety practices.

6.5 Emergency Response Service Organization

For an emergency response system to be effective, good communication between the entire
command structures is vital. Communication, coordination and cooperation are all essential for
successful organisation. The following are a list of features to the organisation of a response:

 Initial reporting: Officially, no response can be made until an incident is reported.

Procedures should be established to ensure swift reporting of incidents and the initiation
of an emergency plan.
 Command Structures: A clear structure of command should exist amongst the response
personnel. When decisions must be made, they must be communicated effectively and
followed through systematically.
 Notification: All relevant bodies should be notified of the situation and kept informed of
developments.
 Record Keeping: Documentation of all aspects of the incident and response must be keep
concerning the incident, decisions taken and the deployment of manpower and equipment.
This facilitates the process of reassessment during operations and provides the basis for
an analysis of the response after the event.
 Flexibility and Reassessment: Although it is important that the structure of an emergency
response should be structured according to predetermined guidelines, sufficient flexibility
must be incorporated so that the response is always appropriate to the circumstance.
 Safety and welfare: Arrangements should be made to provide employees with food, water,
clothing, shelter and medical support in the event of an emergency. Protective clothing

30 | P a g e
 increases the risk of dehydration and overheating and appropriate remedies must be
considered.
 Training and Exercises: All personnel with specific roles must receive appropriate
training. Routine exercises should be performed to ensure that contingency arrangements
function properly and that all those who are involved in the response action become
familiar with their responsibilities.
 Dealing with the Media: The public perception of an emergency is widely influenced by
the media. Effective and sensitive handling of the media will be beneficial to all involved
in a response action.

All decisions made must be communicated to everyone involved and the plans must be
followed through. The emergency plan must be made known to all personnel on the plant,
especially the off-site emergency services which include fire fighters, police, ambulance, hospital
and civil defence. The off-site emergency service must be knowledgeable of the muster points on
the plant and must also be aware of record keeping of the incident.

In the aftermath of the incident there are several things which must be done to ensure that
the incident is controlled. These include the containment of incident effects, checking of
damaged equipment and updating of the media as to the state of causalities and the extent of
damage. Once these actions are performed, a detailed report of the incident must be made and
modifications to the emergency plan may be made to better adapt to similar future scenarios.

6.6 Making the Plan Work

When an emergency plan has been prepared, the following factors must be considered and
implemented so that it actually works:

1) Communication of the plan – Copies of the emergency plan should be circulated to all
relevant personnel in the plant. All employees should be made away of the relevant actions
they must take in the event of an emergency
2) Training – Individuals with specific operational roles must be trained and routine refresher
courses should be implemented.

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3) Provision of resources – When a plan is created, it is essential to compare the resources
which are required to those which are actually available. Action must be made to make up
for any deficiencies.
4) Drills and exercise- It is essential that an emergency plan is tried and tested. New plans
will require an initial full scale exercise to remove any impracticality. All drill are followed
by an assessment of the response and critiqued as to how they may be improved.

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 7.0 HAZARD SCENARIOS
7.1 Pool Fire
Scenario
On the morning of March 9th, 2010 the acetic tank of the Acrylic plant was scheduled for
its regular refuelling. This acetic was supplied via a 4 inch pipeline to acetic storage tank, T-108
having a capacity of 1206m3. A volumetric flow rate of 0.025m3/s is required for refilling the tank.
When the tank has reached a capacity of 90%, the level controller would stop the flow and a level
alarm will sound, notifying the control room that the process has ended. The respective valves are
then locked off after the alarm is sounded. On March 9th at 8:00 am, the control room operator of
the Acrylic plant worked tirelessly for 20 consecutive days and was very exhausted. He instructed
a floor operator to open the inlet valves to begin refilling of the tank. The exhausted control
operator doubled the flow to the tank thus reducing the filling time by a half so that he can go
home sooner.

The floor operator, was not aware of what transpired and averaged the time the tank would
take to be filled normally which was around 8.71 hours and left to pick up his children at school
after three hours since refilling began. Moreover, the control operator wrongly suspected that there
was a lot of time to spare before the tank would be filled and left his post at the control room and
went to the back of the plant to chat with some crew members. Unexpectedly, the level controller
on tank T-108 failed on that day and after approximately 4.4 hours the liquid level had reached
100% and liquid acrylic acid began to overflow into the bund. Since the liquid flowed into a bund
and was not spilled throughout the plant and there was no alarm heard and the overflowing acrylic
acid went un-noticed for about 2 hours.

In the year 2010, Trinidad and Tobago experienced one of its most severe droughts. Since
December of 2009 to March of 2010, the country had recorded approximately quarter of its
expected rainfall with the entire month of March experiencing approximately no rainfall. These
dry weather conditions took a severe toll on the islands causing a number of forest and bush fires,
complete with heavy smoke, destroyed many homes and depleted water reservoirs among other
destructions. Evaporation from the midday sun resulted in the volatile liquid forming a vapour
cloud. Approximately 8m away from the outer edge of the 1m high bund, hot work was being done

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on a section of piping. The welding operations occurring during the hot works produced smoke
which masked the acrylic odour and so the workers did not become aware of the spillage.

The sparks and excess heat emanating from the area where the hot works was occurring
ignited the extremely flammable vapour cloud resulting in a flash fire. The flame front then flashed
back to the acrylic source within the bund resulting in the ignition of a pool fire.

Results
Table 1: Probability of Fatalities for a Pool Fire

Probability of Fatality when exposed for 60 s

Receiver Er (W/m2) Exposure Time Y P Time to Pain
Distance(m) (s) Threshold(s)
5.00 13433.00 60.00 4.45 29.06 2.71
10.00 9800.00 60.00 3.37 5.18 3.93
20.00 5722.00 60.00 1.54 0.03 9.63
30.00 3686.00 60.00 0.03 0.00
40.00 2549.00 60.00 -1.22 0.00
50.00 1858.00 60.00 -2.30 0.00
60.00 1410.00 60.00 -3.25 0.00
70.00 1104.00 60.00 -4.08 0.00
80.00 886.00 60.00 -4.83 0.00
90.00 726.00 60.00 -5.51 0.00
100.00 606.00 60.00 -6.13 0.00

Probability of Fatality when exposed for 1.5 min

Receiver Er (W/m2) Exposure Time Y P Time to Pain
Distance(m) (s) Threshold(s)
5.00 13433.00 90.00 5.49 68.67 2.71
10.00 9800.00 90.00 4.41 27.76 3.93
20.00 5722.00 90.00 2.57 0.76 9.63
30.00 3686.00 90.00 1.07 0.00
40.00 2549.00 90.00 -0.19 0.00

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 50.00 1858.00 90.00 -1.27 0.00
60.00 1410.00 90.00 -2.21 0.00
70.00 1104.00 90.00 -3.04 0.00
80.00 886.00 90.00 -3.79 0.00
90.00 726.00 90.00 -4.47 0.00
100.00 606.00 90.00 -5.09 0.00

Probability of Fatality when exposed for 2 min

Receiver Er (W/m2) Exposure Y P Time to Pain
Distance(m) Time(s) Threshold(s)
5.00 13433.00 120.00 6.22 88.93 2.71
10.00 9800.00 120.00 5.15 55.82 3.93
20.00 5722.00 120.00 3.31 4.55 9.63
30.00 3686.00 120.00 1.81 0.07 19.55
40.00 2549.00 120.00 0.55 0.00
50.00 1858.00 120.00 -0.53 0.00
60.00 1410.00 120.00 -1.47 0.00
70.00 1104.00 120.00 -2.31 0.00
80.00 886.00 120.00 -3.06 0.00
90.00 726.00 120.00 -3.74 0.00
100.00 606.00 120.00 -4.35 0.00

Discussion
Fires primarily cause damage through the thermal radiation which can cause skin burns.
The extent of the damage is dependent on the time of exposure and is even a stronger function of
the distance from the source. The combustion of certain chemicals and materials can also produce
toxic fumes as well as thick smoke with can suffocate those trapped within the affected area. Fires
also cause structural damage by reducing the strength of the material, placing excessive stress onto
the structure which can lead to failure of metal support beams, roofs and walls.

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Fires can be broadly classified into 4 various types; jet fire, pool fire, flash fire and boiling liquid
expanding vapour explosion (BLEVE). Pool fires result when flammable liquid spills out into the
surrounding, forming a pool of liquid which is then ignited by some ignition source. Flash fires
are the ignition of a flammable vapour cloud by some ignition source. Typically flash fires
dissipate under a second, making the thermal radiation released a complex phenomenon to model.
Upon ignition, the flame front may travel back to the source of the gas release, resulting in either
a fire or explosion as seen in this particular scenario.

The release of acetic was primarily due to various factors such as; poor work habits,
inexperience, poor maintenance or an unexpected failure of safety detectors along with an
inadequate safety system design. Acetic is ranked 3 on health and 2 in fire on the NFPA scale. It
can be hazardous in the case of skin or eye contact, ingestion or inhalation where a substantial
over-exposure can result in death. Acetic acid exists as a colourless liquid at room temperature
with a pungent, vinegar-like odour. This liquid however is highly volatile and flammable with
lower and upper flammable limits of 4% to 19.9% respectively.

Due to the high volatility, large exposed surface area and amount which were available, a
relatively large quantity of 17513.78424 kg/hr was estimated to evaporate from the pool contained
within the bund. This vapour cloud reached an estimated ground level concentration of
133436.2487 ppm at a downwind distance of 8m where it was ignited by an ignition source present
during a hot work operation being performed on a section of piping.

Acetic vapour can form an explosive mixture with air. This vapour can travel relatively
large distances to a source of ignition and flash back to the release point which occurred within
the scenario. As acetic acid is a low molecular weight alcohol, it burns with a clean flame
producing little to no soot. The burning of acetic is made considerably more dangerous by it
burning with a near invisible flame. This poses the additional hazard of coming into direct contact
with the flame.

Some physical effects that can be caused by acetic acid contact as well as inhalation are
mild depression of the central nervous system, headaches, nausea, dizziness, drowsiness and

36 | P a g e
incoordination. If allowed to come into eye contact, blindness may develop or severe irritation
may occur. Swallowing or vomiting of the liquid can result in aspiration into the lungs.

From flame height calculations it was estimated that the pool fire would result in flames of
up to 27.64m high. The thermal radiation emitted was approximated by using the point source
model to reach as high as 13.43 kW/m2 for an observer at a distance 5m away. With such high
radiation intensity, the time required to reach the pain threshold would be under 3 seconds. At this
intensity, the probit equation of the effect model estimates a 29% fatality for an exposure of 60
seconds.

At a distance of 10m where the hot work was being performed, the thermal radiation being
received would be approximately 9.8 kW/m2. This intensity produces an estimated probability of
fatality of 5.177% and 55.82% for exposure times of 60 and 120 seconds respectively. At this
energy, the ignition of wood and meting of plastic tubing is expected. Tables 5-7 gives calculated
probability of fatality values at various distances from the fire source for exposure times of 1,1.5
and 2 minutes. For a distance of 60m from the source, a radiation intensity of 1.41 kW/m2 is
estimated. At this intensity, the time before the threshold to pain is reached is about one minute
and the percentage fatality expected is 0%. At a closer distance of about 40m, a calculated intensity
level of 2.549 kW/m2 was determined. At this intensity level pain should set in after about 30
seconds. This distance is still relatively far from the flame source to expect any fatalities. Closing
in to a radius of about 20m from the flame source, an intensity of 5.72 kW/m2 isexpected. At this
intensity, the pain threshold should occur within approximately 9 seconds and the expected
percentage fatality after 2 minutes of exposure is 4.55%. This heat intensity is tolerable enough to
allow for emergency actions of up to a minute by personnel without any shielding or heat
protection. Exposure should not be prolonged above this time limit as blistering of the skin and
second degree burns may begin to occur.

The threshold to pain occurs even faster (about 8 seconds) at a closer distance of 10m. At
this close distance the percentages of fatality become substantial with predicted values of 5.17%,
27.76% and 55.824% for exposure times of 1,1.5 and 2 minutes respectively. Exposure at such
high intensities should be limited to just a few seconds as second degree burns will occur after

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about 20 seconds of exposure. A safe intensity limit of 1.858 kW/m2 is reached at a distance of
50m from the flame source. At this distance no discomfort will be caused for any long exposure
(AIChE 1999) and is therefore taken as the ‘safe distance’.

In addition to the human injuries cause by the heat radiation in the form of burns, this
thermal radiation can also impact nearby equipment and structures. Acetic acid has an auto-
ignition temperature of 561.11oC. Such high temperatures can cause the steel acetic storage tank
located at the centre of the bund to fail due to excessive thermal stress. Upon failure, a large
quantity of acetic would be released into the bund and the flame fuelled further.

A pool fire of this magnitude would require the emergency plan to be put into effect. This
emergency plan needs to have the qualities of being simple and easy to follow, applicable at any
time of the day and flexible. Detection of the fire would be particularly difficult because of the
near invisible flame in which acetic burns. Fire detection however can still be possible through
infrared sensors which sets of an alarm should the nearby temperature rise above its typical range.

Upon recognition of a fire an immediate alarm should be sounded and the appropriate
authorities notified. These would include the on-site fire fighting and medical personnel,
emergency services such as fire, police, ambulance and hospitals and the plant manager or head
engineer. Fire services should also be made aware of the type of chemical involved in the fire and
the recommended fire fighting media and instructions. Since acetic is soluble and disperses in
water, a large fire should be contained using alcohol foam, water spray or fog. Water may be
effective for cooling the nearby structures but not as a means of extinguishing the flames since it
may not cool the acetic acid below its flash point.

During the fire, carbon monoxide, carbon dioxide and other toxic gases may be produced.
As such vapour respirator or even self-contained breathing apparatus should be used by any
personnel venturing close to the flames such as fire fighters. Medical services, both on and off-site
should be informed of the possible injuries expected and the recommended treatment. The most
common injury expected would be burns. Acute exposure to acetic either by ingestion or breathing

38 | P a g e
in high concentrations as may be the case in this scenario can produce symptoms which appear
between 40 minutes to 72 hours after contact.

These symptoms typically manifest within the central nervous system (CNS), eyes and
gastrointestinal tract. Those suspected to be exposed to high concentrations should therefore be
monitored carefully for this time period until certain that there were no adverse effects. After
detection of the incident, a diagnosis should be done to gather information such as the location of
the incident, chemicals involved, scale, type, current extent of damage, fatalities, chance of
escalation and the potential of any off-site impact. An effort should be made to stop the flow of
methanol to the tank if possible. Emergency sprinklers should be activated if installed as a method
of cooling the tanks to prevent them from rupturing and adding additional fuel to the fire.

Immediate evacuation of all personnel within a radius of 50m (distance to safe intensity
limit) of the flame source should be done. An effort should be made by the on-site fire team to
contain the flames within the bund and also cool the tanks until suitable off-site emergency services
arrive. The on-site medical service should begin treatment of any burns or acetic inhalation
immediately until ambulances arrive. The plan should also provide suitable means of relaying
information about the incident to the local community. Information should also be transferred to
the media through an immediate press release which should provide a response advice for the local
area and information about what is currently being done to control the situation.

Environmental and pollution agencies should also be informed of the incident and called
upon if their advice is required. Such advice would be on the control of the materials used to
suppress the incident such as the safe disposal of contaminated water used in fire fighting. Despite
acetic acid being easily biodegradable in water, acetic acid in fresh or salt water can have a severe
impact on aquatic life. Collection of the remaining acetic- water mixture after the fire has been
extinguished should be done using an explosion proof pump and care should be taken to avoid any
being discharged into sewers or waterways.

This incident could have been avoided if a clear description of the piping network for the
tank refilling system had been given. Standard operating procedures (SOP) should contain

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instructions for normal operation, start-ups and shut-downs, actions in emergencies, monitoring,
maintenance programmes, regular inspection programmes and repairs. The SOP could have
entailed an explanation that the closing of one value diverts all additional flow towards all other
open lines, thus lowering the refuelling time.

Additionally cameras should be installed overlooking the bund and tank farm so that any
spill can be quickly identified. Since acetic acid is the primary chemical stored on-site this poses
a large fire hazard especially since acetic fires can go undetected for substantial periods of time
because of its clear flame. Infrared detectors can also be placed to monitor the regions surrounding
the methanol tanks and set to sound an alarm should the temperature exceed that of normal
everyday conditions.

Manual control should not be required in the refilling process. Level sensors should be set
to sound an alarm in the event that the liquid exceeds the liquid high level and should trip close
the valves on the line with the acetic feed to the tank. It is also important in these level control
systems to have the high level trip connected to multiple level indicators since one may fail as seen
in the given scenario.

All components including the software of control systems should be frequently and
thoroughly tested through regular maintenance work. Checks should also be done to ensure that
the current safety and process control systems are adequate for any given process upset or incident
which can occur. This can be done through a HAZOP study or introducing new layers of protection
such as fire or blast walls and sprinkler systems to cool the tanks.

The primary hazard involved in performing any type of hot work and welding is a possible
ignition source for any nearby flammable material. Formal course of action must therefore be taken
when performing this type of maintenance work such as obtaining the appropriate permit.
Additionally to protect nearby equipment from the heat radiation a shielding method can be used.
A fire watch can also be assigned to look out for any fire which may be started. If a fire watch was
allocated he may have notice the strong alcohol smell present in the air and stop the work being
done until the nature of the odour was determined.

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 The decision in the site chosen and plant layout would also play a major role in mitigating
the effects of a fire should one begin. Placing the tank farm away from any major process
equipment and buildings occupied by plant workers would remove them from the direct line of
danger should a fire begin. Having a bund serves to contain any leaks or the entire tank capacity
should a total failure of the vessel occur. In the scenario the presence of the bund reduced the pool
area and helped to provide containment of the fire.

