CHAPTER IV

ENVIRONMENTAL AND SAFETY CONSIDERATIONS

4.1 SAFETY STUDIES

4.1.1 INTRODUCTION

The process of the production of butanol involved reactants which may cause hazard
and exposure. Therefore, in order to protect the plant from any hazardous and allow it to
operate safely, the environmental and safety analysis are compulsory.

In order to ensure that everybody in the working environment is safe, Health,

Safety and Environmental requirements are enforced. Safety is the important criteria
that must be consider in existing plant. It can be defined as the prevention of accidents
by the use of appropriate technologies to identify the hazards in the chemical plants and
to eliminate them before an accident occurs. This can ensure the plant operate longer
and also convince the worker that they are working in safe environment.

All workers are exposed to a thousand of health hazard as well as having their
safety compromised by the condition of working area as well as surrounding
atmosphere on daily basis. Health hazards like dusts, gases, noise, vibration and
extreme temperature may impose the workers with a greater hazard which can even
take their life.

Therefore, a comprehensive training programme in workplace gives many

benefits to the workers in order to counter any future accident or hazard. The training
that may include the skill development and hazard recognition played an important part
for them to recognize any early symptoms and sign of any potential occupational
disease before that can impose a greater and permanent damage to themselves

With the training also, they also can assess their work environment and insist
that management make changes before hazardous conditions can develop.
All the workers will be educated on how to take what action that they need to do in case
of an accident, which can prevent any injuries and even death.

As for chemical plant, we can get a variety of hazards, from mechanical hazard
to the explosion, reactivity and toxic hazards. Mechanical hazard for examples, like
hazards that cause worker injuries from tripping, falling or moving equipment can be
really dangerous hazard to them.

The Health and Safety at Work Act and various directives and industrial health and
safety regulations are increasingly charging employers and employees with duties at
the workplace .
4.1.2.1 Hazard identification

Hazard is defined as a chemical or physical condition that has the potential to cause
damage to people, property or the environment. It is essential to identify the hazards
and reduce the risk well in advance of an accident.

4.1.2.1.1. Propylene

Propylene in the form of colourless gas does not unlikely to cause harm if exposed
through ingestion, contact with skin and eye. However in the liquid form or cold vapour,
propylene may cause several harms. If in contact with eyes, contact with liquid or cold
vapor may cause frostbite, freeze burns, and permanent eye damage. If accidently
ingested in liquid form, the contact with mucous membranes with liquefied product may
cause frostbite and freeze burns. Signs of frostbite include a change in the color of the
skin to gray or white, possibly followed by blistering. Skin may become inflamed and
painful. Direct contact to skin or mucous membranes with liquefied product or cold
vapor may cause freeze burns and frostbite.

In case of inhalation, propylene in the form of vapour can be a mild hazard due to
the fact, that the gas is simple asphyxiant. In high concentrations it will displace oxygen
from the breathing atmosphere, particularly in confined spaces. Signs of asphyxiation
will be noticed when oxygen is reduced to below 16%, and may occur in several stages.
Symptoms may include rapid breathing and pulse rate, headache, dizziness, visual
disturbances, mental confusion, in coordination, mood changes, muscular weakness,
tremors, cyanosis, narcosis and numbness of the extremities. Unconsciousness leading
to central nervous system injury and possibly death will occur when the atmospheric
oxygen concentration is reduced to about 6% to 8% or less. For the combustion of this
gas, in an area without adequate ventilation may result in hazardous levels of
combustion products, including carbon monoxide, and inadequate oxygen levels, which
may cause unconsciousness, suffocation, and death. Propylene is also not a
carcinogenic agent.
4.1.2.1.2 Rhodium

As for our catalyst, the rhodium which has the form of silvery white solid, it can
be hazardous if it was inhaled. Inhalation of the spray mist may produce severe irritation
of respiratory tract, characterized by coughing, choking, or shortness of breath. Irritation
should stop when exposure id discontinued and first aid procedures are followed
.However, in case of consumption, it is non toxic (LD50, rat >2000 mg/kg) and non-
irritation to skin and eyes according to test on rabbits if within the range above. In case
of prolong exposure, signs and symptoms of irritation are itching, redness and swelling,
and in severe cases, burning and pain at the site of exposure. Liquid or spray mist may
produce tissue damage particularly on mucous membranes of eyes, mouth and
respiratory tract. Skin contact may produce burns.

4.1.2.1.3 Synthesis Gas (Hydrogen, Carbon Monoxide)

Synthesis gas which mainly consisted of hydrogen and carbon monoxide played
an important part as second raw material in the production of butanol. For hydrogen, it’s
almost not hazardous at all except in a high concentrations of inhalation so as to
exclude an adequate supply of oxygen to the lungs causes dizziness, deeper breathing
due to air hunger, possible nausea and eventual unconsciousness. Hydrogen is inactive
biologically and essentially nontoxic; therefore, the major property is the exclusion of an
adequate supply of oxygen to the lungs. Hydrogen is not listed in the IARC, NTP or by
OSHA as a carcinogen or potential carcinogen. Persons in ill health where such illness
would be aggravated by exposure to hydrogen should not be allowed to work with or
handle this product.

For carbon monoxide on the other hand is very hazardous colorless gas which
can cause death after sometime of exposure. Furthermore, it’s undetectable because of
its nature for not having odor or color. It’s also a very flammable gas that can cause
flash fire, an abrupt , intense fire caused by ignition of a mixture of air and a dispersed
flammable substance such as a solid (including dust), flammable or combustible liquid
(such as an aerosol or fine mist), or a flammable gas. It is characterized by high
temperature, short duration, and a rapidly moving flame front. Carbon monoxide is not
detectable by odor and headache should be taken as a warning that a dangerous
concentration is being inhaled. In sudden exposures to high concentrations, weakness
and dizziness may be the only symptoms preceding collapse. The amount of
carboxyhemoglobin formed in the blood is dependent on concentration and duration of
exposure, ambient temperature, physical exertion, health, and individual metabolism.
Symptoms are usually not noticeable until the carboxyhemoglobin level reaches 10%.
At 10-40%, symptoms may include increasingly severe headache, dyspnea on exertion,
decreased manual dexterity, impaired judgment and memory, irritability, emotional
instability, dizziness, fatigue, drowsiness, confusion, nausea, vomiting, palpitations, and
impaired vision and hearing. With continuing exposure, there is a progressive worsening
of all symptoms.

At 40-60%, angina pain, in coordination, hallucinations, lethargy, syncope and

collapse, and increased respiration and pulse may occur. At 60-80% there may be
decreased respiration, blood pressure and pulse, and deepening coma with intermittent
convulsions and incontinence of urine and feces. Rarely, there may be a pink or red
skin discoloration, but cyanosis or pallor is more common. Other reported signs and
symptoms include increased temperature, dilated pupils, perspiration, muscle spasms,
hyperreflexia, aching limbs, and retinal hemorrhage or venous engorgement. Above 70-
80%, rapid death from respiratory or cardiac arrest usually occurs. Death may also be
caused by myocardial or cerebral infarction. Cerebral edema may also occur. In non-
fatal cases or when death is not immediate, primary or secondary effects of tissue
hypoxia and some atypical reactions may develop. In case of eye contact, maximum
exposure to this gas can cause frostbite and would resulting blurred vision and also the
same for skin contact except for a blister.
4.1.2.1. 4. Butanol

Our final product, butanol also has lots of hazardous quality. If a worker inhaled too
much butanol fumes, they can be poisoned because of its low volatility. This may
caused irritation to upper respiratory tract. Difficult breathing, coughing, headache,
dizziness, and drowsiness may occur. For ingestion through mouth, the workers may
have experience narcotic effect. It’s also caused abdominal pain, nausea, headache,
dizziness, and diarrhoea. Large doses may affect kidneys and liver and they also may
suffer from the loss of hearing. Hearing loss has been reported in workers chronically
exposed to butyl alcohol.

