Section VIII.

Process Safety
VIII.1. Introduction
Safety is the most important part of a chemical plant, regardless of the production
size. This can be very severe because of the consequences of neglecting process
safety at a plant. Possible effects are detrimental to people including loss of life and
death, environmental damage caused by the release of hazardous materials and
damage to plant facilities. Not only that, it will also impact business performance
due to production disruption and the company's reputation will suffer long term
harm. It is therefore important that an effective process safety program be
implemented to keep the risk of the Biodiesel and Bio-methane production
operation as low as reasonably practicable. A successful safety plan includes a
comprehensive identification of hazards and structural management of potential
threats at all levels of a project from the start of design to operation and up to the
final demolition. For better research, the risks and effects of a large hazardous
incident and the measures for avoid or minimize it, a bowtie diagram is drawn up.
The Hazard and Operational Procedure (HAZOP) describes any danger and concern
related to each equipment and stream in this production plant for Bio-methane and
Biodiesel, and it presents recommendations for monitoring, minimizing and
eliminating the possibilities for mitigating those concerns. The summary of the
safety report for Bio-methane and Biodiesel production consists of a few key parts
that are:

 Identification of possible hazards

 Inherent safety
 Emergency response plan with examples of action plan
 Example of a bowtie diagram
 Example of Hazard and Operational Procedure (HAZOP)

VIII.2. Identification of possible hazards

Hazards can be present in different ways that require reduction, elimination, or
regulation. Hazards can typically be found in the following categories at a
manufacturing plant which are physical, mechanical, ergonomic, and health
hazards. Biodiesel is a pretty stable fuel. This is known to be non-flammable and
biodegradable. Nonetheless, in some cases the components to make biodiesel may
be unsafe. Biodiesel is produced by using methanol and a catalyst to react with
palm oil. Toxic chemicals include methanol, catalysts, acids. Biogas production also
causes some harmful hazards that needs to be prevented. Biogas primarily consists
of 60% methane and 40% carbon dioxide, with small amounts of hydrogen sulphide
and other gases. Any one of these gasses can displace oxygen.

VIII.2.1. Hazards from materials

Biodiesel which is produced as one of the main products is a fuel liquid that is the
least flammable compared to petroleum because it has auto-ignition temperature of
649oC. However, biodiesel should be treated the same as petroleum to avoid any
hazard. The manufacturing of biodiesel would produce routinely rags saturated with
oil or biodiesel. Sawdust or other fibrous materials are also popular but not advised
to be used as an absorbent for spilled biodiesel or palm oil. Such materials pose an
inherent risk of burning, as oily rags or sawdust can easily ignite spontaneously. In
2007, when sawdust saturated with vegetable oil on a sunny day caught fire, a
Pennsylvania barn burned to the ground. Such items, even in open trash cans,
must not be allowed to collect in or near the workspace. Oily rags should be
contained in an airtight metal tank, a bucket of water or enclosed in plastic bags
which have been emptied and properly disposed of in the waste. Until disposing of
the saturated rags, free liquid should be squeezed into an appropriate container. Be
sure to disperse the material when disposing of the saturated sawdust in a
dumpster to prevent any piles that can burn and cause a dumpster fire. [ CITATION
Ste19 \l 17417 ]

Methanol is poisonous and should be used and treated in a well-ventilated

environment. Methanol inhalation or ingestion at higher concentrations can be
extremely dangerous and can lead to death or blindness. This is especially
damaging to the eyes; protective masks, clothing that is chemical-resistant and
gloves must be worn whenever the substance is treated. If air concentrations reach
200 ppm, air-supplied respirators, preferably with a full-face mask, are required.
The degree at which the methanol smell is perceptible reaches 200 ppm. Therefore,
if one "smells" methanol in the production plant, there is already an unhealthy
personal exposure. Producers are advised to alter any manufacturing operation
resulting in obvious odours of methanol. Ingestion of methanol, high concentration
inhalation, and some contact with the eyes call for urgent medical attention. Short-
term methanol vapor exposure can irritate the eyes, nose, and throat and cause
headache, nausea, vomiting, dizziness, and breathing difficulties. Other common
symptoms of drunkenness can also occur, such as light-headedness, giddiness,
blurred vision and dilated pupils. The symptoms depend on the exposure level and
period and can differ from person to person. Methanol is flame retardant and
creates a fire threat. The vapours are heavier than air and can travel a long
distance to the processing unit or methanol storage tank to reach an ignition source
with subsequent flashback. The flash point of methanol is 11 oC which is the point at
which enough vapor is emitted to form a flammable mixture. There is ample
methanol vapor produced at biodiesel processing temperatures to sustain a serious
fire if air mix with the methanol. [ CITATION Ste19 \l 17417 ]

