CHAPTER 7

SAFETY AND ENVIRONMENTAL CONSIDERATIONS

The goal of the chemical plant is not only to produce the chemicals but produce
them safely. Industries should be careful during operation and maintenance of
the plant. Effective safety measures and emergency response are possible only
when we have a thorough understanding of physical, chemical and biological
properties. In spite of all the safety devices provided in the plant, based on
modern industrial practices and conventions, accidents are likely to occur
unless every employ is cautioned all the time. As industrial personnel, we
should have detailed knowledge of the first aid and safety precautions. We
should undertake in case of emergency.

Safety generally involves:

 Identification and assessments of the hazards.

 Control of hazards.
 Control of the process by the provision of the automatic control system,
alarm trips, etc.
 Limitations of the loss.

7.1 SAFETY ISSUES

NATURE OF HAZARD EFFECTS

Effects on cornea, iris or conjunctiva

that are not expected reverse, eye
Eye contact
irritation, causes severe eye damage,
causes burns of eye lesions.

Destruction of skin issue, with sub

categorization based of exposure,
Skin contact causes skin irritation, causes burns.
Onset of effects may be delayed for
several hours.
 Toxic by inhalation, irritating to
respiratory system, causes burns, may
Inhalation
cause cancer, vapours may cause
drowsiness and dizziness.

Harmful to aquatic organisms, may

Environmental hazards
cause adverse effects in the aquatic
environment.

7.2 FIRST AID MEASURES

1) General advice

Immediate medical attention is required after inhalation or after swallowing

Ensure activity of vitally important functions until the arrival of the doctor
(artificial respiration, inhalation of oxygen, heart massage). If patient is
unconscious, or in case of danger of blackout, transport patient in a stabilized
position. In case of first degree burns (painful redness), and second degree
burns (painful blisters), cool the affected area with cold running water for a
long time. In case of third degree burns (redness, cracking pale skin, usually
without pain), do not cool affected skin, dress the area with sterile dry gauze
only.

2) Inhalation

Remove patient to fresh air, keep him warm and in order to rest quietly. Avoid
walking. Seek medical advice.

3) Skin contact

Immediately take off all contaminated clothing and footwear. Flush effected
area with copious quantities of water. Seek medical advice.

4) Eye contact
Immediately flush eyes with clean lukewarm water and continue flushing for at
least 15 minutes – keep the eyelids widely apart and flush thoroughly with mild
water stream from the inner to the outer canthus. Seek medical advice.

5) Swallowing

Never give anything by mouth to an unconscious person, just put patient into a
stabilized position. Seek medical advice immediately.

6) Advice to physician

Contact the Poison Control Centre or toxicologist for guidance.

Fire Fighting Measures

1) Suitable extinguishable media

Use water spray or fog nozzle to keep container cool. Move container away
from fire if there is no risk.

2) Extinguishing media to be avoided

Not applicable.

3) Caution about specific danger in case of fire and fire-fighting procedures

Danger of violent reaction or explosion. Vapours may travel considerable far

distances and cause subsequent ignition. Vapours are heavier than air, may
cumulate along the ground and in enclosed spaces – danger of explosion. Do
not empty into drains. When burning, it emits carbon monoxide, carbon dioxide
and irritant fumes. Containers with the substance exposed to excessive heat
may explode. May polymerize exothermically if heated or contaminated. If the
polymerization takes place inside a container, the container may rupture
violently. Vapours may burn inside a container. Under prolonged exposure to
fire or heat the containers may rupture violently and rocket.
4) Special protective measures for fire-fighters

Wear full protective fire-resistant clothing and self-contained breathing

apparatus. Vapours may react violently with caustic soda, hydrated lime
(quicklime), magnesium chloride, ammonia, alcohols and amines. Most
materials other than stainless steel or nickel will cause polymerization or
decomposition. Decomposition may cause exothermic rearrangement.