May affect sense of balance, liver and kidneys. Estimated mean lethal dose is 3
7 ounces. A constant exposure to the skin may cause skin irritation, due to loss of
natural skin oils .Prolonged skin contact may cause drying and cracking of skin. A
butanol fumes can cause eyes irritation, causing a tearing and pain. Splashes cause
inflammation and blurred vision. Persons with pre-existing skin disorders or eye
problems, or impaired liver, kidney or respiratory function may be more susceptible to
the effects of the substance.
4.1.3 POTENTIAL INCIDENT HAZARDS

Table 4.2 Effects of propylene, hydrogen, carbon monoxide, rhodium and butanol to health

Chemicals Contact Health Effects First Aid Measures

Propylene Eye Liquid or cold vapor may cause frostbite, freeze burns, Immediately flush eyes with lukewarm
and permanent eye damage water for at least 15 minutes while
lifting upper and lower eyelids.

Continue to flush the eyes if there is

any indication of residual chemical.

Skin Skin may become inflamed and painful. For exposure to liquid, warm frostbite
area gently with room temperature
Direct contact to skin or mucous membranes with water.
liquefied product or cold vapor may cause freeze burns Seek medical attention.
and frostbite.

Inhalation May cause asphyxiation symptoms may include rapid
breathing and pulse rate, headache, dizziness, visual
disturbances, in coordination, mood changes, muscular
weakness, tremors, cyanosis,narcosis and numbness
of the extremities.
Remove affected individual to fresh air
while insuring the rescuers utilize
protective equipment.
If breathing is difficult, administer
oxygen.
 [continue]
Table 4.2 Effects of propylene, hydrogen, carbon monoxide, rhodium and butanol to health

Chemicals Contact Health Effects First Aid Measures

Rhodium Eye  Liquid or spray mist may produce tissue damage
particularly on mucous membranes of eyes, mouth and
respiratory tract.
Skin  Symptoms of irritation are itching, redness and
swelling, and in severe cases, burning and pain at the
site of exposure.
 Skin contact may produce burns.
Inhalation Inhalation of the spray mist may produce severe
irritation of respiratory tract, characterized by coughing,
choking, or shortness of breath.
 Flush with water for at least 15 minutes
including beneath eyelids.

 Remove contacts/glasses while
flushing.
 Wash area with soap and water while
removing contaminated clothing.
 Wash for at least 15 minutes.
 Get immediate medical attention. Wash
clothing/shoes thoroughly before reuse.
Remove to fresh air. If breathing has
stopped, administer artificial
respiration.

Irritation should stop when exposure id discontinued If breathing is difficult, give oxygen
and first aid procedures are followed supply.

[continue]
 Table 4.2 Effects of propylene, hydrogen, carbon monoxide, rhodium and butanol to health

Chemicals Contact Health Effects First Aid Measures

Hydrogen Eye Liquid or spray mist may produce tissue damage
particularly on mucous membranes of eyes,
mouth and respiratory tract.
Immediately flush eyes with plenty of water
for at least 15 minutes.
Then get immediate medical attention
medical attention.

Skin Symptoms of irritation is blisters, and in case of If frostbite or freezing occur, immediately
serious exposure, frostbite. flush with plenty of lukewarm water

Skin contact may produce burns. If warm water is not available, gently wrap
affected parts in blanket.

Inhalation High concentrations of inhalation so as to exclude
an adequate supply of oxygen to the lungs
causing dizziness, deeper breathing due to air
hunger, possible nausea and eventual
unconsciousness.
Remove to fresh air. If breathing has
stopped, administer artificial respiration.
If breathing is difficult, give oxygen.
Get immediate medical attention.

[continue]
Table 4.2 Effects of propylene, hydrogen, carbon monoxide, rhodium and butanol to health
Chemicals Contact Health Effects
Carbon Eye Frostbite, blurred vision.
Monoxide
Skin Symptoms of irritation is blisters, and in case of
serious exposure, frostbite.
Skin contact may produce burn.
Inhalation Changes in body temperature, changes in blood
pressure, nausea, vomiting,chest pain, difficulty
breathing,irregular
heartbeat,headache,drowsiness, dizziness,
disorientation, hallucination, pain in extremities,
tremors, loss of coordination, hearing loss, visual
disturbances, eye damage, suffocation, blood
disorders, convulsion, coma.
[continue]
Table 4.2 Effects of propylene, hydrogen, carbon monoxide, rhodium and butanol to health
First Aid Measures
Contact with liquid: Immediately flush eyes
with plenty of water for at least 15
minutes.
If frostbite or freezing occur, immediately
flush with plenty of lukewarm water
(105-115°F; 41-46°C).
DO NOT USE HOT WATER. If warm water
is not available, gently wrap affected parts in
blanket
If adverse effects occur, remove to
uncontaminated area.
Give artificial respiration if not breathing.
If breathing is difficult, oxygen should be
administered by qualified personnel
Chemicals Contact Health Effects First Aid Measures
Butanol Eye Vapours can be irritating, causing tearing and Immediately flush eyes with plenty of water
pain. for at least 15 minutes, lifting lower and
upper eyelids occasionally.
Splashes cause inflammation and blurred vision
Get medical attention immediately.
Skin An irritant to the skin, causing a loss of natural In case of contact, immediately flush skin
oils. with plenty of water for at least 15 minutes.

Can be absorbed through skin with symptoms Remove contaminated clothing and shoes.
paralleling those from ingestion. Wash clothing before reuse.

Call a physician.

Inhalation Causes irritation to upper respiratory tract. Difficult
breathing, coughing, headache, dizziness, and
drowsiness may occur.
May be absorbed into the bloodstream with
symptoms similar to ingestion.
Remove to fresh air. If not breathing, give
artificial respiration.
If breathing is difficult, give oxygen.
4.2 CONTROL AND PREVENTIVE MEASURE

4.2.1 CHEMICAL HANDLING

There are four types of chemicals composed of toxic agents, corrosives,

flammable and reactive. The toxic agents are the chemicals that are poisonous and can
act upon body at a very rapid rate. Some examples of the substances that have this
property are hydrogen sulphide and cyanide. Corrosives are the type of chemical that is
usually an irritant, damaging the body by burning, scalding or inflaming body tissues.
For examples are chlorine, hydrochloric acid, battery acids, etc. Flammables are the
chemicals that can burnt easily and very rapid. They may explode or burn if sparks,
flames or ignition sources are present. For examples are gasoline, benzene and ethyl
ether. The other type of chemical is reactive chemicals. Reactive chemicals are those
that require stability and careful handling. Some of them can explode or react violently if
mixed improperly with other substances. The example of reactive chemical is Nitro
glycerine
For this plant of butanol production, the chemicals that are used as reactants are
propylene and synthesis gas composed of hydrogen and carbon monoxide with the
presence of rhodium which acted as catalyst to fasten this process. Below are the
proper procedures on how to handle the chemicals used and produces in this process.
4.2.1.1 Raw Materials

4.2.1.1.1. Propylene

Propylene is non-corrosive and may be used with any common structural material.
However, this gas is a simple asphyxiant and in high concentrations it will displace
oxygen from the breathing atmosphere, particularly in confined spaces. Therefore, its
crucial to use it in a well-ventilated areas. Valve protection caps must remain in place
unless container is secured with valve outlet piped to use point. Do not drag, slide or roll
cylinders. Use a suitable hand truck for cylinder movement. Use a pressure regulator
when connecting cylinder to lower pressure (<250 psig) piping or systems.