Equipment for extinguishing small fires or controlling larger ones until off-site fire fighting
services arrive should be readily available in convenient locations. These equipments should be
frequently checked and maintained to ensure proper operation and personnel trained in fire fighting
techniques.

Table 2 below shows the estimated likelihood of each event occurring as well as the overall
probability of the event within a specific time period. Over the estimated 15 year lifespan of the
plant the probability of the chain of events which lead to the scenario was determined to be 3.8%.
This scenario produced the highest probability with respect to the 3 various hazards investigated,
showing that the risk of a fire is the dominant hazard within the plant. It can be noted that the
number of years illustrate the probability of event occurring after a given number of years.
Table 2: Estimated likelihood of each event occurring

Fire events Failure rate 1 year 5 years 10 years 15 years

Level indicator 2.000 0.865 1.000 1.000 1.000
(faults/yr)
Level high alarm 0.2 0.181 0.632 0.865 0.950
(faults/yr)
Failure to notice - 0.040 0.040 0.040 0.040
level indicator
Probability of - 0.63% 2.53% 3.46% 3.80%
Scenario
occurring

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 Figure 7: Emittance Radiation vs Receiver at 60s exposure

Er (W/m2) vs Receiver (m) at 60s

exposure time
16000
14000
12000
Er, W/m2

10000
8000
6000
4000
2000
0
0 20 40 60 80 100 120
Receiver distance, m

From the figure, it can be shown that the Emittance radiation decreases exponentially as
receiver distance increase where around 6000 W/m2 posed minimal fatality and around 14000
W/m2 posed the highest fatality rate

Figure 8: Percentage fatality vs Er (W/m2) fatality at different exposure time (s)

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 100

Percentage fatality (%)

80
60
40
20
0
0 2000 4000 6000 8000 10000 12000 14000 16000
Er (W/m2)

Er (W/m2) vs Percetage fatality (%) at exposure time of 60s

Er (W/m2) vs Percetage fatality (%) at exposure time of 90s
Er (W/m2) vs Percetage fatality (%) at exposure time of 120s

From the figure above, it can be illustrated that higher the Er, for different exposure time,
the higher the percentage fatality which. From the graph, it can be shown that an exposure of 120s
posed the most dangerous effect on humans since it resulted in the highest fatality rate.

Figure 9: Receiver distance (m) vs Percentage Fatality at different exposure time (s)

100
Percentage fatality %

80

60

40

20

0
0 10 20 30 40 50 60 70
Reciver distance (m)

Receiver distance (m) vs Percetage fatality at exposure time 60s

Receiver distance (m) vs Percentage fatality at exposure time 90s
Receiver distance (m) vs Percentage fatality at exposure time 120s

Finally, from the figure above, it can be shown that the shorter the receiver distance to
source of fire, the higher the percentage fatality. It can be noted that and exposure time of 120s
resulted in the highest percentage fatality for a longer receiver distance.

43 | P a g e
Conclusion
By applying suitable discharge, source and effect models to demonstrate the hazards of
the pool fire, the following quantitative consequence analysis were obtained as:
 The safe distance for the pool fire was determined to be 50m from the flame source
 The entire event had a probability of 0.63%, 2.53%, 3.46% and 3.80% of occurring
within 1, 5, 10 and 15 years respectively.

Recommendations
Recommendations for further work into this report are:
 An additional hazard can be done to show the effects of extensive long term
environmental damage.
 The effects of the rupture of the acetic storage tank during the respective fire scenario can
be investigated.
 In estimating the likelihood of each event, a more complex probability function can be
assumed for the failure rate distributions such as a Weibull or logarithmic distribution.
 The solid plume radiation model can be used to evaluate the effects of the pool fire and
the results compared to that of the point source radiation model.
LOPA
1. Initiating Events (IE)

The following hazardous events which can result in the overflow or rupture of the acetic
storage tank, T-108 were considered:
 Incorrect estimation of filling time
 Misjudging tank current capacity (% of tank empty)
 Failure of liquid level gauging system
 Tank structural failure
The following hazardous events which can result in the overpressure or rupture of the
acetic storage tank, T-108 were considered:
 Misjudging tank current capacity (% of nominal design pressure)
 Failure of pressure gauging system
 Failure of pressure relief systems

2. Protection Layers (PL)

The following protection layers have been considered:

44 | P a g e
 Operator intervention using operator procedures: This action should be completely
independent of the initiating cause and other protection layers. No risk reduction factor
(RRF) can however be assigned to any operator response that relies primarily on the same
operator to identify the problem and rapidly correct it.
- Process Related Rounds and Inspections: the operator patrol routine should be
sufficiently frequently to detect possible accidents (RRF = 10 (Mannan 2005, 34/10))
- Observational: the operator patrol routine should be sufficiently frequently to detect
possible accidents which are obvious to the operator through normal visual or hearing
range (RRF = 10 ((Mannan 2005, 34/10))
- Corrective Action: For sufficiently slow occurring events where the operator has
suitable time to recognise the incident and take corrective actions (RRF = 10 ((Mannan
2005, 34/10))
- Alarms: The RRF associated with the operator response to a BPCS (Basic Process
Control System) alarm is dependent upon the time existing for the response and the
location.
 Basic Process Control System (BPCS): Since both tanks of the LOPA are the storage
vessels or final products, it is unlikely that any automated BPCS such as flow and
pressure control loops would be present.
 Flame arrester: Flame arresters should be installed on the pressure relief valve vent lines
to prevent any flame front from progressing into the vessel should the vent line be ignited
(RRF = 100 ((Mannan 2005, 34/10))
 Safety instrumented system (SIS): Safety Integrity Level 1 (SIL 1): These systems should
be independent of the BPCS if any is present. The SIS primarily consists of various safety
trips which occur when process conditions reach close to the maximum allowable
working conditions of the particular equipment/vessel. In the case of the T-108 storage
sphere, this would be the MAWP. For a SIL 1 the average probability of failure on
demand lies between 0.1-0.01 with a RRF of 10-100 (ANSI 1996).
 Pressure relief valve (PRF): For storage tank T-108, one PRF (RRF = 100 (Mannan2005,
34/10)) should be sufficient as the product is being stored under atmospheric conditions.
 Blast Wall: A blast wall can be constructed around main facilities and important
equipment within close proximity to the hydrogen storage sphere to either direct or

45 | P a g e
 contain any pressure wave which may occur upon rupture of the vessel (RRF = 1000
(Mannan 2005, 34/10))
 Fire detection with water deluge system: These response systems can be either operator
initiated or automated. For an operator initiated system, the RRF will be dependent upon
the operator’s response to an alarm whereas the typical RRF for an automated system is
given as 10 (Mannan 2005, 34/10)
Table 3: Showing Layer of Protection Analysis

1 2 3 4 5 6 7 8 9
Protection Layers
Initial Initiating Cause Process BPC Alar SIS Additiona Mitigated
Event Cause likelihoo Design S m l event
Descriptio d mitigation likelihoo
n d
Explained (Explaine Low Explaine None None Ye No High
above d above) d above s (explaine
d above)

HAZOP
Table 4:HAZOP Study for Pool Fire

Guide word Deviation Possible causes Consequences Action required

Intention: To fill acetic storage tank at a volumetric flow rate of 0.025 m3/s
None Flow Valve V -109 in Storage tank does Install low level alarm
closed position not full Routine patrolling
Acetic supplier Cavitation in pump and line inspection
restricts flow Flammable liquid
Pump P-109 fails release
Inlet line breakage
High Flow Pumping capacity Tank overflow Install flow rate
increased sensors

46 | P a g e
 Faulty controls Routine patrolling
Suction pressure and regular inspection
increased
Less Flow V-109 blockage Reverse flow Install a non-return
Partial failure of Reduced flow into valve
pump tank Install low level alarm
Reduction in
Leakage in pipeline product Routine patrolling
quality and inspection of
pump
Reverse Flow Check valve Decreased in tank
(Defective one-
way) liquid level
Pump failure Possible rupture of Install non-return
Pump Reversed joints or pipelines valves
Static liquid head Install low level
in alarms
tank greater than Perform regular
line pressure inspection on controls
Incorrect operation and valves

High Pressure Surge problems Rupture of line Regular routine patrol

Relief valves
isolated Damage of pump and inspections on
Failed open PCV controllers and
Blockage in line pipelines
Install high level
pressure alarms
Less Pressure Partial failure of Reverse flow in line Install a non-return

47 | P a g e
 Release of
pump-109 flammable valve
Leakage in pipeline liquid Install flow control
loop
Line 2 - From storage tank to pump
None Flow Pump-110 failure Cavitation of pump Re-fill storage tank
Valve V-110
closed No feed to supplier if empty
manually Flammable liquid Routine patrolling and
No feedstock in
tank release maintenance of pump
Install flow rate
sensors
Provide written
procedures which
require proper line-up
before pump start
High Flow Install flow rate
Pumping capacity Rupture of line or sensors
increased flange leaks Regular inspection
Install flow control
Faulty controls loop
Suction pressure
increased
Failure of P-110
pressure control
loop
Process surge due
to
turbulence in tank

48 | P a g e
 Less Flow Pump-110 failure Cavitation of pump Routine patrolling and
Valve V-110
closed Pump failure and check ups
Loq level liquid in Limited feed to Refill tank
Install low level
tank supplier alarms
Install visual alarm
Reverse Flow V-110 defective Rupture of joints or Perform regular
checkups on
Pump Failure pipelines controllers,
Incorrect operation valves and pipeline
Rupture of pipeline
High Pressure Surge problems line
Relief valves
isolated
Line blockage
Less Pressure Pump-110 failure Reverse flow in line Fit pressure low
Rupture or leak in alarms
pipeline Install non-return
valve
Routine patrolling and
maintenance of pump
High Temperature Faulty Possible line
instrumentation rupture Install thermal relief
and control valve after V-110
V-110 closed Install Temperature
indicator and high
during hot weather alarm
conditions
Storage tank-Acetic Acid 101

49 | P a g e
Less Pressure Regular inspection of
Pumping out when Damage to storage vent
vent line is in
choked tank line
condition
Drastic temperature Failure of tank shell
decrease in
ambient with leak to bund
temperature
Excessive
withdrawal
flow from P-110
Bird guard on vent
High Pressure High feed rate Rupture of storage line
Vent line choked tank installed against
External fire in
bund blockage
Install sprinklers
in and around bund for
cooling of tank
Less Level Release of Routine tank
Faulty level control flammable inspection
Construction of bund
Blockage of V-109 liquid to
and/or line 109 contain a leak
Install low level
while refilling alarms
Leak in tank
High Level Level indicator Overflow of acetic
fails acid Level indicator and

50 | P a g e
 level gauge to be
Tank overfill through vent checked
Construction of bund
Blockage of line in to
and V-109 contain a spill

Figure 10: Position of Acetic Tank in Plant Design

51 | P a g e
7.2 Boiling Liquid Expanding Vapour Explosion (BLEVE)
Scenario
At 7pm on the evening of 5th November, 2016 there was an unexpected power failure in
the plant. The plant was operating at normal conditions before this unexpected occurrence. The
reactor was operating at a flow rate of 5390 kmol/hr of feed into the acrylic acid reactor. At the
time of the power outage, there were three exothermic reactions taking place in the isothermal
reactor at a temperature of 312 oC and 500kPa. Immediately after the plant’s power outage with a
delay time of 5 seconds the backup generators came on. Since the backup generators had to supply
power to the entire plant there was an unknown decrease in the amount of electricity that was
supplied to the pump which resulted in the pump’s power being significantly decreased. This
resulted in a drastic decrease in the cooling water which was supplied to the reactor. Since the
controllers are monitored from the control room, there was no electricity supplied to the control
room since the generator for this area had to be turned on manually. This was difficult to do at the
time since the incident occurred in the night. Therefore, the decrease in the cooling water flow to
the reactor was unknown.

At this point, the flow of cooling water which was used to maintain the temperature
constant in the reactor was too low and there was a continuous increase in the temperature of the
reactor. This led to an increase in pressure of the reactor. There was a pressure relief valve at the
surface of the reactor which allows venting of excess pressure. However, this failed close at this
point which resulted in the rupture of some tubes inside the reactor. This led to a fire within the
reactor. There was a continuous pressure increase in the reactor since it was too risky to manually
open the pressure relief valve after the rupture of the tubes. This then led to a rupture and explosion
of the reactor which caused fragments of the reactor to fly various distances from the explosion.

Results
Table 5: Showing the Percentage Of Fatalities (%) Occurred With Varying Distance for The Thermal Radiation Probit Model

52 | P a g e
Distance from fireball,
Xc, m Heat Flux (kW/m2) Probit Equation Percent fatalities (%)
20 34580.47 28.60 100
40 8645.12 23.87 100
70 2822.90 20.05 100
120 960.57 16.37 100
180 426.92 13.60 100
210 313.66 12.55 100
250 221.31 11.36 100
300 153.69 10.11 100
350 112.92 9.06 100
400 86.45 8.15 99.9

Table 6:Results Were Calculated Using Formulas To Determine The Following Data

Calculated Results Calculated Values

Total moles in vessel, gmol 21 117.7
Total moles of fuel, gmol 15 838.28
Total mass of fuel, kg 1 141 306
Total energy of combustion, kcal 26 890 006
Equivalent mass of TNT, kg of TNT 24 008.93

Table 7: Results Obtained For the Percentage Fatalities for Each Probit Equation

Over Lung Eardru

Distance(m Impuls Structura
z Pressur Haemorrhag % m % %
) e l Damage
e (kPa) e Rupture
10 10
20 0.7 2797609 182 14.79 0 13.05 100 19.55 0
10
40 1.4 659450 190 5.84 68 10.26 100 15.33 0
99. 10
70 2.4 183253 112 -2.09 0 7.79 7 11.59 0
10
120 4.2 60273 70 -8.97 0 5.64 74 8.34 0
180 6.2 29802 49 -13.33 0 4.28 24 6.28 90

53 | P a g e
 210 7.3 23427 42 -14.82 0 3.82 12 5.58 72
250 8.7 18110 36 -16.41 0 3.32 5 4.83 43
10.
300 4 14034 30 -17.99 0 2.83 1.5 4.08 18
12.
350 1 11421 26 -19.27 0 2.43 0.8 3.48 6.5

Discussion
From the scenario discussed above, the disaster experienced was concluded to be a fire
followed by an explosion. This was determined from since the effects matched the criteria from
theory of a Boiling Liquid Expanding Vapour cloud Explosion (BLEVE). Calculations were thus
performed to determine the effects of the fire and explosion from the reactor to the surrounding
structures, environment and the society.

BLEVE Thermal Flux

The calculations performed for this section determined the maximum fireball diameter,
fireball combustion duration, the center height of fireball, the path length and the received flux. It
was estimated that the flammable material, i.e. acrylic acid forming in the reactor was 300 000kg.
Using this estimation, the maximum fireball diameter was calculated to be 388 m which was
combusted for a duration of 21.27 seconds. Additionally, the center height of the fireball was
calculated to be 291m with a path length of 159m. A vertical view factor was assumed since the
reactor was vertically positioned and this was found to be 0.17. Using a distance of 200m from the
fireball center on ground, the radiative flux received by the receptor at this distance was calculated
to be 283.04 kW/m2.

Blast Fragments from a BLEVE

For this calculation, it was assumed that the blast fragments were spherical having a
diameter of 16m. another assumption was made where the liquid fraction in the vessel was 0.75.
Since the vessel was constructed using stainless steel material, due to the acrylic acid being highly
corrosive, the vessel wall thickness was taken to be 0.5cm with a density of 7700kg/m3. The vessel
failure pressure and temperature were 500kPa and 685K respectively. For spherical blast fragments
the drag coefficient was taken to be 0.47 from the Consequences Analysis text. Using the

54 | P a g e
dimensions of the sphere as stated above, the total sphere volume was approximately 2145 m 3
having a liquid and vapour volume of 1609m3 and 536m3 respectively. The mass of TNT from the
explosion was found to be 230.38 kg. Additionally, the number of fragments from the explosion
was found to be 17 each having a mass of 911kg with a surface area of 47m2. From this area, the
average diameter of each spherical fragment was calculated to be 3.88m. The velocity of each
fragment was considered to be 200.24 ms-1 travelling within the range of approximately 400m.

Overpressure from a Combustion in a Vessel

For this calculation, there were several assumptions that were made. Firstly, the volume of
the vessel was assumed to be 200m3 containing 75% acrylic acid with an initial temperature of
412oC and initial pressure of 500 kPa. The heat of combustion of acrylic acid was calculated to be
1698 kcal/gm-mol. From the assumptions stated, the total moles in the vessel was calculated to be
21 117 gm-mol with the total moles of fuel being 15 838 gm-mol. Using the molar weight of
acrylic acid as 72.06, the total mass of fuel was found to be 1 141 306 kg with a total energy of
combustion of 26 890 006 kcal. This then resulted in an equivalent mass of TNT used of 24 008
kg of TNT.

The impact of this vessel explosion on humans and structures were calculated using its
respective probit equations which are seen in the sample calculations. The probit equations that
were used determined the percentage of fatalities at various distances from the explosions. The
probit equations analyzed the effects of lung hemorrhage, eardrum rupture, death from impact,
injuries from flying fragments and structural damage due to the explosion and the fatality for given
dose of thermal radiation from the fire. From Table 7, it was observed that there was a general
trend when analyzing the effects mentioned above. It was seen that with an increase in the distance
from the fire and explosion source there was a decrease in the effects of lung hemorrhage, eardrum
rupture, structural damage and thermal dose of radiation. It was deduced that there was a 0%
fatality with effects due to death from impact and injuries from flying fragments.