7.3 ACCIDENTAL RELEASE MEASURES

1) Person-related safety precautions

Isolate hazard area. Evacuate all unauthorized personnel not participating in

rescue operations from the area. Avoid entry into danger area. Remove all
possible sources of ignition. Stop traffic and switch off the motors of the
engines. Do not smoke and do not handle with naked flame. Use explosion-
proof lamps and non-sparking tools. Avoid contact with the substance. Apply
recommended full protective personal equipment. When escaping from the
contaminated area, wear mask with cartridge against organic vapours. In case
of general average, evacuate personnel from danger area. In places under the
ground level and

in enclosed spaces (including drains) risk of explosion and accumulation of

toxic vapours.

2) Precautions for protection of the environment

Prevent from further leaks of substance. Do not allow substance to enter soil,
water and sewage systems. In case of substance discharge to water courses or
water containers, inform water consumers immediately, stop service and
exploitation of water.

3) Recommended methods for cleaning and disposal

Pump off substance safely, soak up residues with compatible porous material
and forward for disposal in closed containers. Dispose of under valid legal
waste regulations.

7.4 EXPOSURE CONTROL AND PERSONNEL PROTECTION

1) Occupational exposure controls

Collective protection measures: General and local ventilation, effective

exhaust. Individual protection measures: Personal protective equipment (PPE)
for the protection of eyes, hands and skin corresponding with the performed
labour has to be kept at disposition for the employees. In cases, where the
workplace exposure control limits cannot be observed with the help of
technical equipment or where it is not possible to ensure that the respiratory
system exposure does not represent a health hazard for the personnel, adequate
respiratory protection have to be kept at disposition. In the case of continuous
use of this equipment during constant work, safety breaks have to be scheduled,
if the PPE-character requires this. All PPE have to be kept in disposable state
and the damaged or contaminated equipment has to be replaced immediately.

Respiratory protection: If the exposure limit is exceeded and engineering

controls are not feasible, wear a supplied air, full-face piece respirator, airline
hood, or full face piece self-contained breathing apparatus. protective mask
with canister A (brown coloured, protecting against organic vapours), self-
contained breathing apparatus.

Eye protection: Use chemical safety goggles and/or a full face shield where
splashing is possible. Maintain eye wash fountain and quick-drench facilities in
work area.

Hand protection: Wear gloves of impervious material.

Body protection: Wear impervious protective clothing, including boots, gloves,

lab coat, apron or coveralls, as appropriate, to prevent skin contact. Protective
cover all antistatic design recommended, impervious when handling big
amounts (nitrile rubber), sealed leather footwear (free from synthetic
adhesives)

Hygiene Measures: Wash hands, forearms and face thoroughly after handling.
Appropriate techniques should be used to remove potentially contaminated
clothing. Wash contaminated clothing before reusing. Ensure that eyewash
stations and safety showers are close to the workstation location.

2) Environmental exposure controls Proceed in accordance with valid air and

water legislative regulations.

Engineering measures: Use only with adequate ventilation. If user operations

generate dust, fumes, vapor or mist, use process enclosures, local exhaust
ventilation or other engineering controls to keep worker exposure to airborne
contaminants below any recommended limits. The engineering controls also
need to keep gas, vapor or dust concentrations below any lower explosive
limits. Use explosion-proof ventilation equipment

7.5 TOXICOLOGICAL INFORMATION

1) Acute effects

Toxic substance with carcinogenic and mutagenic effects. Acute intoxication

leads to central nervous system attenuation and narcotic effects occur. After
swallowing possibility of aspiration (passage into the lung) and danger of
chemical pneumonia (pulmonary oedema). Product irritates eyes and skin.
High vapour concentrations irritate respiratory system and eyes and may lead
to fast coma and death. Liquid is absorbed through skin and may develop
allergic eruption.

2) Repeated dose toxicity

Chronic effects cause bone marrow damage, haemopoiesis disorder and may
develop leukaemia.

3) Sensitisation May cause skin allergy.

4) CMR effects (carcinogenity, mutagenicity, toxicity for reproduction) Proved
carcinogenic effects for humans. Substance has mutagenic effects.

5) Toxicokinetics, metabolism, distribution: NA.