Do not heat cylinder by any means to increase the discharge rate of product from
the cylinder. Use a check valve or trap in the discharge line to prevent hazardous back
flow into the cylinder. Protect cylinders from physical damage. Store in cool, dry, well-
ventilated area away from heavily trafficked areas and emergency exits. Do not allow
the temperature where cylinders are stored to exceed 130oF (54oC). Cylinders should
be stored upright and firmly secured to prevent falling or being knocked over. Full and
empty cylinders should be segregated. Use a "first in-first out" inventory system to
prevent full cylinders from being stored for excessive periods of time.

It’s crucial to avoid any contact between the gas from any source of ignition due
to the fact that this gas is extremely flammable and can cause serious damage if any
explosion occurred. Post "No Smoking" signs in storage or use areas. Never carry a
compressed gas cylinder or a container of a gas in cryogenic liquid form in an enclosed
space such as a car trunk, van or station wagon. A leak can result in a fire, explosion,
asphyxiation or a toxic exposure.
Earth bond and ground all lines and equipment associated with the product system.
Electrical equipment should be non-sparking and explosion proof.
4.2.1.1. 2. Synthesis Gas (Hydrogen)

Synthesis gas composed of hydrogen and carbon monoxide played a very important
role in the production of butanol where it will act as the main raw material. Therefore,
the presence of synthesis gas needs a very special handling especially in a huge
amount of it.

Hydrogen gas is a non-corrosive and may be used with any common structural
material and does not imposed a great danger due to the fact that it’s a little bit except
in a large quantity. It’s crucial to check whether the valve protection caps remained in
place unless container is secured with valve outlet piped to use point. Only use the gas
in a well-ventilated area. Do not drag, slide or roll cylinders. Use a suitable hand truck
for cylinder movement and use a pressure reducing regulator when connecting cylinder
to lower pressure (<3,000 psig) piping or systems.

Do not heat cylinder by any means to increase the discharge rate of product from
the cylinder. Use a check valve or trap in the discharge line to prevent hazardous back
flow into the cylinder. Protect cylinders from physical damage by storing the cylinder in a
cool, dry, well-ventilated area of noncombustible construction away from heavily
trafficked areas and emergency exits

Do not allow the temperature where cylinders are stored to exceed 125F (52C).
Cylinders should be stored upright and firmly secured to prevent falling or being
knocked over. Full and empty cylinders should be segregated. Use a “first in -first out”
inventory system to prevent full cylinders being stored for excessive periods of time.
Due to the nature if the gas that is flammable, it’s crucial to avoid and placing the
cylinder any source of ignition to avoid combustion. Posting a “No Smoking or Open
Flames” signal in the storage or use area is also a good suggestion.
 Earth-ground and bond all lines and equipment associated with the hydrogen
system. Electrical equipment should be non-sparking or explosion proof. Compressed
gas cylinders should not be refilled except by qualified producers of compressed gases

4.2.1.1. 3. Synthesis Gas (Carbon Monoxide)

Carbon Monoxide, a colorless and odorless gas, is a chemical asphyxiant and can
produce significant, adverse health effects at relatively low concentrations. Over-
exposure to Carbon Monoxide can cause nausea, dizziness, headaches, and collapse.
Therefore, it’s crucial for the workers to be aware to any symptom of dizziness or fatigue
due to the exposures to fatal concentrations of this product could occur without any
significant warning symptoms. Do not attempt to repair, adjust, or in any other way
modify the cylinders containing Carbon Monoxide. If there is a malfunction or another
type of operational problem, contact nearest distributor immediately.

Cylinders should be firmly secured to prevent falling or being knocked-over.

Cylinders must be protected from the environment, and preferably kept at room
temperature (approximately 21°C, 70°F). Cylinders should be stored in dry, well-
ventilated areas, away from sources of heat, ignition, and direct sunlight. Protect
cylinders against physical damage. Full and empty cylinders should be segregated. Use
a first-in, first-out inventory system to prevent full containers from being stored for long
periods of time. These cylinders are not refillable. Compressed gases can present
significant safety hazards. During cylinder use, use equipment designed for these
specific cylinders. Ensure all lines and equipment are rated for proper service pressure.
Make certain that application equipment is locked and tagged-out safely. Always use
product in areas where adequate.

Earth-ground and bond all lines and equipment associated with the hydrogen
system. Electrical equipment should be non-sparking or explosion proof. Compressed
gas cylinders should not be refilled except by qualified producers of compressed gases
4.2.1.1.4. Rhodium

This solid silvery substance a toxic or hazardous material unless exposed it at a huge
amount especially through inhalation. Therefore, to maintain its powdery form, its crucial
to keep the container dry from any moisture. Do not ingest. Do not breathe gas/fumes/
vapor/spray and avoid contact with skin .to operate around this material, the workers
need to wear protective clothing and in case of insufficient ventilation, they need to
wear respiratory equipments.

In case of accidental ingested, they need to seek medical advice immediately.

Rhodium can corrode metallic surfaces and needed to be stored in a metallic or coated
fiberboard drum using a strong polyethylene inner package. Corrosive materials should
be stored in a separate safety storage cabinet or room.

4.2.2.2 Products

4.2.2.2.1. Butanol

Butanol has flammable property and needed an extra precaution and the right method
of handling to ensure no accident will take place.

It’s crucial to keep it away from heat or sources of ignition, because if any of this
sources took place anywhere near the storage area, a catastrophic accident might
occur. Ground all equipment containing material.

To process this alcohol, the workers need to wear a protective clothes and gears
to avoid an accidental ingestion as well as inhalation of the gas, vapor or fumes from
this butanol. A well ventilated area with a proper flow of fresh air is important to avoid
this accident. If ingested, seek medical advice immediately and show the container or
the label. Avoid contact with skin and eyes. Keep away from incompatibles such as
oxidizing agents and reducing agents
 Do not allow the temperature where cylinders are stored to exceed 125F (52C).
Cylinders should be stored upright and firmly secured to prevent falling or being
knocked over. Full and empty cylinders should be segregated. Use a “first in -first out”
inventory system to prevent full cylinders being stored for excessive periods of time.
Due to the nature if the gas that is flammable, it’s crucial to avoid and placing the
cylinder any source of ignition to avoid combustion. Posting a “No Smoking or Open
Flames” signal in the storage or use area is also a good suggestion. Store the butanol in
a segregated and approved area. Keep container in a cool, well-ventilated area. Keep
container tightly closed and sealed until ready for use.

4.2.3 ACCIDENTAL RELEASE MEASURE

The emergency can be minimized if proper immediate response is done when the
hazardous material is accidently spilled out or leak. Therefore, this chapter is will
prepare us in the event of a hazardous spill before using a chemical. Below are the
accidental release measure for each raw materials and product for this plant of butanol
production.
4.2.3.1 Raw Material

4.2.3.1.1. Propylene

Evacuate all personnel and secure all ignition sources. No road flares, smoking or
flames in hazard area. Consider wind direction, stay upwind and uphill, if possible.
Evaluate the direction of product travel. Vapor cloud may be white, but color will
dissipate as cloud disperses. If fire and explosion hazard is still present. Stop the source
of the release, if safe to do so. Do not flush down sewer or drainage systems. Do not
touch spilled liquid (frostbite/freeze burn hazard). Consider the use of water spray to
disperse vapors. Isolate the area until gas has dispersed. Ventilate and gas test area
before entering.