From Table 7, for the lung hemorrhage, it was seen that within a distance of 40m from the source
of explosion there was 68% fatalities and beyond this distance there was 0% fatalities. For the
eardrum rupture the fatalities decreased with distance with varying percentage fatalities ranging
from 100% to 0.8%. From the same table, it was seen that people within a range of 120m had a
significantly higher probability of eardrum rupture than those who were beyond 120m away from

55 | P a g e
the explosion. Similarly, for structures that are within a range of 120m, it was observed that these
equipment will be completely destroyed since it was calculated that they will be experiencing
100% structural damage. Beyond this distance, reaching 400m, it was calculated that only 2% of
the structures will be affects. Thus, it can be deduced that the impacts from structural damage is
relatively high. However, death from impact and injuries from flying fragments were found to
have minimum effects from the explosion since the percentage fatality was at a constant 0% with
a range of 20m to 400m from the effect source. The effects from the fire were determined to be
very detrimental for the entire range of 400m since there was a constant 100% fatality in the plant.
From the analysis above, it was observed that this disaster will have numerous effects due to human
health effects and heat radiation from the fire source.

Figure 11: Results showing the % fatalities for each probit equation used

120

100

80
% fatalities

60

40

20

0
0 50 100 150 200 250 300 350 400 450
-20
Distance, m

Eardrum Rupture Structural Damage

Lung Hemorrhage Heat Radiation

LOPA
1. Analyzing Consequence

There can be a minimum number of failures and errors which can trigger an explosion of a pressure
vessel. Some of the consequences may be:

 An increase in the flow rate of the raw materials into the reactor which leads to a pressure
increase in the vessel operating above the design pressure.

56 | P a g e
  Filling the tank to above its capacity limit i.e. filling the tank to 100% full when the
maximum safe capacity is 75% full.
 Since the three reactions occurring in the reactor are exothermic, increasing the temperature
causes a faster conversion. Therefore, increasing the temperature in the vessel to above its
design temperature which causes a runaway, uncontrolled reaction.
 Structural failure of the pressure vessel which results in vessel rupture.
 Failure of the cooling water system to maintain the isothermal temperature in the reactor
which can result in an increase the pressure and rupture of the pressure vessel.
 Failure of the pressure gauging system.

2. Tolerable Frequency

For the tolerable frequency of events happening on an industrial level needs to be very low. The
higher the consequence the lower the tolerable frequency therefore the company’s standards
should be set at an enterprise level. Such probabilities have known to be very low such as 0.01%
for a single fatality and reduced to even 0.001% for multiple fatalities.

3. Initiating Events

The cause of a deviation in the HAZOP is the initiating event in the LOPA. In this case, the
pump failed which resulted in no cooling water entering the reactor to keep the reactor at
isothermal conditions, resulting in an increase in temperature. This was followed by an increase
in pressure where the pressure control valve failed in the closed position leading to
overpressure of the vessel.

4. Independent Protection Layers

There are mechanisms that would prevent the consequences from occurring. These are more like
safeguards which are mentioned in the HAZOP. For this incident, since there was little cooling
water and a continuous increase in the temperature, there was no backup plan to put in place for
this occurrence. Therefore, some Independent Protection Layers can be reiterated from the
HAZAOP can be:

1. An alarm system can be setup for the temperature. This means that with any temperature
increase with more than 5oC there would be a virtual alarm on the operating system as well

57 | P a g e
 as a sound alarm coming from the plant. Another alarm would also be put in place on the
reactor when there is a change in the pressure. Therefore, for a 5kPa change in pressure
would sound an alarm to ensure that if there is an emergency in the plant it can be under
control before the event of a fire and explosion.
2. Manual flow values must be put onto both the process stream and the cooling water
stream to avoid reoccurrence of an automated valve failing in the case of an electricity
power outage. Along with manual flow valves, alarms should also be placed for both the
process and cooling water streams. This is to ensure that if there is any drastic increase in
the flow on either stream side which would in turn affect the temperature and pressure, it
can be controlled in case this turns into a runway reaction.
3. Additionally, more operators should be placed in charge of the flow, temperature and
pressure in and out the reactor to decrease the likelihood of the emergency occurring.
4. Lastly, routine maintenance checks must be done on all the pipes, valves and alarms on the
plant to decrease the probability of valves failing, pipes corroding and inhibiting flow of
the raw materials in the case of an emergency.

Table 8: Showing The Layer Of Protection Analysis

1 2 3 4 5 6 7 8 9
Protection Layers
Initial Initiatin Cause Process BPC Alar SIS Additiona Mitigated
Event g Cause likelihoo Design S m l event
Description d mitigation likelihoo
(safety d
valves,
dykes,
restricted
access)
Limited Lack of Low a)Pressur None None Ye No High
cooling cooling e relief s
water was water valve was
sent to the supply attached

58 | P a g e
 reactor due to the to the
to a power reactor reactor.
failure b)There
which was a
resulted in flow
an meter on
unwanted the
temperatur cooling
e and water
pressure stream to
increase the
which led reactor.
to a fire
followed
by an
explosion

From the table above, it was seen that since there was very limited Independent Protection
Layers for the system, the probability of a fire and explosion would be high. The expected
frequency of vessel rupture is determined by the Initiating Event frequency and the probability of
failure of safeguards. Since there was no BPCS and additional mitigation such as alarms and
manual valves the probability of safeguard failure would be high. However, due to the fact that the
initiating event frequency was low (power outage at the plant) the overall expected frequency was
considered to be low.

59 | P a g e
60 | P a g e
HAZOP

Guide Deviation Possible Causes Consequences Action Required

Word
Line 8 – Inlet to the Reactor
High Pressure  Relief valve  Rupture of  Regular
fail close pipeline checks on
 Blockage in  Damage to valves to
pipeline pump prevent
 Malfunctio  Decrease malfunction
n in pump conversion  Install high
to the of reaction pressure
reactor  Decreases alarms
 Compressor optimal
malfunction efficiency
of catalyst
Decrease Pressure  Compressor  Decrease  Install
malfunction conversion pressure
 Relief value of reaction alarms
fail open  Decreases  Perform
 Leak in optimal regular routine
pipeline efficiency checkups
of catalyst
Increase Temperature  Increase  Products  Install
inlet readily temperature
temperature reach their alarms on
of one of auto pipeline
the feed ignition
streams temperature

61 | P a g e
  Increases
the rate of
reaction
Decrease Temperature  Decrease in  Decrease  Install
one of the the rate of temperature
inlet feed reaction in alarms on the
temperature the reactor pipeline
 Phase
change
None Flow  Blockage in  No input  Install flow
pipeline for the meters along
 Power reaction to pipeline
malfunction occur
in pump  Reaction
 Breakage in rate and
pipeline to conversion
the reactor decreases


Less Flow  Blockage in  Less input  Install flow

pipeline for the meters along
 Surge in reaction to pipeline
pump occur
 Valve after  Reaction
the pump rate and
not fully conversion
opened decreases
Increase Flow  Malfunctio  Reactor  Install flow
n in pump overflow meters along
power, pipeline

62 | P a g e
 sending
more
cooling
water to the
reactor
 Increase
suction
pressure
Line 9 – Cooling Water to the Reactor
Increase Temperatur  Cooling  Less  Install
e system cooling temperature
malfunctions occurring in alarms for the
the reactor cooling water
Decrease Temperatur  Cooling  Less  Install
e system cooling temperature
malfunctions occurring in alarms for the
the reactor cooling water
None Flow  Blockage in  No cooling  Regular
pipeline water flow checks and
 Power to the maintenance
malfunction reactor on cooling
in pump  Temperatur water pump
 Breakage in e increase  Check and
pipeline to in the monitor
the reactor reactor reliability of
water supply
 Install flow
alarms
Less Flow  Blockage in  Cavitation  Regular
pipeline in pump checks on

63 | P a g e
  Surge in  Increase pipeline and
pump temperature valves
 Valve after of the  Check and
the pump products in monitor
not fully the reactor reliability of
opened  Increase in water supply
 Water heat  Install
supply generation temperature
failure rate alarms along
 Boiling pipeline
Liquid
Expanding
Vapour
Cloud
Explosion
Increase Flow  Malfunction   Install flow
in pump alarms
power,  Perform
sending regular line
more checkups
cooling
water to the
Figure 12: Hazop for the BLEVE Scenario
reactor
 Control
valve fails
 Increase
suction
pressure

64 | P a g e
Mitigation Methods
When a vessel contains a pressurized gas rupture, the resulting stored energy is released
into the surrounding areas. Since the contents are flammable and it is operating above the
autoignition temperature, this causes a fire. This continuous energy in turn generates a shock wave
which causes acceleration of the vessel fragments upon explosion.

From this scenario, it was seen that the fire and explosion affected up to a distance of 400m.
Therefore, various methods should be put in place to decrease these hazardous effects in the case
of a fire and explosion of a reactor. One of the recommendations that should be done to limit the
effects of the disaster is by putting a barrier wall surrounding the reactor or any pressure vessel
that is used throughout the plant. This will lessen the effect of the overpressure as well as decrease
the range of the flying fragments. Since the wall is made of concrete, this will absorb some of the
shockwave that is produced from the reactor. Another recommendation should be a practiced fire
drill at a muster point which is located a safe distance away from the reactor if there is an
emergency in the plant. This will avoid any haphazard behavior of the workers in the plant since
the drill is regularly practiced and therefore all the workers will be accounted for to minimize
injuries or deaths on the plant. Lastly, a sound alarm should be put in place loud enough for the
entire plant as well as the surrounding areas to be heard. This is to make everyone aware that there
is an emergency on the plant and to follow emergency procedures.

Conclusion
For this scenario, there was a fire followed by an explosion of the reactor which as mentioned
previously caused by a decrease in the flow rate of the cooling water to the isothermal reactor. It
was deduced that there would have been fatalities on the plant such as eardrum rupture, lung
hemorrhage and structural damage, with 100% fatalities at a distance of 20m and a decrease in
the fatalities with a decrease in the distance over a range of 210m. From research, it was
concluded that having concrete barrier walls around the reactor as well as sounding alarms when
there was an emergency in the plant could have avoid mishaps like this.

65 | P a g e
7.3 Toxic Gas Release
Introduction
Toxic gas are gases that are harmful to humans when inhaled or ingested in various
quantities. Examples of such gases include ammonia and chlorine. The official definition of a
toxic gas is: “A compressed gas or vapor that has a median lethal concentration (LC50) in air of
200 parts per million (ppm) by volume, or 2 milligrams per liter of mist, fume, or dust, when
administered by continuous inhalation for one hour (or less if death occurs within one hour) to
albino rats weighing between 200 and 300 grams each.

A toxic gas release can cause severe illness, birth defects, poisoning, disease or death
when inhaled or absorbed by living organisms. In the chemical industry, toxic gases are released
into the environment mostly by leakages from vessels and pipelines that usually operate under
high pressure. When comparing major accidents in industries, fires are considered to be the most
likely of occurring, followed by explosions and then toxic gas releases (Casal et al, 2012).

66 | P a g e
Although toxic gas releases is the least likely of occurring, its effects is based on the physical and
chemical behaviour of the gas which will determine the degree of its adversity on the
environment and human health.

Acrylic acid is a liquid at room temperature and pressure. It can burn mucous
membranes and possibly underlying tissues when inhaled or swallowed, even in low
concentrations. Contact with the liquid can cause severe burns of the skin and/or eyes, and
possibly cause permanent eye damage. The American Conference of Governmental Industrial
Hygienists (ACGIH) has a threshold limit value (TLV) of 2 ppm (5.9 mg/m3) for an eight hour
time-weighted average basis with skin notation. Equilibrium concentrations of acrylic acid
vapor in air at room temperature can far exceed this value.

The greatest potential for human exposure to acrylic acid is by dermal contact or by
inhalation. Acrylic acid produces toxic effects mainly at the site of contact: nasal lesions if
inhaled, skin lesions upon dermal contact, and gastrointestinal effects if acrylic acid solutions are
swallowed. Contact with acrylic acid can cause severe burns. Exposure to mists or vapor at
levels above the recommended exposure limits can produce eye, nose, or lung irritation and
injury. Seriousness of injury depends on the degree of exposure. The symptoms can include
respiratory irritation and watering of the eyes.

If acrylic acid vapours are inhaled, the affected person should immediately be removed
from the contaminated area to a well ventilated area. Emergency medical assistance should be
requested. Acrylic acid exposure usually causes mucous membrane irritation, sore throat, and
coughing. Rapid development of respiratory distress with chest pain, difficulty breathing,
swelling of the throat and accumulation of fluid in the lungs (shortness of breath, cyanosis,
expectoration, coughs) may occur. Lung injury may progress over several hours. Medical
professionals or those properly trained may consider administration of oxygen.

67 | P a g e
 Figure 13: Acrylic Acid Dose-Effect Relationship

Properly inhibited acrylic acid is normally stable for up to one year from the date of
production when stored and handled under recommended conditions. Commercially available
acrylic acid is stabilized (inhibited) with 180-220 ppm hydroquinone monomethyl ether
(MEHQ), which prolongs the shelf life, i.e., the time before spontaneous polymerization occurs.

However, this shelf life is reduced exponentially with increasing temperature. Exposure
to high temperatures, therefore, must be avoided. The polymerization of acrylic acid can be very
violent, evolving considerable heat and pressure and ejecting hot vapour and polymer, which
may auto-ignite. An explosion hazard exists due to extremely rapid pressure build up. Several
case histories are known in which vessels of acrylic acid exploded due to violent (“runaway”)
polymerization when proper procedures were not followed. Many serious incidents involving
acrylic acid have been reported. In several cases, explosions due to excessive heating of the
vessel have occurred. Experience has shown that overheating of acrylic acid is by far the most
common cause of inadvertent polymerization.

Scenario
On the morning of February 16th, 2017, plant operators of the Acetic and Acrylic Acid
Plant located in La Brea, Trinidad, initiated a scale up of the original process recipe in the acrylic
acid reactor to produce a higher amount of the product, due to an increased market demand for
acrylic acid.

The standard conversion of propylene to acrylic acid required contacting with mixed
metal oxide catalyst in a highly exothermic reaction. The usual process occurred in a 102 m3
Reactor, R-100 at 312 -313.5˚C. Plant managers decided to scale up the process by increasing the

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propylene batch to the reactor and desired to synthesize the reactions in the same time as the
standard recipe. Mr. Adam, the reactor engineer superintendent, determined the amounts of
propylene to oxygen ratio to the tank. At approximately 9 am that morning, the operators decided
to load all of the additional propylene to the initial reactor charge. The engineers did an
immediate addition of the specified propylene so that a large amount of additional propylene was
shot into the reactor. The operators observed no alarming immediate changes as vessel
conditions seemed to be in a safe range and the cooling operation was normal. Everything was
running as expected and at around 9:30 am some operators left for a breakfast break, leaving
only two on duty.

However, due to the sudden change in propylene concentration within the reactor, the
conversion reaction significantly increased in energy production. Runaway reactions began
occurring within the vessel and a large build-up of heat and thus momentous temperature
increases resulted. Temperatures rose to approximately 400°C and this resulted in the rapid
polymerization of the acrylic acid which exceeded the cooling capability of the mechanism that
was put in place to take away the heat generated inside the reactor.

At around 9:50 am, alarms sounded in the control room concerning significant
temperature increases in R-100. Operators rushed into controls and immediate additional cooling
was implemented into the reactor. On the plant, vapour could be seen venting out from the
reactor manway rapidly. Due to the vigorous polymerization of the acrylic acid within the tank it
caused rapid boiling of the acrylic acid formed and produced concentrated acidic vapour to form,
significantly increasing the vessel pressure.

At 9:53 am, the pressure release valve blew followed by the violent rupture of the top of
R-100 producing a 3.2 m diameter hole and the release of toxic acrylic acid gas into the
atmosphere. The explosion simultaneously caused the ignition of the reactor vessel contents
which encouraged the continuous polymerization of the acid so that acrylic acid vapour was
consequently continuously released into the atmosphere. The acrylic acid vapours was
excessively exposed for over 40 mins in the plant before response units could have subsided the
fire and stop the venting of acrylic acid vapour. Other plant equipment in surrounding areas of
the explosion was affected as well as employees and the neighbouring village. Weather
conditions were quite stable (stability class F) and the wind speeds were 2 m/s.

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Results
Source Release

Discharge Rate Model

Table 9: Shows The Data Required To Calculate The Gas Release Rate.

Heat capacity ratio of gas: 1.026

Hole size, (mm) 3200

Final Pressure, (bar abs) 10

Initial Pressure, (bar abs) 3.5

Temperature, (673) 673

Gas molecular weight, (kg/kmol) 72.064

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 Table 10:Shows The Results Obtained From The Discharge Rate Model

Hole area, (m2) 8.042

Upstream gas density, (kg/m3) 12.879
Expansion factor, Y 0.614
Actual pressure ratio 0.65
Interpolated mass flow, (kg/s) 14,523.978

After carrying of the calculations, the discharge rate of the gaseous acrylic acid from the
ruptured reactor was found to be 14,524 kg/s. The full calculations are shown in appendix. The
duration of the gas release was approximately 40 minutes hence the continuous plume dispersion
model was used. (AIChE, 1999). Since meteorological data for the site is absent, a stability class
F with a wind speed of 2m/s and rural conditions were used.