The catalyst used to produce biodiesel, zeolite CBV 780 is also another hazardous
material. CBV 780 has low oral toxicity but ingestion can cause gastrointestinal
tract irritation. Dust of this catalyst should be avoided. Existing medical conditions
(e.g. asthma, bronchitis) may also be exacerbated by dust exposure. Effects of dust
can be greater and may occur in smokers at lower rates of exposure than non-
smokers. Dust of the catalyst on skin can have a drying effect. Dust of this catalyst
can cause discomfort and moderate irritation. [ CITATION Zeo14 \l 17417 ]
Sodium hydroxide is corrosive and can result in fatality if ingested. Contact with the
skin will cause serious burns and the burned area should be thoroughly cleaned
with water or a dilute solution of vinegar. When the substance is reduced to dust-
sized particles especially during catalyst loading on zeolite CBV 780, inhalation of
the solid NaOH. Each of these conditions is serious and needs urgent medical
attention. Sodium and potassium hydroxide must be stored away from water
because water prevents the biodiesel reaction and induces heat release as a result
of mixing, which can potentially cause fire in adjacent products. NaOH condensed
solutions should never touch aluminium, as explosive hydrogen gas is produced.
Proper NaOH safety equipment includes elbow-length gloves, chemical safety
goggles, a dust mask or respirator, long pants, and shoes. It is also strongly
recommended to have an eyewash station and/or emergency shower within 25 feet
of the workspace. It is also important to wear a dust mask or respirator cartridge
when measuring all but also small quantities of NaOH to avoid inhalation of caustic
particles. A vinegar spray bottle is useful to neutralize any minor drops of a residual
catalyst in the workplace. Fine NaOH particles may create holes in clothing; thus, a
protective apron or jumpsuit is also suggested. It is also good to keep a spare
change of clothes on hand for any person working in the biodiesel store, so
unintentionally polluted clothes can be easily shed if necessary. [ CITATION Ste19 \l
17417 ]

Methane, which accounts for about 60% of biogas, forms explosive mixtures in air.
There is an explosion hazard when biogas is mixed with air with concentration
between 10 % to 30 %. Several explosions on Canadian swine farms in 2003 were
thought to have been caused by the exploding methane in biogas. Hydrogen
sulphide and ammonia may be explosive, too. No open flames should ever be used
near a digester, due to the explosion hazards. Equipment such as massive engines
and electric generators must also be environmentally conscious, so that the gas is
not ignited by a spark. Explosion-proof equipment and electrical service should be
used for digesters and biogas, as well as non-sparking devices. There must be no
smoking near the lines and equipment for the digester or related biogas. In an
enclosed space where sludge is processed, asphyxiation from biogas is a problem.
Osbert and Crapo record one case involving three people who died in an enclosed
space from asphyxiation caused by swine manure gas. Also, open-topped sludge
pits can produce methane at a rate that is enough to move the air above the sludge
and make the space oxygen deficient. Never approach a building where sludge is
stored or where there is a suspected biogas leak as natural ventilation cannot be
trusted to adequately dilute the explosion threat. Airing out a facility does not
provide protection, because some of the gases generated are heavier than air. If a
person is found unconscious in such an installation, do not enter the facility because
you may also be overcome. Contact emergency services so the victim can be
rescued safely by firefighters wearing self-contained breathing equipment (SCBA). [
CITATION Pat19 \l 17417 ]
Biogas primarily consists of 60% methane and 40% carbon dioxide, with small
amounts of hydrogen sulphide and other gases. Any one of these gasses can
displace oxygen. Methane is lighter than air and can move in the building's upper
spaces. It is explosive at concentrations of 5 % to 15 %. While methane is not a
poisonous gas, it displaces air, so it produces an oxygen deficient atmosphere in a
confined space. Carbon dioxide is a heavier odourless gas than air. Carbon dioxide
can be layer near the floor in a quiescent room. Slightly elevated carbon dioxide
concentrations increase heart rate and respiration rate. Higher levels displace the
supply of oxygen in the bloodstream which can lead to unconsciousness and death.
Hydrogen sulphide is heavier than air and highly poisonous substance. It smells like
rotten eggs at very low levels and can cause eye irritation. It kills the sense of
smell at harmful levels and causes respiratory paralysis. Thus, there is no odour to
warn of its existence at harmful and fatal stages, where one can literally drop out
dead. Ammonia is a gas that is lighter than air, has a pungent odour, and can
irritate the eyes and respiratory tract. Ammonia can displace oxygen in the
bloodstream. [ CITATION Pat19 \l 17417 ]