4.2.3.1.2. Synthesis Gas (Hydrogen)

Evacuate all personnel from affected area. Use appropriate protective equipment. If leak
is in user’s equipment, be certain to purge piping with an inert gas prior to attempting
repairs. If leak is in container or container valve, contact your closest supplier location or
call the emergency telephone number listed herein.

4.2.3.1.3. Synthesis Gas (Carbon Monoxide)

For occupational spill and release, avoid heat, flames, sparks and other sources of
ignition. Then, stop leak if possible without personal risk. As prevention procedure, use
water spray to reduce vapours. Keep unnecessary people away, isolate hazard area
and deny entry. Toxic, flammable gas may spread. Before entering area, especially a
confined area, check atmosphere with an appropriate device.

Ventilate closed spaces before entering. This gas is very dangerous since it cannot
be detected by odor. Immediately evacuate all personnel from danger area. Do not
approach area without self-contained breathing apparatus.
4.2.3.1.4. Rhodium
Uncontrolled releases should be responded to by trained personnel using A pre-
planned procedures. Proper protective equipment should be used. In case of a spill,
clear the affected area, protect people, and respond with trained personnel. For small
releases, the minimum Personal Protective Equipment should be rubber gloves and
rubber apron, splash goggles or safety glasses. In the event release situations present
the potential for inhalation of mists or sprays, respiratory protection should be worn. If
necessary, use air-purifying respirator with aid gas cartridges.

In case of a non-incidental spill, clear the affected area, protect people, and respond
with trained personnel. Minimum Personal Protective Equipment should be Level B:
triple-gloves (rubber gloves and nitrile gloves, over latex gloves), chemically resistant
suit and boots, hard-hat, and Self Contained Breathing Apparatus (SCBA).

SCBA should be worn when oxygen levels are below 19.5% or are unknown. Absorb
spilled liquid with polypads or other appropriate materials. Decontaminate the area
thoroughly by rinsing with soapy water. Use litmus paper to test area and ensure
complete decontamination. If necessary, neutralize the area with sodium bicarbonate or
other acid-neutralizing. Place all spill residue in a double plastic bag and seal
4.2.3.2. Product

4.2.3.2.1. Butanol

In case of accidental spill of the butanol, there are several steps needed to be taken.
Firstly, ventilate area of leak or spill. For the persons who will be performing clean-up
work should wear adequate personal protective equipment and a self-contained
breathing apparatus with full face piece operated in the pressure demand or other
positive pressure mode. Keep unnecessary and unprotected personnel from entering.
Remove all sources of ignition.

If small spill occur, firstly isolate spill or leak area for 50 to 100 meters. Eliminate
all potential ignition sources. Stop leak when safe to do so. Ground all approved
equipment used in area. Keep area isolated until any detectable flammable gas has
been dispersed.

For large spill, it required to consider initial downwind evacuation for at least 800
meters. All potential ignition sources have to be eliminated. Stop leak when safe to do
so. Alert stand by emergency and fire fighting personnel. Monitor surrounding area for
build up of flammable gas concentration. Ground all approved equipment used in area.
Evacuate personnel to upwind of the spill area and position at a safe distance. Consider
use of water spray to reduce vapours or divert cloud drift. High expansion foam cover
may help suppress evolution of flammable gas. Prevent flammable or liquids from
entering ditches, drains and sewers or other confined or underground structures.
Accumulations of gas may persist in low areas. Keep isolated until any detectable
flammable gas has been dispersed.
4.2.4 FIRE PREVENTION AND SAFETY PROCEDURE

The major hazard in chemical plant, are fires that will proceed to an explosion if any
accident is occur. In order to prevent fire, the most important element is to keep the
plant away from the preventable presence of ignition sources such as open flame,
sparks and external ignition sources. For the unpreventable presence of ignition
sources in the plant such as the presence of motor, boilers and leakage, a standard
code of practice should be followed to avoid fire. Therefore, the availability of any fire
extinguisher medium as such water supplies, fireman and hydrants and foam is
compulsory.

The fire occurs when these four elements present in the same time . They are:

1. Enough oxygen to sustain oxygen

2. Enough heat to raise the material to its ignition temperature
3. Some sort of fuel or combustion material
4. The chemical reaction that is fire

4.2.4.1 Fire extinguishers

Fire extinguisher is one of the most important components in a chemical plant. The
present of flammable gases in the process stream, especially ethylene, will give a
sensible threat of fire hazard to the plant. Therefore, routines check on flammable
substances and equipment operating flammable substance should be done. Fire
extinguisher should be fitted at easily-accessible location, such as against a wall in a
high-traffic area.

Fire extinguishers are labelled to the kind of fire they will be effective against.
The user must read the label to be sure that the appropriate equipment is used to
extinguish the fire. Labels will indicate: Class A. Class B, Class C.
 1. Class A: Ordinary combustibles
Fires in paper, cloth, wood, rubber, and many plastics require a water type
extinguisher labelled A.
2. Class B: Flammable liquids
Fires in oils, gasoline, some paints, lacquers, grease, solvents, and other
flammable liquids require an extinguisher labelled B.
3. Class C: Electrical equipment
Fires in wiring fuse boxes, energized electrical equipment, computers, and
other electrical sources require an extinguisher labelled C.

4.2.4.2 Smoke detector

Flammable gases such as ethylene gases pose a special safety problem because the
gases are essentially invisible. Therefore, thermal and optical sensors have been
developed to detect burning gases.

Thermal fires detectors can be referred as rate-of-temperature-rise detectors and

overheat detectors are not subject to frequent failure. To cover a large area or volume,
many thermal detectors are required to be installed and must be located at or very near
the possible site of a fire. Optical fires sensors operate in two spectral regions,
ultraviolet and infrared. In general, different sensors and optical components must be
used in each region. Closed-circuit infrared and ultraviolet remote-viewing systems,
equipped with appropriate filters, have been used successfully.

Fire detection systems should be installed in storage and used areas to give alert
whenever a worst allowable condition is exceeded. The fire detectors should give a
rapid and reliable indication of the existence, location, and size of the fire. Automatic
shutdown systems, triggered by multiple fire detectors and activated quickly enough to
prevent large-scale damage, should be considered. Connecting an automatic shutdown
system to a fire-detecting system may not always be effective since alarms may be
triggered by reflections from allowable fires (burn ponds and flare stacks) and sunlight.
The routine check of any sign of leak or hazard materials can also be done.

4.2.4.3 Fire and smoke alarms

The chance of dying from fire can be cut into half when working smoke alarms are
installed. Fire alarm system is invented to notice the presence of unwanted fire by
supervising the environmental changes related to combustion. Generally, the fire alarm
system can be classified as automatically motivated, manually motivated or both. They
can be used to inform people to evacuate in the event of fire or other emergency. In the
same time, the alarms will alerts the Fire Department which responds immediately.
Anyone who heard the fire alarms should react immediately and be prepared to
evacuate during normal operating hours.

4.2.4.4 Leak detector

A leak detector is a very important equipment to have in chemical plant. It can tell us if
the equipment is working properly or not. Furthermore, it also can reveal any potential
hazardous problems with the equipment.