Dispersion Model

Table 11: Shows The Release Concentration (Ppm) Over A Range Of Downwind Distances For Stability Class F At A Wind
Speed Of 2 m/s

Distance Concentration
(m) (ppm)

40 25481793.08

60 22688867.47

100 11810168.21

200 3556036.27

250 990928.80

500 512037.87

750 290431.01

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 1000 200536.28

2500 67060.75

5000 29651.51

7500 19160.84

10000 14409.53

70,000,000 96.91

Figure 14: Shows The Following Graph Illustrates The Concentration Profile Of Acrylic Acid Gas With Respect To Downwind
Distance.

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Plume Isopleth

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 Isopleths for Plume Calculations
2000

1500

1000
Distance Crosswind (m)

500

0
0 5000 10000 15000 20000 25000
-500

-1000

-1500

-2000
Distance Downwind (m)

100 ppm 1000 ppm 5000 ppm 10,000 ppm

25,000 ppm 50,000 ppm 75,000 ppm

Figure 15: Shows The Isopleth For The Plume

120

100
Fatalities (%)

80

60

40

20

0
0 2 4 6 8 10
Exposure Time (min)

100 ppm 250 ppm 500 ppm 750 ppm

1000 ppm 10000 ppm 2500 ppm 5000 ppm

Figure 16: Shows The Change In Percentage Fatality With Increasing Exposure Times For Given Concentrations Of Acrylic
Acid.

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 Table 12: Shows The Concentrations Required To Cause Different % Fatalities For Different Exposure Time

Conc (ppm): 100 250 500 750 1000 2500 5000 10000

Time (min)
% Fatality
5 0.04 4.95 35.4 64.49 81.62 99.52 99.99 100
10 0.35 15.57 60.38 84.36 93.81 99.94 100 100
15 1 26.14 73.77 91.66 97.2 99.98 100 100
20 1.97 35.4 81.62 95.02 98.52 99.99 100 100
25 3.18 43.28 86.57 96.8 99.14 100 100 100
30 4.58 49.94 89.87 97.83 99.46 100 100 100
35 6.11 55.58 92.16 98.47 99.64 100 100 100
40 7.74 60.38 93.81 98.88 99.76 100 100 100

Table 13: Shows The Effects Of Certain Concentrations Of Acrylic Acid

Concentration (ppm) Effects on Humans

1.5-10  Noticeable odour, mild eye irritation, noticeable discomfort
60-100  Eye burning and irritation, respiratory irritation
100 - 250  Alerting discomfort, skin and respiratory irritation. Extreme
eye irritation and skin blisters. Irreversible health effects with
extreme damage or death within 30 minutes of exposure.
500  Life threatening health effects that are irreversible and can
cause death within 10 minutes of exposure.
>5000  Death within short periods of time

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Discussion
The release of toxic gases into the atmosphere poses a lot of dangers to human life and
other organisms in the environment. The release of gases can be particularly dangerous as some
can occur without any form of rapid detection since many gases are colourless with a vast
amount being odourless. Once toxic gases make their way into the atmosphere, they affect the air
quality by reducing the quantity of oxygen or by increasing the concentration poisonous gases in
the air. A hazardous atmosphere is one which may expose employees to the risk of death,
incapacitation, impairment of ability to self-rescue (i.e. escape unaided from a permit space) or
acute illness. (Western Iowa Tech Community College, 2009).

Acrylic acid is not classified as a human carcinogen however it is listed as a human

respiratory toxicant by the US Environmental Protection Agency. Exposure can occur through
inhalation, ingestion, and contact to the eyes and skin. People can be exposed to acrylic acid
through direct contact with product containing it or by inhaling air contaminated with acrylic
acid vapour.

A quantitative analysis of an acrylic acid vapour release from a ruptured vessel was
carried out to gain data and trends to logically assess the effects and risks associated with the
toxic gas release as well as aid in developing a suitable emergency response and mitigation
measures.

Firstly, a discharge rate model was used to determine the rate of release of acrylic acid
vapour from the source. This was then followed by a dispersion model which gave the
concentration in the air at atmospheric conditions. Then, a plume model analysis was carried out
to illustrate the change in concentration at different distances. An isopleth plot was also
generated and finally a probit model analysis was done in order to determine the percentage
fatalities for given concentrations of acrylic acid in air.

Source Release

Discharge Rate Model

Discharge models are the first stage in the development of consequence estimates. The
discharge rate model is a means of quantifying the outflow scenario by approximating the release
rate of the gas (Kakosimos & Assael, 2010). They consider the phase of the fluid release,

76 | P a g e
thermodynamic path, endpoint, hole size and duration (AIChE 1999). The acrylic acid was
release at 4000C and 10 bar, at which it was in a gaseous phase. The rupture size of the vessel
was 3.2m and it had an area of 8.04m2. With these given conditions the mass flow rate of the
acrylic acid gas through the rupture was calculated to be 14,524 kg/s. This large flow rate
resulted from the high operating pressure of the reactor vessel and because of the relatively large
size of the rupture. Also, the duration of the gas release lasted for 40 minutes after the initial
rupture. Since the duration of the release was over 10 minutes, a plum release was used
compared to a puff. It is worth nothing that over the duration of the gas release, 34,857,547 kg
of acrylic acid escaped into the atmosphere.

Dispersion Model

A dispersion model calculation provides an estimation of the area affected and respective
concentrations involved in the gas release. The model depends on the gas release rate,
atmospheric conditions, surface roughness and the size of the release hole. The vapor cloud
behaviour is also important when selecting the appropriate model. The release duration and the
gas buoyance and whether the release is continuous or instantaneous (t < 3 mins) are also key
contributors when choosing a model.

Gaussian Model

This model was can be used to predict the behaviour of a continuous release of a
material. The density of the toxic gas was greater than that of air so an appropriate model had to
be used. The Gaussian model was chosen because it is usually utilized for buoyant gases but can
also be applied to dense gases assuming that the gas is diluted by the surrounding air.

Plume Model

The plume model was chosen since the duration of the gas release was 40 minutes i.e
greater than 10 minutes. (AICHE, Guidlines for Consequence Analysis of Chemical Releases
1995). As such the release through which the gas escaped in the behaviour of the plume was
considered as continuous since it was more than 10 minutes. The plume model calculates the
concentration of the gas at various downwind distances based on the release rate of the vapor, the
height of release and the atmospheric conditions such as temperature, wind speed and pressure.

77 | P a g e
 The scenario occurred between the hours of 9-10 am, it was assumed to be a stable
morning in a rural environment with moderate amount cloudiness. Gas dispersion is influenced
by a variety of factors such as wind speed, atmospheric stability and terrain. The Pasquill
stability classes were used as they provide adequate representations for atmospheric stability and
are easily applied. The Pasquill- Gifford stability ratings, F class was chosen with a wind speed
of 2 m/s.

Table 3 and figure1 shows the concentration of release of the acrylic acid at varying
downward distances. From figure1, it was illustrated that the concentration of acrylic acid started
at a maximum and then sharply decreased as the distance from the point source increased. The
graph then plateaued as the acrylic acid concentration became constant. The Gaussian’s model
was only able to give accurate estimations within the distance range of 100m to 10000m. The
concentration of the acrylic acid peaked at its highest, 25,481,793.08ppm at a distance of 40m
away from the point source. On the other hand, at a distance of 10,000 m the concentration
lowered to a value of 14,409.530pm and concentrations continued to decrease with increasing
distance from the source. This decrease in concentration was due to the dispersion of the acrylic
acid into the atmosphere.

At a distance of 70,000,000m from the source it was found that the acid concentrations
decreased to less than 100 ppm. That is to a concentration which may not cause immediate death
but may just be slightly discomforting. However, as can be seen from figure 17, at times exposed
greater than 5 minutes deaths are likely to occur. Ultimately, it was found that acid
concentration at close distances were extremely high (> 5000) such that it can cause immediate
death.

Plume isopleth

By using the Gaussian plume model, an isopleth can be created which gives a three-
dimensional surface representation of the boundary of a fixed gas concentration. The downwind
distance was varied from 100 to 10000m which are the limit of the Gaussian model. The Pasquill
stability was kept constant as class F, with a surface wind speed of 2 m/s. The isopleths that were
produced gave the area of the plume and the maximum plume width.

78 | P a g e
 When plotting the plume isopleths graph, both negative and positive values were
considered because it would increase the accuracy of the results and define the plume. It can be
observed from the plume isopleth, that as the distance downwind increases from the point
sources, so does the plume width and area. This implies that the gas begins to disperse to a
higher degree and as a result cover a larger area. Consequently, the concentration of the acrylic
acid begins to decrease with increasing dispersion.

Consequence Model

This model gives a statistical representation of a consequence. This was used in

conjunction with the probit equation. The exposure to acrylic acid gas of a particular
concentration for a said duration was assessed. The extent of the human effect may be estimated
of data permits. The consequence under consideration is death through inhalation. The same
concentration s that was used to construct the plume isopleth were inputted into the probit
equation and the percentage fatality was found. The exposure time and downward distance were
also varied and the respective percentage fatalities were calculated. From table 4 it can be see
that as the exposure time was increased, so did the percentage fatality. The same can be said for
increasing the concentration level. This is also illustrated on the plot of percentage fatality versus
concentration.

Conclusion
 The total discharge rate of toxic gas was calculated to be 14,524 kg/s while the total
amount if acrylic acid released over the duration of the escape was found to be
34,857,547 kg.
 The concentration of acrylic acid in the atmosphere decreased exponentially with
increasing downwind distance.
 As the concentration of gas in the atmosphere decreased, the isopleth area and maximum
width increased.’
 At concentration of 1000ppm and over the chances pf fatality were either 100% or very
close to 100% .
 The longer the duration of exposure, the higher was the chance of fatality.

79 | P a g e
Recommendations
 The accident could have been easily prevented if the scale up procedure was carried out
in a more systematic and controlled approach.
 Routine inspections and regular maintenance work rather than pushing production to its
rim.
 The toxic gas release model can be improved by repeating the concentration isopleths
with various stability classes and wind speeds. The results will therefore provide a more
accurate comparison.
 The Gaussian dispersion method only holds for up to 10,000m. The distance downwind
at acid concentrations of <25 ppm is greater than 10,000. Therefore, an alternative
method should be employed to better represent these calculations graphically.
Calculations to qualitatively illustrate the likelihood of this toxic gas release occurring
were not determined. More complex probability functions including the Weibull
distribution should therefore be utilized to provide more efficient/ accurate
representations of the likelihood.
 The acrylic acid vapor was a dense gas, consequently a dense gas model should have
been used e.g The Britter Mc-Quaid Model.
 The effect of topography can be studied as well as the environmental implications of the
toxic gas release

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LOPA
Acrylic Acid Reactor, R-100

1. Analyzing Consequences
There are limited ways of which a toxic gas release can occur from the acrylic acid reactor.
Consequences may be:
 Immediate addition of feed which may increase reactions as well as induce runaway
reactions, increasing the pressure of the tank and cause increased venting.
 Rupture of the pressure release valve
 Temperature increases may cause acid polymerization or even boiling of contents and
lead to overpressure and increased venting
 Failed cooling may cause temperature rise and ultimately increased venting as mentioned
previously.
 Overpressure can also cause vessel rupture and expose acrylic acid vapour to the
atmosphere.

2. Tolerable Frequency
This indicates the risk tolerance the company can withstand. It estimates the tolerance, for
this case, the toxic gas release from the reactor and in terms of percentage; values should
normally be very small, ranging from 0.001% to 0.1% per year.

3. Initiating Event
For the toxic gas scenario, the initiating even involved an incorrect over scaling of reactants
flow into the reactor which elevated temperatures and vessel pressures leading to significant
overpressure of the reactor and consequently vessel rupture. The vessel rupture provided
means for the acrylic acid vapour to escape into the atmosphere.

4. Identifying Protection Layers

Protection layers can be considered as mechanisms which prevent the consequences from
occurring. For this scenario, mechanisms include:
 Following operational procedures and reaction requirements when adding ingredients
to the reactor.
 Ensure routine maintenance of all streams, investigating valves and checking for
leakages.

81 | P a g e
  Add check valves to exit streams to prevent backflow and level buildup and
overpressure within the reactor
 Add temperature, pressure alarms and controllers to the equipment that alert
operations for high and low temperatures and pressures.
 Install level controllers to control production levels within the reactor. Also, high and
low level alarms should be installed to alert operators of any dangerous changes.
 A scrubber can be implemented to the reactor to reduce concentrations of acid
released from venting.

Table 14 :Layer of Protection Analysis for the Scenario

1 2 3 4 5 6 7 8 9
Protection Layers
BPC Alarm SIS Additiona Mitigate
S l d event
Initial Event Description

mitigatio likelihoo
n (safety d
Cause likelihood
Initiating Cause

valves,
Process Design

dykes,
restricted
access)
Improper Inefficien Lo a)Pressur None Only Yes No High
scale- up of t cooling w e relief temperat
process by water valve ure alarm
immediatel supply to was for the
y adding the attached reactor
large reactor to the
amounts of reactor.
reactants b)There
which was a
caused flow
temperature meter on

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 increases the
and cooling
exothermic water
runaway stream to
reactions the
leading to reactor.
vessel
overpressur
e and
rupture
releasing
toxic
acrylic acid
gas.

Inferred for the above table, it was observed that there was very limited Independent
Protection Layers for the system so that the probability of a fire and explosion would be high.
The expected frequency of vessel rupture is determined by the Initiating Event frequency and the
probability of failure of safeguards. Since, there was no BPCS and additional mitigation such as
controllers, sufficient alarms and manual valves, the probability of safeguard failure would be
high. However, due to the fact that the initiating event frequency was low (wrong scaling-up of
the reactor process) the overall expected frequency was therefore considered to be low.

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HAZOP
Acrylic Acid Reactor, R-100

Figure 17: Schematic of Reactor, R-100

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 Table 15: HAZOP For The Reactants Feed Stream To Reactor

Reactants Feed To Reactor Vessel

Guide Process
Parameter Causes Consequence Recommendations
word Deviation
Flow No No Flow  V-1 fails  Reduced  Regular
 Line blockage production of maintenance of
 Vessel crude products the feed stream
overpressure  Reaction doesn’t  Input a flow
have desired meter
ingredients for  Input an
effective reaction expansion valve
 Overpressure  Expansion valve
blocks flow to alarm
exit line and
increase in vent
release
Flow Increase Increase  V-1 Faulty  Increase addition  Regular
flow  Upstream of reactants maintenance and
process upset  Runaway inspection of
reactions may valves
occur  Expansion valve
 Increased used
temperature and  Flow meter
pressure  Level controller
 Polymerization of  High level alarm
acrylic acid
 Overpressure
vessel

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  Increased venting
 Increased product
formation and exit
stream flow

Decreased Decreased  V-1 Faulty  Reduced  Installation of a

flow  Line reaction rate low level alarm
blockage within vessel
 Process  Reduced
upset production of
upstream crude products
 Pressure rise  Reduced flow of
in vessel exit stream
 Increased
venting due to
increased
pressure

Temperature low Decreased  Increased  Reduce the rate  Installation of

temperature cooling of reaction temperature
 Reduce controllers
production of
desired products
 Reduce flow of
exit stream
High Increased  Reduced  Produce runaway  Install
Temperature cooling or reactions temperature
cooling  Acrylic acid controllers
malfunction polymerization  Install
 Increased temperature
pressure alarms

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  Increased  Increased venting
flow of  Increased reaction
reactant feed rate
 Increased
products formed
 Increase exit
stream flow
 Cause
overpressure if
cooling is
ineffective
Pressure low Decreased  Leakage in  Reduced flow to  Install pressure
Pressure line the reactor due controllers
to leakage  Install pressure
 Production rate alarms
decreases  Do frequent
 Exit stream flow inspections and
decreases maintenance
 Break in line  Check for
exposes leakages
propylene which
may lead to
explosions, fires
and damage to
plant personel.
High Increased  Pressure  Rupture of line  Install pressure
Pressure build up due  Explosions release valves
to faulty V-1  Increased  Install pressure
 Overpressure venting out of controllers and
in vessel reactor alarms.