VIII.2.2. Hazards from equipment

Several compressors are used in the bio-methane and biodiesel manufacturing
plant where high ambient noise level is produced. Excessive noise can cause
tiredness and permanent harm to long-term hearing

VIII.3. Inherent safety

An inherently safer design is one that avoids hazards rather than regulates them,
particularly by reducing the amount of hazardous material and the number of
hazardous operations at the plant. These standards have been developed to
enhance the inherent health, hygiene and protection of the environment.
Nonetheless, an objectively safer method should not be viewed as completely
secure because risks are not removed entirely. No chemical process is without risk
but by incorporating fundamentally safer principles, all chemical processes can be
made safer.

The equipment is built with strong robust materials of considerable thickness to

withstand pressure above the pressures of their operations. As a precaution, each
equipment is installed at a safe distance of 10 m from each other, should any
accident occur. The control room is in close but safe proximity to the production
lines for rapid operator responses. The storage tanks are supposed to contain
chemical products up to a week's worth to reduce the possibility of leakage and
then release flammable vapor into the atmosphere. The Anaerobic reactor,
esterification reactor and transesterification reactors are supplied with cooling water
to cool down the equipment because all the reactions in the equipment stated are
exothermic processes. Water and steam are chosen instead of hot oil as heat
transfer fluids, as they are safer choices. The wastewater treatment facility is
situated at the corner of the facility site so that the biological risks of the
contaminants in the sludge and sewage from impacting the workers in the plant are
not readily available. Administrative buildings and area of management are put
away from the area of development. Workers will be briefed on the daily processes
and procedures to ensure complete awareness of the use of equipment at the plant
during routine operations as well as in emergency situations.

VIII.4. Emergency response plans

The actions taken within the first few minutes of an emergency are crucial and may
make a significant difference in the damage and injuries sustained. Employees
should be given prompt warning to evacuate from the situation. Providing full and
correct details when calling for help would make it easier for dispatchers to send
the appropriate personnel and equipment as quickly as possible. Each of the
workers must recognize this emergency response plan and be available in all areas
of the factory. In an emergency one's survival is the focus. Employees with process
management and design experience can help monitor the situation and mitigate
harm to the building and environment. It is possible to split the emergency plan
into a few parts, which are the action plan for various events, emergency contacts
and emergency evacuation plan.

Figure VIII.4.1 displays production facility's emergency evacuation program. The

emergency assembly points at considerable distances from all process equipment
which is the main source of the plant hazards and should be avoided during
emergencies. All workers will be relocated to their workstations at the nearest
assembly and return to their respective places as soon as possible.