Leaks of process materials are the process industries biggest hazard. Most of the
materials handled will not burn or explode unless mixed with air in certain proportions or
it may release as poisonous gas. To prevent fires and explosions, we must therefore
keep the fuel in the plant and the air out of the plant. The latter is relatively easy
because most plants operate at pressure.

The main problem in preventing fires and explosions is thus preventing the
process material leaking out of the plant, which is maintaining plant integrity. Similarly if
toxic or corrosive materials are handled, they are hazardous only when they leak.
4.2.4.5 Safety at works

From Occupational Safety and Health Act 1994, Part IV, Section 15, states that:
(1) It shall be the duty of every employer and every self-employed person to ensure,
so far as is practicable, the safety, health and welfare at work of all his
employees.

Therefore, the employer is responsible to ensure safety and health of the

employee. The employer must have knowledge about the risk and ways to reduce it.
Their level of knowledge has to be reasonable; it can be seen from their common
practice and knowledge throughout the industry.

There are a few basic safety rules, which must be observed and practiced by
employees when working in chemical manufacturing areas :

i. Observe all safety policies, regulations, safe work practices and job
instructions for certain occupation.
ii. Must be familiarized with the company safety programs which affect their
job.
iii. Correct the safety hazards and unsafe conditions that can be handled by
them. Others should be reported to the supervisor or person in charge.
iv. Avoid congested storage, poor housekeeping, poor lighting, broken
equipment, blocked exits and passages, and other unsafe conditions that
may lead to accidents.
v. Observe all warning signs and safety colour coding: “Red” colour is used to
identify fire protective equipment, dangerous conditions, a biological hazard,
or stop signs/stop controls on machinery. “Orange” colour is used to indicate
a warning and “yellow” colour is used to denote caution and physical
hazards.
vi. Inform others associate employee when seeing an accident about to
happen, or if they are committing any unsafe act.
 vii. Know the personal protective equipment required for the job.
viii. Be familiar with the company’s Fire & Emergency Response Plan and know
how to report a fire and the escape route.
ix. Do not block or obstruct fire doors, escape routes or sprinkler heads.
x. Avoid running, except in emergency situations.
xi. Use step-ladder instead of climbing desks, shelves or stacked materials.
xii. Never enter a “confined space” such as manhole, pit, underground vault,
chamber tank, a place with little ventilation, or a place where they could be
trapped or locked inside.
xiii. Avoid carrying loads that block your vision.
xiv. Keep the shelves and storage free from any accumulation of materials that
may cause tripping, failing objects and fires.
xv. Make sure tools and equipment are in safe condition before using them.
xvi. Use machinery only when authorized to do so and after receiving safety
training.

4.2.4.6 Personal protective equipment (PPE)

The use of personal protective equipment (PPE) is required by Occupational Safety and
Health Administration (OSHA) to reduce employee exposure to hazards when
engineering and administrative controls are not feasible or effective in reducing these
exposures to acceptable levels .

From Occupational Safety and Health Act 1994, Part VI, Section 24(1c), states
that:
It shall be the duty of every employee while at work to wear or use at all times any
protective equipment or clothing provided by the employer for the purpose of
preventing risks to his safety and health
 Therefore, the employee should wear or use all the personal protective
equipment provided by the employer. If the PPE is not suitable, the employee should
inform the employer regarding the problem.

A wide range of clothing and equipment for protecting protection in a variety for
materials is generally available and the chemical operative should seek the advice of his
supervisor as to the correct type to use for each task he may be required to perform.
Below are the list of hazard and types of PPE to be used .

Table 4.5 Lists of hazard and recommended PPE

Part of bodies Hazard PPE

Eyes Chemical or metal splash,
dust, projectiles, gas and
vapor, radiation
Head Impact from falling or flying
objects, risk of head
bumping, hair entanglement.
Breathing Dust, vapor, gas, oxygen
deficient atmospheres.
Hands and arms Abrasion, temperature
extremes, cuts and
punctures, impact,
chemicals, electric shock,
skin infection, disease or
contamination.
Feet and legs Wet, electrostatic buildup,
slipping, cuts and punctures,
falling objects, metal and
chemical splash, abrasion.
Safety spectacles, goggles,
face shields, visors.
A range of helmets and
bump caps.
Disposable filtering faces
piece or respirator, half or
full-face respirators, air fed
helmets, breathing
apparatus.
Gloves, gauntlets, mitts,
wrist cuffs, armlets.
Safety boots and shoes with
protective toe caps and
penetration resistant
midsole, gaiters, leggings,
 spat.
Protecting the Temperature extremes, Chainmail aprons, high
body adverse weather, chemical. visibility clothing.

4.2.4.7 Threshold limit value (TLV)

For body to be able to detoxify thus eliminate all the agents without any traceable effect,
the workers needed to stay below the threshold dose. Threshold dose is the lowest
value on the toxic response versus dose curve.

To standardize this limit, The American Conference of Governmental Industrial

Hygienists (ACGIH) established a threshold doses with the name of called threshold
limit values (TLVs), for a large number of chemical agents, referring to the airborne
concentration which no adverse effects are expected during the worker’s lifetime. The
exposure occurs only during working hours, eight hours per day, and five days per
week. It was formerly known as maximum allowable concentrations (MAC).

TLV – TWA or time-weighted average stated that for a normal 8-hour workday or
40-hour work week which mean nearly all workers can be exposed, day after day,
without adverse effects to themselves. Excursions above the limit are allowed if
compensated by excursions below the limit. OSHA also has defined its own threshold
dose, called permissible exposure level (PEL). PEL values follow the TLV-TWA of
ACGIH closely. The values of TLV-TWA and PEL for propylene, rhodium, carbon
monoxide, hydrogen and butanol are shown in table 4.6 .

Table 4.6 TLVs and PELs for chemical substances

Substance OSHA PEL TLV-TWA

 ppm ppm
Propylene Not established 600/1032.62
(mg/m3 )
Carbon 50/57.29 25/28.62
Monoxide
(mg/m3 )
Hydrogen Not established Not established
(mg/m3 )
Rhodium 0.02375/0.1 10.1/1
(mg/m3 )
Butanol 100/303.14 50/151.574
(mg/m3 )

There is no information on hydrogen substances, but according to its chemical

properties, hydrogen can be considered as really mild hazard substance. Higher
threshold limit means it’s less dangerous to the workers to be exposed off.

4.2.4.7.7 Propylene

4.2.4.7.1 .1 Exposure Limits

Table 4.7 Data for Exposure Limits

Chemical Name ACGIH NIOSH OSHA
Propylene 500 ppm no established 4 m

4.2.4.7.1.2 Fire and Explosion Measures

Liquid releases flammable vapors at well below ambient temperatures and readily forms
a flammable mixture with air. Dangerous fire and explosion hazard when exposed to
heat, sparks or flame. Vapors are heavier than air and may travel long distances to a
point of ignition and flash back. Container may explode in heat or fire. Runoff to sewer
may cause fire or explosion hazard.

4.2.4.7.1.3 Accidental Release Measures

Evacuate nonessential personnel and secure all ignition sources. No road flares,
smoking or flames in hazard area. Consider wind direction, stay upwind and uphill, if
possible. Evaluate the direction of product travel. Vapor cloud may be white, but color
will dissipate as cloud disperses. If fire and explosion hazard is still present. Stop the
source of the release, if safe to do so. Do not flush down sewer or drainage systems.
Do not touch spilled liquid (frostbite/freeze burn hazard). Consider the use of water
spray to disperse vapors. Isolate the area until gas has dispersed. Ventilate and gas
test area before entering.