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  Do regular
maintenance

Table 16: HAZOP For Cooling Stream To Reactor

Cooling Water To Reactor Vessel

Guide Process
Parameter Causes Consequence Recommendations
word Deviation
Flow No No Flow  V-3 fails  Rise in  Regular
 Plugged temperature of maintenance of
cooling coils reactor the stream
 Water source  Increased  Install cooling
failure reaction rate water flow meter
 Runaway  Install high
reactions will temperature
occur alarm
 High
temperature will
cause acid
polymerization
Increased Increase  V-3 Faulty  Increased  Regular
flow  Temperature cooling maintenance and
rise in  Reduce reaction inspection of
reactor rate valves

Decreased Decreased  V-3 Faulty  Increase reactor  Regular

flow  Line temperature maintenance and
blockage  Increase the rate inspection of
 Need to of reaction valves
increase

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 reactor  Can cause acid  Install flow
temperature polymerization controller
 Partial if temperature  Install high
Water increase temperature
source significantly alarm
failure  Increase vessel
pressure
 Increased
venting
 Increased exit
stream flow
 Inefficient
cooling

Temperature increase Increased  High  Limited capacity  Install cooling

Temperature temperature of the cooling water high
of water system temperature
supply alarm

Table 17: HAZOP For Crude Product Stream From Reactor

Crude Product Stream From Reactor Vessel

Guide Process
Parameter Causes Consequence Recommendations
word Deviation
Flow No No Flow  V-2 fails  Reduced  Regular
 Line blockage production of maintenance of
 Reactor crude products the feed stream
shutdown  Product buildup  Input a flow
within vessel meter
 Install a level
meter and alarm

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 Increase Increase  Increase flow  Increased  Install Flow
flow of feed pressure within meter
 Increased stream  Level controller
rate of  Line rupture within reactor
reaction  Install high level
within alarm for reactor
reactor  Install pressure
 Increased controller
level within  Install high
tank pressure alarms
 Overpressure
in vessel
Decreased Decreased  V-2 Faulty  Reduced  Install flow
flow  Line production of controller on
blockage crude products stream
 Reduced  Line blockage  High and low
flow of or faulty valve level alarms on
reactant feed can cause reactor
 Catalyst product buildup
deactivation within vessel
or reduction  Overcooling
 Over cooling and catalyst
reduction can
reduce the rate
of reaction form
product
formation

Temperature low Decreased  Over cooling  Reduce the rate  Installation of

temperature of reaction temperature

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  Reduce meters on the
production of stream
desired products
 Reduce flow of
exit stream
High Increased  Reduced  Increased  Install
Temperature cooling or pressure of line temperature
cooling due to increased controllers
malfunction flow  Install
 High  Increased amount temperature
temperatures of products alarms
within reactor formed
vessel  Increase stream
flow

Pressure low Decreased  Leakage in  Decreased  Install pressure

Pressure line production of controllers
 Decrease crude product  Install low
reaction rate  Exit stream flow level alarms
 Low level in decreases  Install pressure
reactor  Break in line alarms
exposes acrylic  Do frequent
acid which may inspections and
lead to injury to maintenance
plant personnel.  Check for
leakages
High Increased  Overpressure  Rupture of line  Install pressure
Pressure in vessel  Explosions release valves

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  High product  Install pressure
levels in controllers and
reactor alarms.
 Do regular
maintenance

7.4 Explosion
Scenario
On April 2nd 2010, a nearly twenty year old heat exchanger violently ruptures causing an
explosion killing 7 workers. The second heat exchanger, E-102 in the acrylic acid plant; E-102 is
a shell and tube heat exchanger with cooling water flowing in the tubes and acetic acid, acrylic
acid, propylene, steam and air flowing in the shell side of the heat exchanger. The catastrophically
failed due to long-term damage from high pressure in the shell side. The water that flows through
the tubes contain contaminants which condenses from the process, the contaminants builds up on
the wall of the tubes resulting in fouling; hindering the transfer of heat in the process. The fouling
reduces the efficiency of the heat exchanger and thus the tubes are cleaned every 6 months. To
avoid shut down of the plant, new valves were installed for the heat exchanger that was connected
in series to allow for operation of one heat exchanger at a time while the other heat exchanger is
on shut down for cleaning.

On March 28th 2010, one heat exchanger was taken offline and disassembled for cleaning
while the other heat exchanger remained in service. By midafternoon on April 1st, the cleaning was
complete and operators initiated the start up on the offline heat exchanger. The procedure required
an inside board operator monitoring the control and one outside operator monitoring the large
manually operated valve but the heat exchanger had a history of developing leaks during start up,
something that the operator personnel came to see as normal. Additional operators from nearby
units were called upon to assist on the startup including mitigation of potential leaks. By 10:30
p.m. the outside operator was joined by 6 workers from within the plant and were located around
the heat exchanger where start up activates continued passed mid night. Unfortunately, unknown
to the workers, the steel shells for the heat exchangers had been severely weakened due to cracking

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caused by high temperature hydrogen attack; stressing the steel and over time causing fissures.
Over time, the fissures grew to form large internal cracks.

Unfortunately, the valves created a hazard since it isolated the heat exchanger from its
protected pressure relief valve. The water level dropped in the heat exchanger and it was assumed
to be caused by fouling. A maintenance worker increased the water level flowing into the heat
exchanger; increasing the pressure in the tubes. The increase in pressure caused an expansion of
the cracks in the tubes of the heat exchanger causing a leak of the gases in the heat exchanger.
Propylene along with other gases leaked from the tube which is high flammable causing a violent
rupture of the heat exchanger.

Results
Table 18:Percentage Of Fatalities For The Distance Of The Range Of The Fragments.

Distanc z Over Impuls Lung % Eardru %

e Pressure e Hemorrhag m
/ Pa e Rupture
3 1.391 655053 190 15.30805 100 41.44747 100
6 2.781 135909 100 4.456212 29 38.4121 100
9 4.17 59943 70 -1.19207 0 36.83222 100
12 5.56 35980 54 -4.71404 0 35.84709 100
15 6.95 25131 44 -7.19018 0 35.15448 100
18 8.34 19128 37 -9.07353 0 34.62769 100
21 9.73 15369 32 -10.5833 0 34.20541 100
24 11.12 12811.71 28 -11.839 0 33.85416 100

Table 19: Percentage Of Fatalities For The Distance Of The Fragments.

Distance z Over Impuls Structura % Injurie %

Pressure e l Damage s from
/ Pa Impact
3 1.391 655053 190 1208.307 100 -4.7476 0

93 | P a g e
 6 2.781 135909 100 1063.616 100 -7.4819 0
9 4.17 59943 70 988.3057 100 -9.0014 0
12 5.56 35980 54 941.3461 100 -10.106 0
15 6.95 25131 44 908.3309 100 -10.979 0
18 8.34 19128 37 883.2196 100 -11.717 0
21 9.73 15369 32 863.0899 100 -12.336 0
24 11.12 12811.71 28 846.3466 100 -12.904 0

Discussion
Explosions are characterized by shock- waves, which can be heard as a bang. This shock
wave can cause damage to both buildings and people. The direct effects of overpressure can be
fatal but the indirect effects of collapsing buildings, flying glass and debris can cause far more loss
of life and severe injuries.

Types of explosions:

1. Gas explosions- occurs when considerable quantities of flammable gases are released,
mixing with air to form an explosive vapour cloud before ignition takes place.
2. Vapour cloud explosions:
i) Confined- such as those which occur within some form of containment (e.g. Vessels,
pipe-work), or in less obvious situations.
ii) Unconfined- occurring within the open air.
3. Dust explosions- occur when flammable solids, in the form of very fine powder, are
intensively mixed with air and subsequently ignited.

The greatest danger arises from the sudden massive release of flammable material, producing
a large cloud of flammable and possibly explosive vapour. When this cloud becomes ignited, the
effects associated with it depend on a number of factors including wind speed and the degree of
dilution of the cloud with air. These effects can lead to large amount of casualties and wholesale
damage both on site and beyond. However, even in major incidents, the effects are generally
limited to a few hundred meters from the site.

The calculations of a TNT equivalent energy and the shockwave correlations were used for
this scenario. Brode’s expression, 1959 determines the energy required to raise the pressure of
the gas at constant volume from the atmospheric pressure to the initial or burst pressure; 1.601

94 | P a g e
bar abs. Assuming that the expansion occurs isothermally and the ideal gas laws applies, the
TNT equivalent mass was calculated to be 10.01 kg. Available energy represents the maximum
mechanical energy that can be extracted from a material as it moves into equilibrium with the
environment, which was calculated using Crowl (1992) to be 47.11 MJ.

Baker et al method was used to estimate the overpressure for a rupture of a gas filled
container. Firstly, Brode’s equation was used to calculate the energy of the explosion, 94.22 MJ.
The scaled pressure, distance and impulse was calculated from the target was calculated to be
0.104 bar, 2.27m and 0.0224 k Pa.ms. The final pressure was calculated to be 0.2678 bars was
lower than the vessel pressure thus the vessel pressure was used as the vessel over pressure.

When a high explosive detonates, a large number of small fragments with high velocity and
chunky shape result. In contrast, a BLEVE only produces only a few fragments, varying in size
(small to large), shape (chunky or disked shape) and initial velocities. Fragments can travel long
distance because large, half- vessel fragments can “rocket” and disk shaped fragments can
“Frisbee”. In calculating the projectile effects, the method considers only fracture of cylinder and
spherical vessels into 2, 10 and 100 fragments. For this scenario, a cylindrical vessel was
rupturing with 3 fragments occurring.

Once fragments are accelerated, they will fly through the air until they affect another object
or target on the ground. The second part of the calculations involves estimating the distance the
projectile can travel which as 19 m. The scaled pressure and the speed of sound for an ideal gas
was calculated to be 0.000191 bars and 457 m/s respectively. These parameters were then used
to calculate the initial fragment velocity, 20 m/s, which was then used to calculate the distance
the fragment would fly. The maximum distance and the safety distance estimated are 40.82 m
and 22.44m respectively.

For “chunky” fragments, which are normally expected, the lift coefficient is zero for these
objects and the lift to drag ratio is thus zero which was used to calculate the scaled initial
velocity, 2.58 m/s.

In general, vessels of pressurized gas do not have sufficient stored energy to represent a
threat from a shockwave beyond the plant boundaries. Thus, these techniques will be more

95 | P a g e
beneficial for applications involving plant risks. However, these types of incidents will result in
domino effects particularly from the effects of the projectiles produced.

A boiling liquid expanding vapour explosion (BLEVE) occurs when there is a sudden loss of
containment of a pressure vessel containing a superheated liquid or liquefied gas. A BLEVE is a
sudden release of a large mass of pressurized superheated liquid to the atmosphere. In this
scenario, the BLEVE occurred due to manufacturing defects. The sudden containment failure
allows the superheated liquid to flash which increases the volume by approximately by 200
times. This will be sufficient to generate a pressure wave and fragments. Since our released
liquid is mixture of acetic acid, acrylic acid, propylene and water, the liquid is flammable thus,
fireball will result.

The blast wave produced by a sudden release of fluid depends on many factors
(AIChe,1994). Factors such as fluid released, energy it can produce on expansion, rate of energy
release, shape of the vessel, type of rupture, and the presence of reflecting surfaces in the
surroundings. A power law correlation was used to correlate the BLEVE diameter to the duration
of the mass and the maximum fireball diameter was found to be 269.2m. The mass of fuel
involved and the fireball diameter, duration and thermal emissive power was used to calculate
the thermal radiation.

Disadvantages of using the BLEVE method are that it required actual distribution of the
flame temperature, the composition of the gases near the fireball, the geometry of the fireball,
absorption of the radiation by the fireball itself, and the geometric relationships of the receiver
with respect to the fireball.

The effects of BLEVE mainly relate to human injury thus a geometric view factor for a
sphere to a receptor required. Generally, a fireball center has a height, H above ground. The
distance was measured from a point at the ground directly beneath the center of the fireball to the
receptor at ground level. Thus for a horizontal surface, the view factor and received flux was
calculated to be, 0.16 and 34.63 kW/m2.

The probability of this event occurring is low due low flow rates entering the heat exchanger.
Also, this scenario occurred since the heat exchangers were operating for 20 years without a

96 | P a g e
change in the pipes. Additionally, improper control system and placement of valves were done
hence the explosion.

Conclusions
According to calculations, persons in the range of 22.5m will experience ear drum rupture
and structural damage. Person in the range of 6m will be affected with lung hemorrhage and
since there is only two fragments, the probability of persons being injured by the explosion is
small.

Recommendations
This scenario can be prevented by proper alarm systems and implementations of fail to close
valves. Additionally, proper safety checks of the shell and tube and piping should be done more
often and pipes should be replaced when fissures are noticed before cracks are formed.

LOPA
Heat Exchanger

1. Analyzing Consequences
There are minute ways of which a heat exchanger can rupture and these may include:
 High thermal stresses within the heat exchanger my lead to collapsing of the tubes and
heat exchanger rupture.
 Corrosion of tubes, causing tube failures.
 Deterioration of shell
 Increased flow into vessel
 Overpressure within heat exchanger

2. Tolerable Frequency
For this case, the rupture of the heat exchanger should be designed to have frequencies very
small, ranging from 0.001% to 0.1% per year.

3. Initiating Events

97 | P a g e
 The scenario involves the initiating events as failure of the heat exchanger tubes due to
overpressure caused by increased water flow. This caused huge leakage of the tube contents
(mostly propylene) and thus a violent rupture of the heat exchanger.

4. Identifying Protection Layers

 On all inlet streams for both the tube and shell side install pressure controllers, meters
and alarms so that the pressure can be controlled and that any significant pressure drop or
increase would alert operators.
 Install flow valves and alarms on all streams so flow can be monitored, overpressure due
to increased flow can be prevented as well as equipment wear can be reduced.
 Install temperature meters and alarms in the equipment to prevent heat exchanger wear
and thermal stressing.
 Do regular maintenance of equipment, streams and valves.

Table 20: Layer of Protection Analysis for the Explosion Scenario

1 2 3 4 5 6 7 8 9
Protection Layers
BPC Alarm SIS Additional Mitigate
Initial Event Description

S mitigation d event
(safety likelihoo
Cause likelihood
Initiating Cause

valves, d
Process Design

dykes,
restricted
access)
Increase in Faulty or Mediu 1.Remo None No Yes No High
pressure wearing m vable
caused an of heat tube
expansion exchange bundle
of the tubes design
cracks in could . Tube
the tubes of withstand can be

98 | P a g e
 the heat increased remov
exchanger pressure ed for
causing a of flow. cleani
leak of the ng
gases in the .
heat
exchanger.
Propylene
along with
other gases
leaked from
the tube
which is
highly
flammable
causing a
violent
rupture of
the heat
exchanger.

From the above table, it was observed that there were very limited Independent
Protection Layers for the system which indicates that the probability of the heat exchanger
rupture, would be high. Since, there was no BPCS and additional mitigation such as controllers,
alarms, valves and even meters, the probability of safeguard failure would also be high.
Additionally, the initiating event frequency was considered medium as vessel malfunction due to
wearing caused by age may be common in some industries. Thus, the overall expected frequency
would therefore be considered to be moderately high.

99 | P a g e
HAZOP
Tube side entering:

Guide Property Cause Consequence Action

word word
Less Flow Pipe blockage Temperature of High Temperature
process fluid is Alarm
constant
More Flow Failure of cooling Temperature of Low Temperature
water valve process fluid decrease Alarm
Reverse Flow Failure of process Product offset Install valve
fluid inlet valve
More Pressure Failure of process Bursting of fluid Install of high
fluid valve pressure Alarm
Less Pressure Failure of process Reverse Flow Install of high
fluid valve pressure Alarm

100 | P a g e
 Less Temperature Reactor Malfunction Denatured Catalyst Low Temeperature
Alarm
More Temperature Reactor Malfunction Denatured Catalyst High Temperature
Alarm

Tube side leaving:

Guide Property Cause Consequence Action

word word
Less Flow Pipe blockage Temperature of process High Temperature
fluid is constant Alarm
More Flow Failure of cooling Temperature of process Low Temperature
water valve fluid decrease Alarm
Less Flow Leakage of tube and Contamination of Proper maintenace
cooling water process fluid and operator alert
entering
Less Flow Hardness of cooling Less cooling and Proper maintenance
water cracking of tube
More Pressure Failure of process Bursting of fluid Install of high
fluid valve pressure Alarm
Less Pressure Failure of process Reverse Flow Install of high
fluid valve pressure Alarm
Less Temperature High shell side Valve malfunction Install Flow valve
flowrate Alarm
More Temperature Low shell side Valve malfunction Install Flow valve
flowrate Alarm

Shell side entering:

Guide Property Cause Consequence Action

word word

101 | P a g e
 Less Flow Failure of inlet Process fluid Install Temperature
pneumatic check temperature not heated indicator
valve to open properly
More Flow Failure of pneumatic Output of Process fluid Install Temperature
check valve to close temperature too high indicator
Reverse Flow Electronic control No water to absorb Isolate the gate
valve fails heat valve and enable by
pass
More Pressure Inlet check valve More water flowing in Install High Flow
closes the shell side Alarm
Less Pressure Inlet check valve Less water flowing in Install Low Flow
opens the shell side Alarm
Less Temperature Temperature control More cooling Maintenance of
system fail control system
More Temperature Temperature control Insufficient cooling Maintenance of
system fail control system

Shell side outside

Guide Property Cause Consequence Action

word word
Less Flow Failure of inlet Process fluid Install Temperature
pneumatic check temperature not heated indicator
valve to open properly
More Flow Failure of Output of Process fluid Install Temperature
pneumatic check temperature too high indicator
valve to close
Reverse Flow Electronic control No water to absorb Isolate the gate
valve fails heat valve and enable by
pass

102 | P a g e
 More Pressure Outlet check valve Less water flowing Install Low Flow
closes out of the shell Alarm
More Pressure Failure of process Bursting of fluid Install of high
fluid valve pressure Alarm
Less Pressure Failure of process Reverse Flow Install of high
fluid valve pressure Alarm
Less Temperature Temperature More cooling Maintenance of
control system fail control system
More Temperature Temperature Insufficient cooling Maintenance of
control system fail control system

8.0 REFERENCES
AIChE (American Institute of Chemical Engineers). 1999. Guidelines for Consequence. Analysis
of Chemica Releases. New York: AlChe.

AIChE. 1999. "American Institute of Chemical Engineers). Guidelines for Consequence."

Functional Safety: Safety Instrumented Systems for the Process Industry Sector. ANSI (American
National Standards Institute). ANSI/ISA 84.01. Functional Safety: Safety Instrumented
Systems for the Process Industry Sector. United States: ANSI.

Chemicals, Cameo. 2016. Chemical Data Sheet, Acrylic Acid. Accessed April 2, 2017.
https://cameochemicals.noaa.gov/chemical/17021.

Goldstein, M. 2008. Journal of Emergency Nursing: JEN:." 538-542.

Mannan, Sam. 2005. Lee’s Loss Prevention in the Process Industries Vol 1-3. 3rd ed.

Perry et al. 1997. Perry's Chemical Engineers’ Handbook 7th ed. New York: McGraw-Hill.