VIII.4.1. Examples of Action Plan

Action plan 1: Injured individual

1. Inform the plant manager or the safety officer and immediately receive
medical assistance from the emergency department.
2. If required, or if possible, shift victim to a safe location.
3. Notify the first aid team to carry out first aid assistance and stopping injuries
from getting worse.
4. Send the injured person to a local hospital to conduct a full body check-up if
the first aid service is insufficient.
5. Inform the safety officer to test and decide if that specific location is safe to
operate.
6. Ensure that the area with warning signs or tapes is barricaded if the location
contains hazards.
7. File a report on the incident

Action plan 2: Fire incidents

 1. Switch on the fire alarm and call the fire service department to notify the
location of the fire when the fire is detected.
2. Shut down production and strictly stick to the emergency response plan.
3. Using a fire extinguisher to put out the fire and prevent it from spreading to
other places where the fire is small.
4. Proceed to the nearest exit and evacuate the plant using the designated
escape route if the fire is too big to be extinguished.
5. Close the door to the room you are in and stuff the wet towels or cloths
under the door to keep smoke from getting in If you are unable to evacuate
the plant because of smoke or fire in the corridor.
6. To stop breathing in smoke when evacuating use a wet towel or cloth to
cover the nose and mouth.
7. Keep your stance low when fleeing to avoid breathing in smoke.
8. Continue to the emergency assembly point and perform headcounts to
ensure that all personnel and employees have left the danger zone.
9. Submit number of insufficient workers to the authorities arriving afterwards.
10. The safety officer will compile a report of potential causes of fire and
plant conditions with more information after the accident.

VIII.4.2. Information Needed During Emergency Report

During an emergency call the following information is needed:

 Name of the individual disclosing the incident

 Incident Date
 Incident site
 Incident summary
 Chemicals name
 Amount of Chemicals
 Categorization of incident
 Injuries extend

VIII.4.3. Emergency Contacts

Table VIII.6.1 indicates the divisions contactable in case of an emergency.

Table VIII.6.1: Emergency contact numbers

Department Contact number

Balai Bomba dan Penyelamat Serian 08-287 4190
Serian District Police Headquarters 08-284 7201
Serian Hospital 08-287 4311
Emergency hotline 911
VIII.5. Process Safety Analysis
VIII.5.1. Bowtie Diagram
A bowtie offers a visual guide to make process safety more successful by having a
clearer perspective on consequences and how to minimize these. The bowtie
diagram provides a visual illustration of the precautions required to avoid various
causes of a hazardous accident and the mitigating steps needed if an incident
occurs. This can be used to show results of different forms of risk assessment and
is useful for training assistance. Figure VIII.5.1 displays a bowtie diagram to
evaluate an anaerobic reactor R-001A fire or explosion.

On the left side, the anaerobic reactor R-001A is defined as leading to fire or an
explosion. Excessive feed heating would be one of the potential factors that could
cause the vessel to overheat or overpressure. This build-up of pressure and
temperature will result in a breakdown in the reactor's activity, which will
eventually lead to an internal fire within the reactor, as it also contains the
flammable methane, which in combination with the build-up of pressure can cause
the reactor to explode.

On the other side of the bowtie diagram are the reactor catching fire results, or the
reactor explosion. This involves the loss of labour due to injuries or workers'
accidents as well as financial loss as production is halted. The bowtie diagram also
discusses preventive measures such as the installation of a high temperature and
pressure warning and control device, and the installation of pressure relief valve
and bursting disk.

VIII.5.2. Hazard and Operational Procedure (HAZOP)

A HAZOP research is a coordinated and effective review of a planned or ongoing
complex project that can recognize and analyse issues that can affect either
personnel or equipment. It describes the major hazards and operability issues in
industrial and process equipment, which could limit the ability to safely achieve the
target productivity. A HAZOP snippet performed on reactor R-301 is shown in Table
VIII.5.2. Appendix AV provides for complete HAZOP analysis.

The causes of the deviations which may occur in the knock out flash drum V-001A
is established. It then recommends measures and suggestions as well as
precautions to resolve pressure variations in the vessel. For example, having no
vessel level can be triggered by a severe rupture, which can lead to flammable
methane leakage. A pressure indicator and controller PIC-A03 with a low-pressure
alarm PAL-A03 would be among the controls added to the operation. The alarm
should inform the operator that an emergency response plan is being implemented.
Installation of a fire detection and extinguishing device is recommended.