4.2.4.7.1.4 Personel Protection

Use under well-ventilated conditions. Exhaust ventilation should be used at any

operation capable of releasing vapors. Maintain oxygen level above 19.5%. Confined
spaces where an oxygen deficient atmosphere may exist should be checked for oxygen
content before entry.

Wear a NIOSH/MSHA-approved airline or air-supplied respirator when oxygen

levels drop below 19.5%. Use in accordance with manufacturer's use limitations and
OSHA Standard 1910.134 (29 CFR). Wear chemical goggles with face shield and wear
protective gloves and clothing as needed to prevent contact with liquefied propylene.

4.2.4.7.1.5 Environment Information

Liquid release is only expected to cause localized, non-persistent environmental

damage, such as freezing. Biodegradation of this product may occur in soil and water.
Volatilization is expected to be the most important removal process in soil and water.
This product is expected to exist entirely in the vapor phase in ambient air .

4.2.4.7.2 Synthesis Gas (Hydrogen)

4.2.4.7.2.1 Exposure Limits

Table 4.8 Data for Exposure Limit
Chemical Name ACGIH NIOSH OSHA
Carbon monoxide Simple Asphyxiant Not established Not established

4.2.4.7.2.2 Fire and Explosion Measures

If possible, stop the flow of hydrogen. Cool surrounding containers with water spray.
Hydrogen burns with an almost invisible flame of relatively low thermal radiation and
can be considered mild hazardous. The fire fighter should use water, carbon dioxide or
dry chemical based fire extinguisher to stop this from further spreading.
Hydrogen is very light and rises very rapidly in air. Should a hydrogen fire be
extinguished and the flow of gas continue, increase ventilation to prevent an explosion
hazard, particularly in the upper portions.

4.2.4.7.2.3 Accidental Release Measures

Evacuate all personnel from affected area. Use appropriate protective equipment. If leak
is in user’s equipment, be certain to purge piping with an inert gas prior to attempting
repairs. If leak is in container or container valve, contact your closest supplier location or
call the emergency telephone number listed herein.

4.2.4.7.2.4 Personal Protection

Wear safety glasses with side shields, chemical goggles or a full face shield to avoid
burns or tissue damage from frostbite if the hydrogen is in the liquid phase.Avoid
repeated or prolonged skin conta by wear protective clothing as required

This product is a known simple asphyxiant and air supplied respirators are
required if there is a potential for decreased oxygen concentrations.therefore , a normal
regulation of air is important to avoid oxygen depletion in case of leakage . Please be
ensure that the oxygen concentration remains above 19.5% and Carbon Dioxide
concentration does not exceed 5000 ppm, Local exhaust at points of emission
preferred. Except in the confined or low air regulation space, a respirator is not required.

4.2.4.7.2.5 Environmental information

Since the gas is not toxic, it can be release directly to the air. As for animal and plant,
any adverse effect on animals would be related to oxygen deficient environments. No
adverse effect is anticipated to occur to plant-life. Cylinders should be returned in the
original shipping container, properly labelled, with residual product, valve outlet plugs or
caps secured and valve protection cap in place.

4.2.4.7.3 Synthesis Gas (Carbon Monoxide)

Table 4.9 Data for Exposure Limits

Chemical Name ACGIH NIOSH OSHA
Carbon monoxide 25 ppm 200 ppm 50 pm

4.2.4.7.3.1 Fire and Explosion Measures

Containers contain this chemical may rupture or explode if exposed to heat. If rupture or
explode occur, move container from fire area if it can be done without risk. Then, cool
containers with water spray until well after the fire is out.

Stay away from the ends of tanks. For fires in cargo or storage area, cool containers
with water from unmanned hose holder or monitor nozzles until fire is out. If this is
impossible then take the following precautions. Firstly, keep unnecessary people away,
isolate hazard area and deny entry. If the fire burn can’t control, exit immediately. If
leakage occur in tank, rail car or tank truck top so it required to stop leak if possible
without personal risk.

4.2.4.7.3.2 Accidental Release Measures

For occupational spill and release, avoid heat, flames, sparks and other sources of
ignition. Then, stop leak if possible without personal risk. As prevention procedure, use
water spray to reduce vapours. Keep unnecessary people away, isolate hazard area
and deny entry. Toxic, flammable gas may spread. Before entering area, especially a
confined area, check atmosphere with an appropriate device.

Ventilate closed spaces before entering. This gas is very dangerous since it cannot
be detected by odor. Immediately evacuate all personnel from danger area. Do not
approach area without self-contained breathing apparatus.
4.2.4.7.3.3 Personal Protection

Wear splash resistant safety goggles. Contact lenses should not be worn. Provide an
emergency eye wash fountain and quick drench shower in the immediate work area.
Then, wear appropriate protective and cold insulating clothing and wear insulated
gloves. Under conditions of frequent use or heavy exposure, respiratory protection
may be needed. Respiratory protection is ranked in order from minimum to maximum.
Consider warning properties before use.
 For the gas phase, eye protection not required, but recommended. For the liquid it’s
crucial to wear splash resistant safety goggles. Contact lenses should not be worn.
Provide an emergency eye wash fountain and quick drench shower in the immediate
work area. Besides that, wear appropriate gloves and protective clothing like synthetic
apron to prevent skin exposure.

Use vapor respirator and be sure to use an approved respirator or equivalent.

Protective clothing is not required for the gas phase however for the liquid, wearing the
appropriate protective, cold insulating clothing would be the best since any contact with
liquidized carbon monoxide can cause frostbite. Suggested protective clothing might not
be sufficient and consult a specialist before handling this product.

4.2.4.7.3.4 Environmental information

Before releasing any residue or waste from the gas, it’s important to treat it to prevent
the waste from contaminating the surrounding environment. Keep personnel away. To
discard any product, residue, disposable container, or liner, it’s crucial to do it in an
environmentally acceptable manner, with full compliance with federal, state, and local
regulations. If necessary, call your local supplier for assistance

4.2.4.7.4 Rhodium
Table 4.10 Data for Exposure Limits
Chemical Name ACGIH NIOSH OSHA
Rhodium 10.1 ppm 0.02375 ppm 4.2 ppm

4.2.4.7.4.1 Fire and Explosion Measures

Though rhodium is not flammable, it can be one when heated to decomposition level,
creating the product to emit acid mists and toxic gases (including oxides of sulfur and
rhodium oxides) which is very harmful to human. This product may generate heat when
in contact with water. Contact with many inorganic and organic chemicals also can
cause potentially vigorous and violent reactions producing Sulfuric Acid (a component of
this product).

Sulfuric acid is not flammable substance, however when in contact with metals, it
will liberate hydrogen gas that may form an explosive with the mixture of air. Incipient
fire responders should wear eye protection. Structural fire fighters must wear self-
contained breathing apparatus and full protective equipment. If possible, fire-fighters
should control run-off water to prevent environmental contamination.

4.2.4.7.4.2 Accidental Release Measures

Uncontrolled releases should be responded to by trained personnel using A pre-

planned procedures. Proper protective equipment should be used. In case of a spill,
clear the affected area, protect people, and respond with trained personnel. For small
releases, the minimum Personal Protective Equipment should be rubber gloves and
rubber apron, splash goggles or safety glasses. In the event release situations present
the potential for inhalation of mists or sprays, respiratory protection should be worn. If
necessary, use air-purifying respirator with aid gas cartridges.