103 | P a g e
2016. Pubchem. November 7th.
https://pubchem.ncbi.nlm.nih.gov/compound/acetic_acid#section=Top.

Seader, J.D.& Henly, E.J. 2006. Separation Process Principles. Danvers: John Wiley & Sons
Inc.

Sinnott, R.K. 2005. Coulson & Richardson's Chemical Engineering Volume 6, 4th ed. Elsevier
Butterworth-Heinemann.

Seader, J. H. (2006). Separation Process Principles. Danvers: John Wiley & Sons Inc.

Zhang, Wu, HAZOP Introduction, January 2007

9.0 APPENDIX
9.1 Pool Fire Scenario
Table 21: Shows The Design Specifications And Capacity Of Tank , T-108

Volume of tank, Vt (m3) 1000

dtank 12.2
Htank 10.3
Qin (m3/s) 0.025

Cross-sectional area of storage tank:

2
𝜋𝑑𝑡𝑎𝑛𝑘
𝐴𝑡 =
4
𝜋 × 12.22
𝐴𝑡 =
4

Therefore 𝐴𝑡 = 116.9 𝑚2

The bund capacity is usually taken as 110% of the total capacity of the tank:

𝑉𝑏 = 1.1(𝑉𝑡 )

104 | P a g e
 𝑉𝑏 = 1.1(1000)

Therefore 𝑉𝑏 = 1326 𝑚3

For a perfect square bund of height 1m, the length of one side of the bund is:
𝐼𝑏 = √𝑉𝑏

𝐼𝑏 = √1326

Therefore 𝐼𝑏 = 36.4𝑚

Hence total area of acetic pool is :

𝐴𝑝 = 𝐴𝑏 − 𝐴𝑡

𝐴𝑝 = (36.4 ∗ 36.4) − (116.9)

Therefore 𝐴𝑝 = 1209.5 𝑚2

Initial liquid level % in tank 1 = 35%

Time it takes for tank to be 100% filled:

(1 − 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 % 𝑙𝑖𝑞𝑢𝑖𝑑) ∗ 𝑉𝑡
𝑡𝑓 =
𝑄𝑖𝑛 ∗ (60𝑚𝑖𝑛𝑠)

𝑡𝑓 = 522.6 𝑚𝑖𝑛𝑠
Since the flow rate was doubled, the new time to fill the tank would therefore be halved which
results to:
522.6
2

𝑇𝐹 ’ = 261.3 𝑚𝑖𝑛𝑠
The maximum spillage time that is allowable , that is, the time before the process operator
returns to control room is:
𝑡𝑠 = 261.3 𝑚𝑖𝑛𝑠 = 4.36 ℎ𝑜𝑢𝑟𝑠

Specified time of spillage will be 2 hours

105 | P a g e
Evaporation Model
Table 22: Showing The Input Information For The Pool Fire Scenario

Boiling point of Acetic Acid (oC) 118

Mr of Acetic Acid 60.05
Cp of Acetic acid (kJ/kg0C) 2.043
Latent heat of vaporization of Acetic Acid 402
(kJ/kg)
k of concrete (W/mK) 0.0264
Density of concrete (kg/m3) 2400
Cp of concrete (kJ/kg0C) 8.6944 x107
H (W/m2K) 10
Tin (oC) 27
Temp of concrete (oC) 37
Pool Temperature (oC) 30
Time after spill (s) 900
Kg 0 (m/s) 0.0083
Mr of water 18.02

Assuming that the tank is surrounded ground which is made of concrete and thermal diffusivity
is given by:
𝑘
𝛼=
𝜌𝑐𝑝

1.565
𝛼=
2400 ∗ 750

𝛼 = 8.69 𝑥 10−7 𝑚2 𝑠 −1

It can be noted that heat transferred from the ground is modelled by a simple one dimensional
heat conduction equation given as (American Institute of Chemical Engineers). Guidelines for
Consequence 1999, 63)):
𝑘 × (𝑇𝑔 − 𝑇)
𝑞𝑔 =
(𝜋𝛼𝑡)1/2

106 | P a g e
 1.565 × (37 − 30)
𝑞𝑔 =
𝜋 × (8.69𝑥10−7 ) × 9001/2

𝑄𝑔 = 220.95

It can be assumed that conduction to air is negligible and that solar insolation qr is 1366 W/m2

Furthermore, the heat lost by convection can be modelled by the Newton’s law of cooling

𝑞𝑐 = ℎ × (𝑇𝑝 − 𝑇∞ )

𝑊
𝑞𝑐 = 10 × (30 − 27) = 30
𝑚2

The total heat into the pool can therefore be calculated:

𝐻𝑇 = (𝑞𝑐 + 𝑞𝑏 + 𝑞𝑟 ) × 𝐴𝑝

𝐻𝑇 = (30 + 1366 + 220) × (1209.5) = 1956𝑘𝑊

The total volume of liquid spilled in 7200 seconds or 2 hours is calculated by:
𝑉 = 𝑄𝑡𝑠

𝑉𝑠 = 0.025 × (7200) = 180𝑚3

Therefore the mass of Acetic Acid can be determined by the using the following equation:
𝑀 = 𝜌𝑉𝑠

𝑀 = 1050 × 180 = 189 000𝑘𝑔

Height of this Acetic Acid pool within the bund is:

𝑉𝑠
𝑉=
𝐴𝑝

180
𝑉= = 0.15𝑚
1209.5

Hence the mass transfer evaporation for a high volatility liquid (Acetic Acid) is calculated by:
𝐻𝑇
𝑚=
𝐿𝑣

107 | P a g e
 1956 𝑥 103 𝑘𝑔
𝑚= = 4.865
402𝑥 103 𝑠

Dispersion model
Meteorological conditions

The table below illustrates the conditions and meteorological conditions present at the time of
release.

Table 23: Meteorological And Gas Release Data For Ignition Of Vapour Cloud

Region Urban
Wind speed at 10m (m/s) 4
Release time Day
Daytime insolation Strong
Height of release (m) 0.15
Stability class C
Duration of release (mins) 15
Discharge rate (kg/s) 4.865
Ambient pressure (Pa) 101325
Ambient temperature (K) 300

Wind Speed

The wind speed at the allocated release height can be obtained by using the following formula of
power

Law approximation:
𝐻 𝑝
𝑢𝑧 = 𝑢10 ( )
10

Where:
p is the exponent for an urban region under stability class C which is given as 0.20:
0.15 0.20 𝑚
𝑢𝑧 = 4 ( ) = 1.72
10 𝑠

108 | P a g e
Pasquill-Gifford Dispersion Coefficients

Under a stability class of C for an urban region, the dispersion coefficients are given for the
following empirical correlations:
𝜎𝑦 = 0.22𝑥(1 + 0.0004𝑥)−0.5 𝑎𝑛𝑑 𝜎𝑧 = 0.2𝑥

At downwind distance 𝑥 = 8𝑚, the dispersion coefficients determined from Equations above
are:
𝜎𝑦 = 1.76𝑚 𝑎𝑛𝑑 𝜎𝑧 = 1.6𝑚

Ground Level Concentration

The average ground level concentration can be calculated and obtained using the Gaussian
Plume Equation:

2
𝐺 1 𝑦 1 𝑧−𝐻 2 1 𝑧−𝐻 2
< 𝐶 >= exp [− ( ) ] {exp [− ( ) ] + exp [− ( ) ]
2𝜋𝜎𝑦 𝜎𝑧 𝑢𝑧 2 𝜎𝑦 2 𝜎𝑧 2 𝜎𝑧

With ground level source assumed directly downwind from the source of release, the values of y
and z are set to 0. By substituting the respective terms in the above equation, the ground level
concentration at an 8m downwind distance is:

< 𝐶 > = 0.318 𝑘𝑔/𝑚3

The conversion of the above value is calculated below:

< 𝑐 > 𝑅𝑇
𝑝𝑝𝑚 =
𝑃𝑀𝑟

0.318𝑥 106 (0.08206)(307)

𝑝𝑝𝑚 = = 133436.25 𝑝𝑝𝑚
1 ∗ 60.05

It can be noted that the flammability limits of acetic acid is between 40,000 -200,000 ppm.

Since the calculated concentration is within this range, it is likely that the gas would ignite if it
comes into contact with an ignition source.

Pool Fire Model

Table 24: Showing Values Used In The Calculation Of The Pool Fire Model

109 | P a g e
 Heat of combustion of acetic acid (J/mol) 786425
Heat of combustion of acetic acid (kJ/kg) 13096.17
Boiling Point of acetic acid (K) 391
Ambient temperature (K) 303
Density of acetic acid (kg/m3) 1050
Heat capacity of acetic acid (J/mol.K) 124.4
Relative humidity % 74
Air Density at ambient conditions (kg/m3) 1.164

𝑇𝐵 𝑝
∆𝐻 ∗ = ∆𝐻𝑣 + ∫ 𝐶𝑃 𝑑𝑇
𝑇𝑎

∆𝐻 ∗ = 23390 + 124.4(391 − 303) = 34337.2

The vertical rate of liquid level decreases according to (AIChE 1999, 211))

∆𝐻𝑐
𝑦𝑚𝑎𝑥 = 1.27 𝑥 10−6 ( )
∆𝐻 ∗

786425
𝑦𝑚𝑎𝑥 = 1.27 𝑥 10−6 ( )
34337.2
𝑚
𝑦𝑚𝑎𝑥 = 2.9087 × 105
𝑠

Mass burning rate can be calculated by using the following relation:

𝑚𝐵 = 𝜌 × 𝑦_𝑚𝑎𝑥

𝑚𝐵 = 1050 × 2.9087 × 10−5

𝑘𝑔
𝑚𝐵 = 0.03054 .𝑠
𝑚2

The H/D or ratio of flame height to the pool diameter is given by (AIChE 1999, 214):
0.61
𝐻 𝑚𝐵
= 42 ( )
𝐷 𝜌𝑎 √𝑔𝐷

110 | P a g e
Where:
𝐷 is the equivalent diameter of the square bund:
0.61
𝐻 0.03054
= 42 ( ) = 0.759
𝐷 1.164√9.81 × 36.42

Therefore, the flame height is given by:

𝐻 = 0.759(36.42) = 27.635𝑚

The Point Source model for a receiver distance R =10m is applied

It was assumed that the point source is at the centre of the bund, where it is equal to a height at
half the height of the flame, hence point source height is given by:
𝐻
ℎ𝑠𝑜𝑢𝑟𝑐𝑒 =
2

27.635
ℎ𝑠𝑜𝑢𝑟𝑐𝑒 = = 13.82𝑚
2

Distance from this point source to the receptor is determined by:

2
𝑥 = 𝑆𝑞𝑟𝑡(𝐻𝑠𝑜𝑢𝑟𝑐𝑒 + (𝑅 + 0.5𝐿𝐵 )2 )

𝑥 = 𝑆𝑞𝑟𝑡(13.822 + (10 + 0.5(36.42)2 )

𝑥 = 31.412𝑚
View at this distance can be calculated as follows:
1
𝐹𝑝 =
4𝜋𝑥 2

1
𝐹𝑝 = = 8.065𝑥10−5 𝑚−2
4𝜋 ∗ 31.4122

Partial pressure of water can be calculated as:

5236
𝑃𝑤 = 101.325(𝑅𝐻)𝑒 14.4114− 𝑇

Where relative humidity (RH) = 74%

5236
𝑃𝑤 = 101.325(0.74)𝑒 14.4114− 303

𝑃𝑤 = 3140.8 𝑃𝑎

111 | P a g e
The atmospheric transmissivity is determined by (AIChE 1999, 191)
𝜏 = 2.02(𝑃𝑤 𝑥)−0.09

𝜏 = 2.02(3140.8 ∗ 31.412)−0.09 = 0.717

By assuming a conservative value of 0.35 for the fraction of energy that is converted to radiation,
the thermal flux is given by:

𝐸𝑟 = 𝜏𝑎 𝑚𝐵 ∆𝐻𝑐 𝐴𝐹𝑝 𝜂

𝐸𝑟 = 0.717 ∗ 0.0305 ∗ (13096.17x103 1209.5 ∗ 8.065𝑥10−5 0.35 = 9800 𝑊𝑚−2

Thermal Effect Model

Thermal Dose Probit

The probit equation is normally used to estimate fatality level for certain thermal dose from pool
or flash fires and is given by (AIChE 1999, 264)
4
𝑡𝐼 3
𝑌 = −14.9 + 2.56ln( 4 )
10

Where:
𝑡 is the duration of exposure in seconds and I is thermal radiation intensity in W/m2

𝐴 receiver at distance 5m from source have an time of exposure at 60s:

𝑊
𝐸𝑟 = 13433
𝑚2
4
60(13433)3
𝑌 = −14.9 + 2.56ln( )
104

𝑌 = 4.45

Percentage fatality

The percentage fatality is given by using the following equation:

𝑌−5 |𝑌 − 5|
𝑃 = 50[1 + erf( )
𝑌−5 104

112 | P a g e
 4.45 − 5 |4.45 − 5|
𝑃 = 50[1 + erf ( ) = 29%
4.45 − 5 𝑠𝑞𝑟𝑡(2)

9.2 BLEVE SCENARIO

BLEVE Thermal Flux
The following table shows the design specifications for the reactor, T-101, when calculating the
thermal flux.

Table 25: Input data for BLEVE thermal flux

Initial flammable mass, M (kg) 300 000

Distance from fireball centre on ground, L 200
(m)

Maximum Fireball Diameter

1
𝐷𝑚𝑎𝑥 = 5.8𝑀3

1
𝐷𝑚𝑎𝑥 = 5.8(300 000)3 = 388.27 𝑚

Fireball Combustion Duration

1
𝑡𝐵𝐿𝐸𝑉𝐸 = 2.6𝑀6 𝑓𝑜𝑟 𝑀 > 30 000 𝑘𝑔

113 | P a g e
 1
𝑡𝐵𝐿𝐸𝑉𝐸 = 2.6(300 000)6 = 21.27 𝑠

Centre Height of Fireball

𝐻𝐵𝐿𝐸𝑉𝐸 = 0.75 𝐷𝑚𝑎𝑥

𝐻𝐵𝐿𝐸𝑉𝐸 = 0.75 (388.27) = 291.20 𝑚

Initial Ground Level Hemisphere Diameter

𝐷𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 1.3 𝐷𝑚𝑎𝑥

𝐷𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 1.3 (388.27) = 504.75 𝑚

Surface Emitted Flux

The radiation fraction, R, was assumed to be 0.9.

𝑅𝑀𝐻𝑐
𝐸= 2
𝜋𝐷𝑚𝑎𝑥 𝑡𝐵𝐿𝐸𝑉𝐸

Where:

𝐻𝑐 is the heat of combustion of the fuel, acrylic acid

𝑘𝐽
𝐻𝑐 = 98 578.08
𝑘𝑔

𝑘𝐽
0.9 × 300 000 𝑘𝑔 × 98 578.08 𝑘𝐽 𝑘𝑊
𝑘𝑔
𝐸= = 2643.12 = 2643.12
𝜋 × 388.272 × 21.27𝑠 𝑚2 𝑠 𝑚2

View Factor

Assuming a vertically oriented target:

2
𝐷
𝐿 ( 𝑚𝑎𝑥 )
𝐹21 = 2
3
(𝐿2 + 𝐻 2 )2

388.27 2
200 ( 2 )
𝐹21 = 3 = 0.17
(2002 + 291.22 )2

114 | P a g e
Path Length

𝐷𝑚𝑎𝑥 fireball

Path Length
𝐻𝐵𝐿𝐸𝑉𝐸 = 291.2 𝑚

Receptor
𝐿
= 200 𝑚

The path length is calculated from the surface of the fireball to the receptor and is equivalent to
the hypotenuse minus the radius of the BLEVE fireball.

2
𝐷𝑚𝑎𝑥
𝑃𝑎𝑡ℎ 𝐿𝑒𝑛𝑔𝑡ℎ = √𝐻𝐵𝐿𝐸𝑉𝐸 + 𝐿2 +
2

388.27
𝑃𝑎𝑡ℎ 𝐿𝑒𝑛𝑔𝑡ℎ = √291.22 + 2002 + = 159.13 𝑚
2

Transmissivity

𝜏𝑎 = 2.02(𝑃𝑥 𝑋𝑐 )−0.09

Where:

𝑃𝑤 is the vapour pressure of water

𝑋𝑐 is the path length

𝜏𝑎 = 2.02 (2810 × 159.13)−0.09 = 0.63

115 | P a g e
Received Flux

𝐸𝑟 = 𝜏𝑎 𝐸𝐹21

𝑘𝑊
𝐸𝑟 = 0.63 × 2643.12 × 0.17 = 283.04
𝑚2

Blast fragments from a BLEVE

Table 26: Design Specifications When Calculating The Blast Fragments From A BLEVE.

Diameter of Sphere (m) 16

Vessel Failure Pressure (kPa) 500
Vessel Liquid Fraction 0.75
Vessel Wall Thickness (cm) 0.5
Vessel Wall Density (kg/m3) 7700
Temperature (K) 685
Drag Coefficient of Fragments, CD 0.47

Volume of Sphere

𝜋𝐷3
𝑉=
4

𝜋 × 163
𝑉= = 2144.66 𝑚3 = 2144.6 × 3.28083 = 75 735.21 𝑓𝑡 3
4

𝐿𝑖𝑞𝑢𝑖𝑑 𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉𝐿 = 0.75 × 75 735.21 𝑓𝑡 3 = 56 801.41 𝑓𝑡 3 = 1608.5 𝑚3

𝑉𝑎𝑝𝑜𝑢𝑟 𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉𝑣 = 75 735.21 − 56 801.41 = 18 933.8 𝑓𝑡 3 = 536.17 𝑚3

Energy of Explosion

It is assumed that the pressure effects are due to the vapour alone, thus the energy of explosion
due to the loss of physical containment can be calculated using the following formula.