VIII.6. Conclusion
Overall, the hazards associated with the process procedure have been carefully
analysed and assessed in this safety study. In the initial stage of process design,
intrinsic safety standards were also a concern. Contingency plans and emergency
contacts to demonstrate that the plant is prepared to face the threat of an incident
such as chemical spill was also added. The bowtie diagram was used as the initial
analysis, after which the data from the bowtie diagram was used in the HAZOP. An
initial HAZOP analysis of the process was performed, and another group member
carried out process control referred to this. After development of the process
control systems in P&ID, a further round of HAZOP analysis was then carried out to
integrate the suggested control system.
Figure VIII.4.1: Evacuation plan for Renewable Gas and Green Chemicals production plant
Table VIII.5.2: Snippet of moisture knock out drum V-001A HAZOP

Project: Production of Renewable Gas and Green Chemicals from Palm Oil Date: 20/4/2020
Effluent 
Section: Moisture knock out drum   Group: 3 
Equipment Code: V-001A  Stream: 8, 10, 11 
Parameter Guide Deviation Causes  Consequences Safeguard Action  Recommendation 
Word 
Level  NONE  No level  Leakage in No supply of raw Install level Investigat Increase the maintenance
pipeline material control LIC- e the of valve XV -A05, control
to moisture to moisture knock A03    leakage in valve, pipelines and
knock out drum out drum V-001A    pipeline  moisture knock out drum
V-001A due to   Install level   V-001A 
corrosion of Separation does indicator LT- Repair the  
gasses  not occur  A03  faulty Increase the monitoring of
      valve  level
    control system performance
Valve XV -A05 m Initiate often 
alfunction  evacuation  
  due to Install pipelines that are
  release of resistant to the corrosion 
Control valve flammable  
CV-A07 and CV- gas  Isolate moisture knock out
A08 drum V-001A from ignition
malfunction  sources 
 
 Overpressure Legend

Install high pressure alarm Mitigating

(PAL) Cause
control

Install pressure relief

valve and rupture disk

High temperature of feed Install high temperature Install temperature control

in reactor alarm (TAH) system (TIC) Major Pre-occurrence
Reactor failure
inciden
High level of materials in Install level control system
reactor (LIC)

Stop all operations Consequence

Blockage in outlet Install high level alarm
pipeline in reactor (LAH)

Prevent ignition drum any

High temperature in feed Install high temperature Install temperature control source
inlet alarm (TAL) system (TIC)

Install auto-shut down Property loss

Evacuate the area Install blast wall Install ventilation
system

Install fire detecting Get insurance Profit loss

Fire/Explosion Install ventilation
system

Install blast wall Evacuate the area Get medical assistance Injury/fatality

Install composition Increase the inspection of

analyzer feed

Impurities in feed

Design reactor that is Increase the maintainance Install gas leakage Shut down and initiate
Corrosion Leakage of materials Fix the leakage evacuation
resitant to corrosion of reactor detector

Systematic inspection of
Human Error Proper training is given
safeguard

Design according to
Design defect operating conditions Figure VIII.5.1: Bowtie diagram for anaerobic reactor
Section IX. References
Patricia A. Westenbroek, Sullivan County, Cornell Cooperative Extension & Jerry
Martin II, 2019. FARM ENERGY. [Online]
Available at: https://farm-energy.extension.org/anaerobic-digesters-and-biogas-
safety/
[Accessed 25 4 2020].

Steiman, M., 2019. FARM ENERGY. [Online]

Available at: https://farm-energy.extension.org/safety-in-small-scale-biodiesel-
production/
[Accessed 25 4 2020].

Zeolyst International, 2014. Zeolyst International. [Online]

Available at: https://www.zeolyst.com/our-products/standard-zeolite-
powders/zeolite-
y/_jcr_content/par/textimage.stream/1505127067462/4126607f242eac53c2044
7250001d433ea936d2a/y-product-cbv-780-sds.pdf
[Accessed 25 4 2020].