In case of a non-incidental spill, clear the affected area, protect people, and respond
with trained personnel. Minimum Personal Protective Equipment should be Level B:
triple-gloves (rubber gloves and nitrile gloves, over latex gloves), chemically resistant
suit and boots, hard-hat, and Self Contained Breathing Apparatus (SCBA).

SCBA should be worn when oxygen levels are below 19.5% or are unknown. Absorb
spilled liquid with polypads or other appropriate materials. Decontaminate the area
thoroughly by rinsing with soapy water. Use litmus paper to test area and ensure
complete decontamination. If necessary, neutralize the area with sodium bicarbonate or
other acid-neutralizing. Place all spill residue in a double plastic bag and seal.

4.2.4.7.4.3 Personal Protection

In case to avoid inhalation, proper ventilation played an important part. Use a

mechanical fan or vent area to regulate the air to outside. Respiratory protection is not
normally required for routine use of this product. Maintain airborne contaminant Use a
corrosion-resistant exhaust system. In case of accident, it’s crucial to have eye-
wash/safety shower stations should be near locations in which this product is stored or
handled. If respiratory protection is needed (i.e., an air-purifying respirator with an acid-
gas cartridge when mists or sprays can be generated), use only protection authorized in
applicable State regulations. Use supplied air respiratory protection when oxygen levels
are below 19.5% or are unknown.

The following are the NIOSH respiratory protection guidelines for Rhodium
Compounds (soluble):

Concentration Respiratory Protection

 0.010 mg/m : Any air-purifying respirator with a high-efficiency particulate 3 filter;

supplied air respirator.

 0.025 mg/m3: Any supplied-air respirator in continuous-flow mode; any powered,

air-purifying respirator with a high efficiency particulate filter.
  0.050 mg/m3: HiEF/PAPRTHiE/SCBA/SAF; Any air-purifying, full-face piece
respirator with a high-efficiency particulate filter; any powered, air-purifying
respirator with a high-efficiency particulate filter and a tight face-piece; full face
piece Self Contained Breathing Apparatus; or, Supplied Air Respirator.

 2.0 mg/m3: SAF: PD, PP Supplied Air Respirator operated in pressure demand
or positive-pressure mode. Emergency or Planned Entry into Unknown
Concentrations or IDLH Conditions: Positive pressure, full faces piece Self
Contained Breathing Apparatus; or positive pressure, full face piece Supplied Air
Respirator with an auxiliary positive pressure Self Contained Breathing
Apparatus.

For eyes protection, a splash goggles or safety glasses should be used for routine
operations. Face-shield should be worn when working with more than 1 gallon of this
product or during operations in which mists or sprays may be generated.

Wear neoprene gloves for routine industrial use for hand protection. Use triple
gloves for spill response. Rubber apron for routine use

4.2.4.7.4.4 Environmental information

This product will react with a wide variety of materials in the environment. The primary
effects on plant, aquatic, or animal life would be caused by the low Ph of the material.
The exact effects depend on the extent of exposure. Lowered pH can be harmful or fatal
to animal life. Spills of large amounts of this material into water could lower pH
sufficiently to be harmful or fatal to animals or aquatic life in contaminated bodies of
water.
 Therefore it is important for the manufacturer to ensure a proper treatment,
aimed at eliminating environmental contamination. Precious metal recovery can be
considered as a potential waste-handling option. Otherwise, disposal must be in
according to the state rules and regulations.

4.2.4.7.5 Butanol
Table 4.11 Data for Exposure Limits
Chemical Name ACGIH NIOSH OSHA
Butanol 50 ppm 50 ppm 4 ppm

4.2.4.7.5.1 Fire and Explosion Measures

Butanol is a combustible and flammable liquid, sensible to static discharged and can
imposed great dangerous fire hazard when exposed to heat and flame and ignition
sources. Vapor-air mixtures are explosive above flash point and may travel
considerable far distances.

In the event of a fire, move the containers from fire area, if only it can be done
without risks. Apply cooling water to sides of containers that are exposed to flames until
well after fire is out. Stay away from the ends of the tanks. For massive fire in cargo
area, use unmanned hose holder or monitor nozzles; if this is impossible, withdraw from
the area and let fire burn. Withdraw immediately in case of rising sound from venting
safety device or any discoloration of tank due to. Isolate for 500 meters in all directions
if tank, rail car or tank truck is involved in fire.

For the Protection of fire-fighter, In the event of a fire, wear full protective clothing
an approved self-contained breathing apparatus with full face piece operated in the
pressure demand or other positive pressure mode. Use suitable fire extinguishing media
is important to ensure its effectiveness in extinguishes the fire, which in this case the
foam type. For a small fire incident, dry chemical and carbon dioxide is enough. To cool
the tanks, using sprayed water would do the job. Avoid using water stream, since the
water stream will tend to scatter thus spreading the fire bigger.

4.2.4.7.5.2 Accidental Release Measures

In case of accidental spill of the butanol, there are several steps needed to be taken.
Firstly, ventilate area of leak or spill. For the persons who will be performing clean-up
work should wear adequate personal protective equipment and a self-contained
breathing apparatus with full face piece operated in the pressure demand or other
positive pressure mode. Keep unnecessary and unprotected personnel from entering.
Remove all sources of ignition.

If small spill occur, firstly isolate spill or leak area for 50 to 100 meters. Eliminate
all potential ignition sources. Stop leak when safe to do so. Ground all approved
equipment used in area. Keep area isolated until any detectable flammable gas has
been dispersed.

For large spill, it required to consider initial downwind evacuation for at least 800
meters. All potential ignition sources have to be eliminated. Stop leak when safe to do
so. Alert stand by emergency and fire fighting personnel. Monitor surrounding area for
build up of flammable gas concentration. Ground all approved equipment used in area.
Evacuate personnel to upwind of the spill area and position at a safe distance. Consider
use of water spray to reduce vapours or divert cloud drift. High expansion foam cover
may help suppress evolution of flammable gas. Prevent flammable or liquids from
entering ditches, drains and sewers or other confined or underground structures.
Accumulations of gas may persist in low areas. Keep isolated until any detectable
flammable gas has been dispersed.

4.2.4.7.5.3 Personal Protection

Use an air supplied respirator when working in confined space or where local exhaust or
ventilation does not keep exposure below Threshold Level Value. Select in accordance
with the provincial regulations or guidelines. Selection should also be based on the
current CSA standards Z94.4, "Selection, care and use of respirators". Respirators
should be approved by NIOSH and MSHA.

Wear nitrilic rubber gloves when handling cylinders and wear safety glasses
when handling cylinders.Select in accordance with the current CSA standard Z94.3,
"Industrial Eye and Face Protection", and any provincial regulations, local by laws or
guidelines. Avoid using contact lenses at work. The working area will be equipped with
eyewash fountains.

Wear impervious protective clothing (full suit), including boots, lab coat, apron or
coveralls, as appropriate, to prevent skin contact. The protective equipment
contaminated with butanol will be immediately took out and washed. The contaminated
equipment will not be stored near clean clothing and in will not be taken home because
the family member must not be exposed.