116 | P a g e
 𝑃1 𝑃1
𝑊 = 1.39 × 10−6 𝑉𝑣 ( ) 𝑅𝑔 𝑇0 ln ( )
𝑃0 𝑃0

Where:

𝑃1 is the vessel failure pressure

𝑃0 is the ambient pressure

𝐵𝑇𝑈
𝑅 = 1.989
𝑙𝑏 𝑚𝑜𝑙𝑒 °𝑅

500 𝐵𝑇𝑈 500

𝑊 = 1.39 × 10−6 (18 933.8 𝑓𝑡 3 ) ( ) (1.989 ) (1233 𝑅) ln ( )
101.325 𝑙𝑏 𝑚𝑜𝑙𝑒 °𝑅 101.325
= 507.90 𝑙𝑏 𝑇𝑁𝑇

Number of Fragments

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐹𝑟𝑎𝑔𝑚𝑒𝑛𝑡𝑠 = −3.77 + 0.0096𝑉

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐹𝑟𝑎𝑔𝑚𝑒𝑛𝑡𝑠 = −3.77 + 0.0096(2144.66𝑚3 ) = 17

Volume of Vessel Shell

𝜋 3
𝑉𝑠 = (𝐷 − 𝐷13 )
6 2

Where:

𝐷2 is the outer diameter of the vessel

𝐷1 is the inner diameter of the vessel

0.2
𝑉𝑒𝑠𝑠𝑒𝑙 𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 = 0.5 𝑐𝑚 = 0.2 𝑖𝑛 = 𝑓𝑡 = 0.017 𝑓𝑡
12
𝜋
𝑉𝑠 = ((52.49 + 0.017)3 − 52.493 ) = 71.02 𝑓𝑡 3 = 2.01 𝑚3
6

Mass of Vessel

𝑀𝑣 = 𝜌𝑉𝑠

117 | P a g e
 𝑘𝑔
𝑀𝑣 = 7700 × 2.01 𝑚3 = 15 487 𝑘𝑔
𝑚3

It is assumed that the weight of the vessel is distributed evenly among the 17 fragments. Thus,
the average weight of each fragment will be as calculated below.

𝑀𝑣 15487
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐹𝑟𝑎𝑔𝑚𝑒𝑛𝑡𝑠, 𝑊𝑓 = = = 910.99 𝑘𝑔
17 17

Initial Velocity of Fragments

𝑃𝐷3
𝑢 = 2.05√
𝑊𝑓

Where:

𝑃 is the rupture pressure

𝐷 is the diameter of the fragment

14.7 14.7
𝑃 = 𝑃1 × = 500 × = 72.54 𝑝𝑠𝑖𝑎
101.325 101.325

𝑇𝑜𝑡𝑎𝑙 𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑆𝑝ℎ𝑒𝑟𝑒 = 𝜋𝐷2 = 𝜋(162 ) = 804.25 𝑚2 = 8656.64 𝑓𝑡 2

𝑇𝑜𝑡𝑎𝑙 𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑆𝑝ℎ𝑒𝑟𝑒 804.25

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 𝑓𝑜𝑟 𝑒𝑎𝑐ℎ 𝐹𝑟𝑎𝑔𝑚𝑒𝑛𝑡 = = = 47.31𝑚2
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐹𝑟𝑎𝑔𝑚𝑒𝑛𝑡𝑠 17
= 509.21 𝑓𝑡 2

𝐴 47.31
𝐷𝑖𝑎𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑆𝑝ℎ𝑒𝑟𝑒, 𝐷 = √ = √ = 3.88𝑚 = 12.73 𝑓𝑡
𝜋 𝜋

72.54 × 3.88 𝑚 𝑓𝑡
𝑢 = 2.05√ = 200.24 = 656.94
910.99 𝑠 𝑠

The approximate range of a missile was calculated by using the Baker’s method.

𝜌𝑜 𝐶𝐷 𝐴𝐷 𝑢2
𝑆𝑐𝑎𝑙𝑒𝑑 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 =
𝑀𝑔𝑐

118 | P a g e
Where:

𝜌0 is the density of the ambient air

𝑘𝑔 𝑚2
0.52 3 × 0.47 × 47.31 𝑚2 × 200.24 2
𝑆𝑐𝑎𝑙𝑒𝑑 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 = 𝑚 = 51.52
𝑚
910.99 𝑘𝑔 × 9.81 2
𝑠

It was assumed that the fragments were “chunky”, where the life coefficient, CL is zero, the life-
to-drag ratio will also be zero.

𝐶𝐿 𝐴𝐿
𝑇ℎ𝑎𝑡 𝑖𝑠, =0
𝐶𝐷 𝐴𝐷

Using the graph below, the scale fragment range was determined.

For a scaled initial velocity =51.52

𝜌𝑜 𝐶𝐷 𝐴𝐷 𝑟
𝑅= =5
𝑀𝑓

Solving for r:

119 | P a g e
 910.9 𝑘𝑔 × 5
𝑟= = 397.06 𝑚
𝑘𝑔 2
0.52 3 × 0.47 × 47.31 𝑚
𝑚

Fatalities Due to Thermal Flux from A BLEVE Fireball

The total flammable mass, M was found to be 300 000 kg.

Time Duration

The time duration was calculated using the formula as shown below:

𝑇𝑖𝑚𝑒 = 2.6 × 𝑀0.1667 = 2.6 (300 000)0.1667 = 21.27 𝑠

Heat Flux (kW/m2)

The heat flux used in the probit equations was found by the formula below using a distance of
20m for the sample calculation below:

8.28 × 103 𝑀0.771

𝐸=
𝑋𝑐2

Where

I is the emissivity flux or heat flux (kW/m2)

𝑋𝑐2 is the distance fireball centre to the receptor which was varied

8.28 × 103 ( 300 000)0.771 𝑘𝑊

𝐼= = 34 580
𝑋𝑐2 𝑚2

The next step was to determine the percentage of fatalities using the Probit equation for the
thermal radiation. The following Probit model was used:

4
𝑡𝐼 3
𝑌 = −14.9 + 2.56 ln ( 4 )
10

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Overpressure from A Combustion in a Vessel
Table 27: Data Used for Overpressure Calculations

Input Data for Overpressure from Combustion Value

in a Vessel
Mole Fraction of Fuel 0.75
Molecular Weight of fuel 72.06
Volume of Vessel (m3) 200.0
Energy of combustion of fuel (kcal/gmol) 1697.79
Initial Temperature (oC) 412
Initial Pressure (barg) 5

For the total moles in vessel:

𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑠 𝑖𝑛 𝑣𝑒𝑠𝑠𝑒𝑙=

𝑇𝑟𝑒𝑓 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 + 1.01325 𝑔𝑚𝑜𝑙

= 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑣𝑒𝑠𝑠𝑒𝑙 × ( )×( ) × (1 )
𝑇𝑟𝑒𝑓 + 273 1.01325 0.0224 𝑚3
= 21 117.7 𝑔𝑚𝑜𝑙

For the total moles of fuel:

𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙 = 𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑖𝑛 𝑣𝑒𝑠𝑠𝑒𝑙 × 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 = 21 117.7 × 72.06
= 15 838.3

For total mass of fuel:

𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙 = 𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙 × 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑢𝑒𝑙

= 15 838.3 × 72.06 = 1 141 306.32 𝑘𝑔

For the total energy of combustion:

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙 × 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑢𝑒𝑙

𝑘𝑐𝑎𝑙
= 15 838.3 𝑔𝑚 𝑚𝑜𝑙 × 1697.8 = 26 890 006 𝑘𝑐𝑎𝑙
𝑔𝑚 𝑚𝑜𝑙

121 | P a g e
For the Equivalent mass of TNT:

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛

𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑇𝑁𝑇 = = 24 008.93 𝑘𝑔 𝑜𝑓 𝑇𝑁𝑇
1120

Where 1kg of TNT is equivalent to 1120 kcal of TNT.

Performing a trial calculation for the distance from the blast to determine the scaled distance,
over pressure and impulse.

𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑏𝑙𝑎𝑠𝑡 20 1

𝑆𝑐𝑎𝑙𝑒𝑑 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒, 𝑧 = 1 = = 0.693 𝑚/𝑘𝑔3
24 008.93
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑇𝑁𝑇 3

From the Consequence Anaylsis book used from Table 3.1 the range 1 was used for the
overpressure, po with the respective constants for the formula 𝑎 + 𝑏 × log(𝑧) and it was found to
be 2797609 kPa at a distance of 20m. Using the same Table 3.1 the range was also used for the
respective constants and it was found to be 18 Pa.s at a distance of 20m.

The overpressure and impulse values was then used into the following probit equations, where P
refers to the overpressure and the J refers to the impulse, to determine the percentage fatalities
(%) on the plant:

𝐿𝑢𝑛𝑔 𝐻𝑎𝑒𝑚𝑜𝑟𝑟ℎ𝑎𝑔𝑒, 𝑌 = −77.1 + 6.91𝑙𝑛𝑃

𝐸𝑎𝑟𝑑𝑟𝑢𝑚 𝑅𝑢𝑝𝑡𝑢𝑟𝑒, 𝑌 = −15.6 + 1.63𝑙𝑛𝑃

𝐷𝑒𝑎𝑡ℎ 𝑓𝑟𝑜𝑚 𝐼𝑚𝑝𝑎𝑐𝑡, 𝑌 = −46.1 + 4.82 𝑙𝑛𝐽

𝐼𝑛𝑗𝑢𝑟𝑖𝑒𝑠 𝑓𝑟𝑜𝑚 𝑓𝑙𝑦𝑖𝑛𝑔 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡𝑠, 𝑌 = −27.1 + 4.26𝑙𝑛𝐽

𝑆𝑡𝑟𝑢𝑐𝑡𝑢𝑟𝑎𝑙 𝐷𝑎𝑚𝑎𝑔𝑒, 𝑌 = −23.8 + 2.92𝑙𝑛𝑃

122 | P a g e
9.3 Toxic Gas Release Scenario
Discharge rate model
Table 28: Data Used To Calculate Rate of Gas Release Through Hole

Heat capacity ratio of gas: 1.026

Hole size, (mm) 3200
Final Pressure, (bar abs) 10
Initial Pressure, (bar abs) 3.5
Temperature, (673) 673
Gas molecular weight: 72.064

Hole area

𝜋 2
𝐴𝑟𝑒𝑎 = 𝑑
4
Where:
d is the diameter
𝜋 3200
𝐴𝑟𝑒𝑎 = 4 (1000)2 = 8.0424 m2

123 | P a g e
Upstream gas density

𝑅𝑀𝑀
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 = 𝑃𝑈𝑃 × × 105
8.314 × 𝑇
72.064
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 = 10 × × 105 = 12.88 𝑘𝑔𝑚−3
8.314 × 673

Sonic pressure ratio

𝑙𝑛𝑦 = 𝐴(𝑙𝑛𝐾𝑓 )3 + +𝐵(𝑙𝑛𝐾𝑓 )2 + 𝐶(𝑙𝑛𝐾𝑓 ) + 𝐷

2
𝑦 = exp[𝐴(𝑙𝑛𝐾𝑓 )3 + +𝐵(𝑙𝑛𝐾𝑓 ) + 𝐶(𝑙𝑛𝐾𝑓 ) + 𝐷]

𝐾𝑓 = 1.5

A= 0.0011 B=- 0.0302 C= 0.238 D=0.6455 For k = 1.4

𝑦𝑠𝑜𝑛𝑖𝑐 = 𝑒𝑥𝑝[0.0011(𝑙𝑛1.5)3 − 0.0302(𝑙𝑛1.5)2 + 0.238(𝑙𝑛1.5) + 0.6455]

𝑦𝑠𝑜𝑛𝑖𝑐 = 0575

Expansion Factor

𝑙𝑛𝑌 = 𝐴(𝑙𝑛𝐾𝑓 )3 + +𝐵(𝑙𝑛𝐾𝑓 )2 + 𝐶(𝑙𝑛𝐾𝑓 ) + 𝐷

2
𝑌 = exp[𝐴(𝑙𝑛𝐾𝑓 )3 + +𝐵(𝑙𝑛𝐾𝑓 ) + 𝐶(𝑙𝑛𝐾𝑓 ) + 𝐷]

𝐾𝑓 = 1.5

A= 0.006 B= 0.0185 C= 0.1141 D=-0.5304

𝑌 = 𝑒𝑥𝑝[0.006(𝑙𝑛1.5)3 + 0.0185(𝑙𝑛1.5)2 + 0.1141(𝑙𝑛1.5) − 0.5304]

Y= 0.614

Actual pressure ratio

𝑃𝑈𝑝 − 𝑃𝐷𝑂𝑊𝑁
𝑃𝑢𝑝

124 | P a g e
 10 − 3.5
= 0.65
10
Chocking pressure

𝑃𝑐ℎ𝑜𝑐𝑘𝑖𝑛𝑔 = 𝑃𝑈𝑃 − (1 − 𝑦𝑠𝑜𝑛𝑖𝑐 )

𝑃𝑐ℎ𝑜𝑐𝑘𝑖𝑛𝑔 = 10 − (1 − 0.575) = 4.25

Mass flow

𝑚 = 𝑌𝐴√2𝑔𝑐 𝜌𝑢𝑝 (𝑃1 − 𝑃2 /∑𝑘𝑓

𝑚 = 0.614 ∗ 8.04√2(1)(12.88)(10 − 4.25)/ 1.5

𝑚 = 15522.75 𝑘𝑔𝑠 −1

Figure 18: Showing The Mass Flow Rate At Different Heat Capacity Ratio

125 | P a g e
The interpolated mass flow rate was found to be 14524 kg/s

Dispersion Model
Plume Model

On dispersion of the acrylic acid vapor, it was considered to be continuous therefore, the plume
model was chosen. Before carrying out this section of calculations, it was assumed that:

 The vapor plume release model is to be used since the release duration was greater than
40 minutes.
 The area was assumed to be rural with a stable weather condition (clear still night
conditions) of class F with wind speeds of 2 m/s.
 It was assumed that the height of release would be 11 m which was the height of the tank.
 Gas release rate is stable at a constant, continuous rate. T
 he gas under consideration is neutrally buoyant.
 Meteorological conditions (wind speed) are stable both in terms of time and height.
 Gas mixture does not react in the atmosphere.

The average concentration for continuous release is given by:

Where:
x is the Downwind (m)
y is the Cross Wind Direction (m)
z is the Distance Above The Ground (m)
σy, σz is the Dispersion Coefficients In The y And z Directions (m)
H is the Release Height Above The Ground (m)
u is the Wind Velocity (m/s)

126 | P a g e
Using: x = 40m, y = 0m, z = 10m

𝜎𝑦 = 0.04𝑥(1 + 0.0001𝑥)−0.5

Then substituting in known values:

𝜎𝑦 = 0.04(40)(1 + 0.0001(40))−0.5 = 1.6 𝑚

𝜎𝑧 = 0.016𝑥(1 + 0.0003𝑥)−1.0

𝜎𝑧 = 0.016(40)(1 + 0.0003(40))−1.0= 0.63m

Using:

Then substituting in known values:

< 𝐶 > (40,0,10)

14524 0 2 10−11 2 10+11 2

−0.5( ) −0.5( ) −0.5( )
=[ ] × [𝑒 1.6 ] × [𝑒 0.63 ] + (𝑒 0.63 )
(2)(𝜋)(1.6)(0.63)(2)

< 𝐶 > (61,0,10) =3.28E-02 kg/m3

Conversion Of Concentration To PPM

Using:
0.06820𝑇 < 𝐶 >
𝐶𝑃𝑃𝑀 =
𝑃𝑀

0.06820𝑇 < 0.0328 >

𝐶𝑃𝑃𝑀 = = 25,481,793 𝑝𝑝𝑚
𝑃𝑀
To plot the Plume Model

127 | P a g e
This model was used to illustrate the isopleth at varying downwind distances.

 The downwind distance was incremented by 100m intervals until 6000m was reached.
 The dispersion coefficients in the y and z directions were calculated for the
corresponding downwind distances using the recommended equations for an rural
environment with stability class of F.

For x =300m

𝜎𝑦 = 0.04𝑥(1 + 0.0001𝑥)−0.5

Then substituting in known values:

𝜎𝑦 = 0.04(300)(1 + 0.0001(300))−0.5 = 4.4𝑚

For σz

𝜎𝑧 = 0.016𝑥(1 + 0.0003𝑥)−1.0

𝜎𝑧 = 0.016(300)(1 + 0.0003(300))−1.0 = 11.82

Determine the downwind centreline concentration C<x,0,0,t>

2
14523978 1 11
𝐶(𝑥.0.0.𝑡) = (𝜋)(4.4)(11.82)(2)
(300) exp (− (300) ( )) = 1960.736 𝑔𝑚𝑚−3
2 11.82

𝐶(𝑥.0.0.𝑡) = 152376.3 ppm

Determine the crosswind distance at varying downwind distance by specifying the isopleth
concentration, e.g. C(x,y,0.t) = 100 ppm.
Using

128 | P a g e
 < 𝐶 > (𝑥, 0, 𝑧, 𝑡)
𝑦 = 𝜎𝑦 √2 𝑙𝑛
< 𝐶 > (𝑥, 𝑦, 𝑧, 𝑡)

Where:
y is the centre distance to the isopleth (m)

152376.3
𝑦 = 4.4√2 𝑙𝑛 = 45.3 𝑚
100

 The concentration was then varied from different concentrations and the corresponding y
values were plotted in a graph as seen below.
 The total isopleth area was calculated according to the following formula:
𝑇𝑜𝑡𝑎𝑙 𝐴𝑟𝑒𝑎 = 2∑𝐴𝑟𝑒𝑎 𝑎𝑡 𝑒𝑎ch 100𝑚 𝑖𝑛𝑐𝑟𝑒𝑚𝑒𝑛𝑡
 This total area was then calculated for each isopleth of varying concentration.
 After the location of the isopleth, y, was found for each downwind distance, the largest y
value was assumed to be the maximum width of the plume.

The Probability of Death

The probability of death when there is a toxic release is dependent on both the exposure
concentration and time period, which can be easily be calculated from the Probit equation below.

𝑌 = 𝑎 + 𝑏 (𝐶 𝑛 × 𝑡𝑒 )
Where:
Y is the Probit value
a, b and n are constants (Obtained from Table 3.0 in Appendix)
te is the exposure time in minutes
C is the concentration of toxic chemical in ppm by volume

The concentration of H2S in ppm was calculated at various downwind distances (m) from the
dispersion model. The exposure time were ranged from 1 minute to 60 minutes at various
increments, which was then applied to the probit equation.

For Cppm = 500

129 | P a g e
a = -8.29
b = 0.92
n=2
te = 10 minutes

𝑌 = −8.29 + 0.92 (5002 × 10) = 5.26

This value has no direct meaning and as such converted to a useful form, i.e. in percentage
probability of death which is done through the use of the probit to percentage table

Percentage fatality = 60.38%

9.4 Explosion Scenario

Baker’s Method for Overpressure of a Ruptured Vessel: (24)
The material used for construction of the heat exchanger was Stainless steel, which has a
design stress of 131 N/mm2 (Table 13.2 Chemical Engineering Design, Volume 6). The design
stress of the material was used as the vessel burst pressure.

Table 29: Data for Overpressure Calculations

Vessel Burst Pressure 651.69 bar abs

Distance from vessel center 19 m
Vessel Volume 0.2 m3
Final Pressure 1.601018 bar abs
Heat capacity ratio 1.276
Molecular weight of gas 21.97017 kg/kmol
Gas Temperature 433 K
Speed of sound in ambient gas 340 m/s

Calculation of Energy

Brode’s equation for constant volume expansion:

105 𝑃𝑎
(𝑉𝑒𝑠𝑠𝑒𝑙 𝑏𝑢𝑟𝑠𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 − 𝐹𝑖𝑛𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒) × ( ) × 𝑉𝑒𝑠𝑠𝑒𝑙 𝑉𝑜𝑙𝑢𝑚𝑒
𝑏𝑎𝑟
𝐸𝑛𝑒𝑟𝑔𝑦 =
(𝐻𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑟𝑎𝑡𝑖𝑜 − 1)

130 | P a g e
 (651.69 − 1.601018) × 105 × 0.2
=
(1.276 − 1) × 106

=47.11 𝑀𝐽

𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑒𝑥𝑝𝑙𝑜𝑠𝑖𝑜𝑛
𝑇𝑁𝑇 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑀𝑎𝑠𝑠 =
𝑇𝑁𝑇 𝐸𝑥𝑝𝑙𝑜𝑠𝑖𝑜𝑛 𝐸𝑛𝑒𝑟𝑔𝑦

47.11 𝑀𝐽
= 4.69 𝑀𝑗/𝑘𝑔

= 10.04 𝑘𝑔 𝑜𝑓 𝑇𝑁𝑇

𝐸𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑒𝑥𝑝𝑙𝑜𝑠𝑖𝑜𝑛 = 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝐸𝑥𝑝𝑙𝑜𝑠𝑖𝑜𝑛

= 47.11 × 2

= 94.22 𝑀𝐽

𝐹𝑖𝑛𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 1/3

𝑆𝑐𝑎𝑙𝑒𝑑 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒, 𝑅 = 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑣𝑒𝑠𝑠𝑒𝑙 𝑐𝑒𝑛𝑡𝑒𝑟 × ( )
𝐸𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒 𝐸𝑛𝑒𝑟𝑔𝑦

𝑃𝑎
1.6010 𝑏𝑎𝑟 𝑎𝑏𝑠×( 105 )
= 19𝑚 × ( 𝑏𝑎𝑟
)1/3
94.22 𝑀𝐽 ×106

= 2.27 𝑚

Using interpolation and the data from the Over pressure curves of Ln (R) vs. Ln (P):

Table 30: Ln (R) and Ln(P) Values from Overpressure curves

Ln ( R ) Ln (P)
0.790138 -2.23208
0.81859 -2.25822
0.838838 -2.2768

131 | P a g e
Ln (R) = 0.81859

Ln (P) = -2.25822

P = 0.104537

Using the data from the Impulse pressure curves of Ln ( R) vs. Ln (I):

Table 31: Ln (R) and Ln (I) values from Impulse Curves

Ln (R) Ln (I)
0.802405 -3.781935
0.81859 -3.7976
0.824468 -3.803285

Ln (R) = 0.81859

Ln (I) = -3.7976

I = 0.022424

Vessel Shape: Cylindrical

Overpressure multiplier for cylinder: 1.6

𝐶𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑆𝑐𝑎𝑙𝑒𝑑 𝑂𝑣𝑒𝑟𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑂𝑣𝑒𝑟𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑚𝑢𝑙𝑡𝑖𝑝𝑙𝑖𝑒𝑟 × 𝑆𝑐𝑎𝑙𝑒𝑑 𝑂𝑣𝑒𝑟𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

= 1.6 × 0.104537

= 0.1673

𝐴𝑐𝑡𝑢𝑎𝑙 𝑂𝑣𝑒𝑟𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝐶𝑜𝑟𝑟𝑒𝑒𝑐𝑡𝑒𝑑 𝑆𝑐𝑎𝑙𝑒𝑑 𝑂𝑣𝑒𝑟𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 × 𝐹𝑖𝑛𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒

= 0.1673 × 1.601018

= 0.2678 𝑏𝑎𝑟

= 3.88 𝑝𝑠𝑖

Impulse multiplier for cylinders: 1

𝐶𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑠𝑐𝑙𝑎𝑒𝑑 𝑖𝑚𝑝𝑢𝑙𝑠𝑒 = 𝑆𝑐𝑎𝑙𝑒𝑑 𝐼𝑚𝑝𝑢𝑙𝑠𝑒 × 𝐼𝑚𝑝𝑢𝑙𝑠𝑒 𝑚𝑢𝑙𝑡𝑖𝑝𝑙𝑖𝑒𝑟

132 | P a g e
 = 1 × 0.022424

= 0.0224224
2 1
𝐶𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑆𝑐𝑎𝑙𝑒𝑑 𝐼𝑚𝑝𝑢𝑙𝑠𝑒 × (𝐹𝑖𝑛𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 × 105 )3 × (𝐸𝑥𝑝𝑙𝑜𝑠𝑖𝑜𝑛 𝐸𝑛𝑒𝑟𝑔𝑦 × 106 )3
𝐴𝑐𝑡𝑢𝑎𝑙 𝑖𝑚𝑝𝑢𝑙𝑠𝑒 =
𝑆𝑝𝑒𝑒𝑑 𝑜𝑓 𝑠𝑜𝑢𝑛𝑑

0.0224 × (1.601018 × 105 )2/3 × (47.11 × 106 )1/3

=
340

= 70.23 𝑘𝑃𝑎 − 𝑚𝑠

Velocity of Fragments from a Vessel Rupture

Table 32: Data Used For Velocity of Fragments form a Vessel Rupture

Total Mass of vessel 100 kg

Total volume of vessel 0.2 m3
Number of Fragments 3
Mass fraction of total for fragment 0.2
Pressure of gas within vessel 0.121 MPa
Ambient gas pressure 0.101 MPa
Temperature of gas within vessel 433 K
Heat capacity ratio of gas within vessel 1.276
Molecular weight of gas within vessel 21.97

Speed of sound of gas within vessel

2 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑜𝑓 𝑔𝑎𝑠 ×𝐻𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑟𝑎𝑡𝑖𝑜 𝑜𝑓 𝑔𝑎𝑠 𝑤𝑖𝑡ℎ 𝑣𝑒𝑠𝑠𝑒𝑙×8314

=√ 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑔𝑎𝑠 𝑤𝑖𝑡ℎ𝑖𝑛 𝑣𝑒𝑠𝑠𝑒𝑙

2 433×1.276×8314
=√ 21.97

= 457 m/s

Adjustment factor for unequal mass = 𝑀𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 × 1.31 × 0.3084

= 0.2 × 1.305997 × 0.308446

133 | P a g e
 = 0.5696

(𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑔𝑎𝑠 − 𝐴𝑚𝑏𝑖𝑒𝑛𝑡 𝑔𝑎𝑠 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒) × 106 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑣𝑒𝑠𝑠𝑒𝑙

𝑆𝑐𝑎𝑙𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 =
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑣𝑒𝑠𝑠𝑒𝑙 × 𝑆𝑝𝑒𝑒𝑑 𝑜𝑓 𝑠𝑜𝑢𝑛𝑑 𝑜𝑓 𝑔𝑎𝑠 2

(0.121𝑀𝑃𝑎−0.101 𝑀𝑝𝑎)×106 ×0.2𝑚3

= 𝑚
100 𝐾𝑔×(457 )2
𝑠

Dimensionless velocity for cylinders:

For n=2:

Dimensionless velocity = 𝑒 (0.814896×ln(𝑆𝑐𝑎𝑙𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒)+0.355218)

For n=10:

Dimensionless velocity = 𝑒 (0.598255×ln(𝑆𝑐𝑎𝑙𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒)+0.564998)

The dimensionless velocity for 3 fragments were calculated using interpolation:

Table 33: Results obtained for Dimensionless Velocity of Fragments

Number of fragments Dimensionless velocity

2 0.001331
3 0.002477
10 0.010493

𝐴𝑐𝑡𝑢𝑎𝑙 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 = 𝐷𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑙𝑒𝑠𝑠 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 × 𝐴𝑑𝑗𝑢𝑠𝑡𝑚𝑒𝑛𝑡 𝑓𝑎𝑐𝑡𝑜𝑟 × 𝑆𝑝𝑒𝑒𝑑 𝑜𝑓 𝑠𝑜𝑢𝑛𝑑

𝑚
𝐴𝑐𝑡𝑢𝑎𝑙 𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 = 0.002477 × 0.569645 × 457 𝑠

𝑚
= 0.65 𝑠

Range of a Fragment in Air

Table 34: Data Used to Calculate Range of Fragments in Air

Mass of Fragment 20 kg

134 | P a g e
 Initial fragment velocity 20 m/s
Drag coefficient of fragment 0.35
Lift to drag ratio 1
Exposed area of fragment 3.05 m2
Temperature of ambient air 298 K
Pressure of ambient air 1 atm

𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑎𝑚𝑏𝑖𝑒𝑛𝑡 𝑎𝑖𝑟 ×29

Density of ambient air = 0.082057×𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑜𝑓 𝑎𝑚𝑏𝑖𝑒𝑛𝑡 𝑎𝑖𝑟

1 𝑎𝑡𝑚×29
= 0.082057×298 𝐾

= 1.19 kg/m3

𝑆𝑐𝑎𝑙𝑒𝑑 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡

𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑎𝑚𝑏𝑖𝑒𝑛𝑡 𝑎𝑖𝑟 × 𝐷𝑟𝑎𝑔 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 × 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 × ( 𝑖𝑛𝑖𝑡𝑎𝑙 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 2 )
=
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 × 9.8

𝑚
(1.19 𝑘𝑔/𝑚3×0.35×3.05 𝑚2 ×(25 )2
𝑠
= 20 𝐾𝑔×9.8

= 2.58 m/s

Table 35: Interpolated Values From Figure For Various Lift To Drag Ratios

Lift to drag Scaled Range

ratio Range (m)
0 1.420494 22.44
0.5 1.469698 23.22
1 1.701987 26.89
3 1.932924 30.54
5 0.632368 9.99
10 0.258561 4.08
30 0.081068 1.28
50 0.04848 0.77

135 | P a g e
 100 0.02345 0.37

Therefore:

-The interpolated range for the lift to drag ratio is 26.89 m

The maximum possible range (with lift)is 30.54 m

(𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑓𝑟𝑎𝑔𝑚𝑒𝑛𝑡 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦)2

𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑟𝑎𝑛𝑔𝑒 (𝑛𝑜 𝑙𝑖𝑓𝑡) =
𝑔

(20𝑚/𝑠)2
Theoretical maximum range (no lift) = 9.8

Theoretical maximum range (no lift) = 40.82 m

BLEVE Thermal Flux

Table 36: Data Used to Calculate BLEVE Thermal Flux

Initial flammable mass 50 000 kg

Water partial pressure in air 2810 Pa
Radiation Fraction, R 0.3
Distance from fireball center 70 m
Heat of Combustion of fuel 46350 kJ/kg

𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 = 5.8 × 𝐼𝑛𝑖𝑡𝑎𝑙 𝑓𝑙𝑎𝑚𝑚𝑎𝑏𝑙𝑒 𝑚𝑎𝑠𝑠1/3

1
= 5.8 × (50000)(3)

= 212.7 𝑚

1
𝐹𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 𝑑𝑢𝑟𝑎𝑡𝑖𝑜𝑛 = 2.6 × 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑓𝑙𝑎𝑚𝑚𝑎𝑏𝑙𝑒 𝑚𝑎𝑠𝑠 (6)
1
= 2.6 × (50000)(6)

= 15.8 𝑠

136 | P a g e
𝐶𝑒𝑛𝑡𝑒𝑟 ℎ𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 = 0.75 × 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟

= 0.75 × 212.7

= 160.3 𝑚

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑔𝑟𝑜𝑢𝑛𝑑 𝑙𝑒𝑣𝑒𝑙 ℎ𝑒𝑚𝑖𝑠𝑝ℎ𝑒𝑟𝑒 𝑑𝑖𝑎𝑚𝑡𝑒𝑟 = 1.3 × 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑑𝑖𝑎𝑚𝑡𝑒𝑟

= 1.3 × 212.7

= 277.8 𝑚

𝑅𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 × 𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑓𝑙𝑎𝑚𝑚𝑎𝑏𝑙𝑒 𝑚𝑎𝑠𝑠 × 𝐻𝑒𝑎𝑡 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑒𝑚𝑖𝑡𝑡𝑒𝑑 𝑓𝑙𝑢𝑥 =
3.14 × 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 2 × 𝐹𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 𝑑𝑢𝑟𝑎𝑡𝑖𝑜𝑛

0.3 × 50000 𝑘𝑔 × 46350 𝑘𝐽/𝑘𝑔

=
3.14 × 213.7𝑚2 × 15.8𝑠

= 307.3 𝑘𝑊/𝑚2

1
𝑃𝑎𝑡ℎ 𝑙𝑒𝑛𝑔𝑡ℎ = (𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑐𝑒𝑛𝑡𝑒𝑟 2 + 𝐶𝑒𝑛𝑡𝑒𝑟 ℎ𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 2 )2

−0.5 × 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟

1
= (70𝑚2 + 160.3𝑚2 )2 − 0.5 × 213.7𝑚

= 68 𝑚

𝑇𝑟𝑎𝑛𝑠𝑚𝑖𝑠𝑠𝑖𝑣𝑖𝑡𝑦 = 2.02 × (2810𝑃𝑎 × 68 𝑚)−0.09

= 0.679

𝐶𝑒𝑛𝑡𝑒𝑟 ℎ𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 × ((𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟)/2)2

𝑉𝑖𝑒𝑤 𝐹𝑎𝑐𝑡𝑜𝑟 = 3
(𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 𝑐𝑒𝑛𝑡𝑒𝑟 2 + 𝐶𝑒𝑛𝑡𝑒𝑟 ℎ𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑖𝑟𝑒𝑏𝑎𝑙𝑙 2 )(2)

213.7𝑚 2
160.3𝑚 × ( )
= 2
2
(70𝑚 + 160.3𝑚 )2 3/2

= 0.34

𝑅𝑒𝑐𝑖𝑒𝑣𝑒𝑑 𝑓𝑙𝑢𝑥 = 𝑉𝑖𝑒𝑤 𝑓𝑎𝑐𝑡𝑜𝑟 × 𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑒𝑚𝑖𝑡𝑡𝑒𝑑 𝑓𝑙𝑢𝑥 × 𝑇𝑟𝑎𝑛𝑠𝑚𝑖𝑠𝑠𝑖𝑣𝑖𝑡𝑦

137 | P a g e
 𝑘𝑊
= 0.34 × 307.3 × 0.676
𝑚2
𝑘𝑊
= 71.06 𝑚2

Fatality
𝑆𝑐𝑎𝑙𝑒𝑑 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 = 𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 𝐵𝑙𝑎𝑠𝑡 𝑇𝑁𝑇 𝑀𝑎𝑠𝑠1/3

3𝑚
=
10.04𝑘𝑔1/3

𝑚
= 1.3906
𝑘𝑔1/3

𝑎 + 𝑏𝑙𝑜𝑔(𝑧) = −0.2143 + 1.3503 × 𝑙𝑜𝑔10 (𝑆𝑐𝑎𝑙𝑒𝑑 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒)

= −0.2098

11

𝑙𝑜𝑔10 𝑖𝑝 = ∑ 𝑐𝑖 ( 𝑎 + 𝑏𝑙𝑜𝑔(𝑧))
𝑖=0

= 189.81 𝑃𝑎𝑠

The scaled distance was varied from 0 to the maximum range of fragment and the percentage
fatalities were calculated.

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