4.2.4.7.5.4 Environmental information

Keep out of sewers and watercourses by dyking or impounding. Advise appropriate

authorities of any spills especially if product has entered or may enter sewers, water
courses, or extensive land areas. When release to water, this material is expected to
quickly evaporate and when release in the soil, this material will both evaporate and
leach into ground water due to its relatively high vapor pressure and low absorption to
the soil.
 Due to its high volatility, the main exposure path is through the contaminated
atmosphere Federal and provincial regulations must be followed in the clean up and
disposal of this product and associated wastes. Butanol is dangerous for aquatic
organisms. Insufficient data regarding long term effects on plants, birds or land animals.
Do not allow it to enter waters, waste water or soil.

4.3. HAZARD AND OPERABILITY STUDIES (HAZOP)

4.3.1 General Objectives of Hazard and Operability Studies (HAZOP)

A Hazard and Operability (HAZOP) study is a structured and systematic examination of

a planned or existing process or operation in order to identify and evaluate problems
that may represent risks to personnel or equipment, or prevent efficient operation.
4.3.2 HAZOP Study Methodology

As general, the Hazop study process involves applying in a systematic way all relevant
keyword combinations to the plant in question in an effort to uncover potential
problems.  The results are recorded in columnar format under the following headings:

Table 4.10 Example columnar format to record data

Deviation Cause Consequence Safeguards Action

4.3.2.1 Hazard and Operability Studies (HAZOP) Procedures

Select a 'Sub System'

Applied a 'Property Word' (also refers to as a parameter)

Apply a 'Guide Word' to a property word to give a

'Deviation'

Identify the 'Causes'

 Identify the 'Consequences'

Identify the existing 'Safeguards'

Decide on any 'Action' to eliminate or

mitigate the identified problems

Repeat for others guide word as relevant

Repeat for others Property Words as relevant

Repeat for all Sub System

Figure 4.1 Procedures in HAZOP studies

4.3.2.2 Hazard and Operability Studies (HAZOP) Techniques

In this process is more emphasis on questioning and systematic analysis. So, the use of
keywords are very important to indicate the attention of the team upon deviations and
their possible causes. These keywords are divided into two which are:
 Primary Keywords which focus attention upon a particular aspect of the design
intent or an associated process condition or parameter.
  Secondary Keywords can be used when combined with a primary keyword to
suggest possible deviations

Table 4.11 Primary Keywords

Parameter Key Word Definition
Flow No No Flow
One Quantitative Increase
More Quantitative Decrease
Less Opposite Direction
Reserve

Pressure More More than Normal

Less Less than Normal
Temperature More More than Normal
Less Less than Normal
Level More More than Normal
Less Less than Normal
Composition Different from Solid instead of liquid (if
As well as applicable)
Corrosive
Explosive
Out of specification

Other Contamination Leakage of release to

Leakage and spillage atmosphere
Maintenance

Table 4.12 Secondary Keywords

Guide Word Meaning Example of Deviation
No or Not No part of the intended result is No flow to reactor
achieved and nothing else happens
Less Quantitative decrease in the intent Less flow to the reactor
More Quantitative increase in the intent More flow to the reactor
 Part of Qualitative decrease in the intent Part of the reactants to the
reactor
As well as Qualitative increase in the intent Cooling water in the
reactor

Reverse Logical opposite of the intention Reverse flow into the

reactor

Other than Complete substitution Another material besides

reactants in the reactor

4.3.2.3 HAZOP Team

The team who will conduct the Hazop study should consist of personnel with a good
understanding of the process and plant to be reviewed.  The group should ideally
contain about six members, with perhaps an absolute upper limit being set at nine.  In a
study in which both contractor and client are participating, it is desirable to maintain a
balance between the two in terms of team membership so that neither side feels
outnumbered.

4.3.2.3.1 Emergency Response Management Team (ERMT)

4.3.2.3.1.1 Responsibility of ERMT

1. Oversees the preparation of the Site Emergency Plan.
2. Assist in the selection of other ERMT members.
3. Runs the Command Centre.
4. Obtains initial information regarding a crisis situation. “Briefs” the other ERMT members
regarding the nature and status of the crisis.
5. Determines the need for emergency response.
6. Determines what outside agencies should be notified.
7. Determines if evacuations are in order, and for what area(s).
8. Instructs team members as to their movement within the plant during the crisis.
9. Activates “replacement members” of the ERMT whenever original Team Members are
unavailable, and appoints additional replacement members if necessary.
10. Orders “shutdowns” if called for.
11. Assigns “in-house” resources (such as fire brigade) as appropriate.
12. Establishes initial interfaces with outside agencies.
13. Determines what information should be released to the media

4.3.2.3.1.2 ERMT Chair - Desirable Characteristics

1. Should be able to work efficiently in highly pressurized situations.

2. Should be a verbal communicator, able to both give and obtain information clearly
and concisely.
3. Should have strong organizational capabilities and experience, and be able to
recognize and understand the functional relationships between ERMT Members.
4. Should have strong managerial capabilities and experience, and be able to manage
and direct people. Should be able to coordinate a large number of activities
occurring both simultaneously and rapidly.
5. Should have strong leadership qualities, able to command respect and instil
confidence in other Team members and employees.
6. Should have strong analytical skills, and be able to examine a situation and draw
appropriate conclusions.
7. Should have strong “conceptualization” skills, being able to “draw a picture” of a
crisis situation based on information from outside the Command Centre.
8. Should have good, overall knowledge of the plant.
9. Should be readily available 24hrs a day, seven days a week.

4.4 Material Safety Data Sheet (MSDS)

To operate using chemical substances, it a wise decision to learn the details regarding
the materials before proceeding to next level. MSDS is a detailed, well organized data
prepared by the manufactures or importers of the chemical substances that explain the
physical and chemical properties, effect of exposure, safe handling and storage, first-aid
procedures, and control measures.

All these important information is crucial, that can help employers and the workers
to respond effectively to the daily exposure situations and also in case of emergency
incidents. Below shows fire and explosion measures, accidental release measures,
personal protection and environmental information for propylene, rhodium, hydrogen,
carbon monoxide and butanol.

4.4.1 SUMMARY OF MSDS

4.4.1.1 PHYSICAL AND CHEMICAL PROPERTIES

All the physical and chemical properties of the chemicals used and produced in the
process are listed in the table below:-

Table 4.1 Physical and chemical properties of raw material and product

Properties Propylene Rhodium Synthesis gas Butanol

Hydrogen/carbon
monoxide
Molecular Formula C3H6 Rh H2 CO C4H10O
Molecular Weight (g/mol) 42.08 102.9055 1.00794 28.010 g 74.122
0
Density (g/L)
613.9 0.01241 0.08988 789 809.8
Specific Gravity 0.516 12.41 0.0696 0.9667 0.810 -
0.812
3 -7
Solubility in water (g/m ) @ 6.1 x 10 Not 0.0016 0.0026 0.7
 20oC soluble
Freezing point/melting point − 185.2 1964 259.1 −205 −89.5
(°C ,K ,° F) 88 2237 -14.01 68 184
-301 3567 - 434 -337 -129

Boiling point − 47.6 3695 252.8 −191.5 117.7

(°C ,K ,° F) 226 3968 -20.28 82 391
-54 6683 -423. ° -313 244

Viscosity (µPa·s) 8.34 N/A N/A N/A 3

Table 4.1 Physical and chemical properties of raw material and product

Properties Propylene Rhodium Synthesis gas Butanol

H2 CO
Vapour Density (air = 1.81 N/A 0.0899 1.250 2.6 k
1)
(kg/m3 )
Appearance Colourless Silvery-white Colourless Colourles Colourles
gas solid gas s gas s liquid