7.6 MATERIAL SAFETY DATA SHEET (MSDS)

7.6.1 Terephthalic acid

Flammability of the Product : May be combustible at high temperature.

Auto-Ignition Temperature: 495°C (923°F)

Flash Points: OPEN CUP: 260°C (500°F).

Flammable Limits: Not available.

Products of Combustion: These products are carbon oxides (CO, CO2).

Fire Hazards in Presence of Various Substances: Not available.

Explosion Hazards in Presence of Various Substances:

Risks of explosion of the product in presence of mechanical impact: Not

available. Risks of explosion of the product in

presence of static discharge: Not available.

Fire Fighting Media and Instructions:

SMALL FIRE: Use DRY chemical powder. LARGE FIRE: Use water spray,
fog or foam. Do not use water jet.

Special Remarks on Fire Hazards: Not available.

Special Remarks on Explosion Hazards: Not available.

7.6.2 Mono ethylene glycol

Physical state and appearance: Liquid. (syrupy)

Odor: Odorless.

Taste: Mild sweet

Molecular Weight: 62.07 g/mole

Color: Clear Colorless.

pH (1% soln/water): Not available.

Boiling Point: 197.6°C (387.7°F)

Melting Point: -13°C (8.6°F)

Critical Temperature: Not available.

Specific Gravity: 1.1088 (Water = 1)

Vapor Pressure: 0.06 mmHg @ 20 C; .092 mmHg at 25 C

Vapor Density: 2.14 (Air = 1)

Water/Oil Dist. Coeff.: The product is more soluble in water; log(oil/water) = -

Ionicity (in Water): Not available.

Solubility: Soluble in cold water, hot water, acetone. Slightly soluble in diethyl
ether. Miscible with lower aliphatic alcohols, glycerol, acetic acid, acetone and
similar ketones, aldehydes, pyridine, similar coal tar bases. Practically
insoluble in benzene and its homologs, chlorinated hydrocarbons, petroleum
ether.

Fire and Explosion Data

Flammability of the Product: May be combustible at high temperature.

Auto-Ignition Temperature: 398°C (748.4°F)

Flash Points: CLOSED CUP: 111°C (231.8°F). (Tagliabue.)

Flammable Limits: LOWER: 3.2%

Products of Combustion: These products are carbon oxides (CO, CO2).

Fire Hazards in Presence of Various Substances: Slightly flammable to

flammable in presence of open flames and sparks, of heat. Non-flammable in
presence of shocks.

Explosion Hazards in Presence of Various Substances:

Risks of explosion of the product in presence of mechanical impact: Not

available. Risks of explosion of the product in presence of static discharge: Not
available.

Fire Fighting Media and Instructions:

SMALL FIRE: Use DRY chemical powder. LARGE FIRE: Use water spray,
fog or foam. Do not use water jet.

Special Remarks on Explosion Hazards:

Explosive decomposition may occur if combined with strong acids or strong

bases and subjected to elevated temperatures.

7.6.2 PET

Physical State Solid HEALTH 0

Color Typically clear or off‐white FLAMMABILTY 1

Odor Waxy, mild

Boiling Point: Not determined Vapor Density (Air = 1): Not

applicable

Specific Gravity (@ 23°C): 1.1 Soluble (% in

Water): Negligible
Melting Point: 165 °C Appearance: Solid

Evaporation Rate: Not applicable Odor: Characteristic waxy

Vapor Pressure: Not applicable pH: Not applicable

Odor Threshold: Not determined Auto Ignition Temperature: Not

determined)

Solubility in water: Negligible Viscosity (SUS @ 100°F): Not

applicable

Decomposition Temperature: Not determined Flash Point: Not

determined

Flammability Limits in Air (% by Volume) Lower: Not

applicable Upper: Not applicable

. SAFETY IN PROCESS DESIGN

Accidents are minimized by correct deign using scientific and performance

data without false economy.

1. Reactor:

The reactor is a heart of plant and vital for safety. Most reactions have hazard
potential. Here, reaction is exothermic and at higher pressure compared to
atmospheric pressure and also deals with the materials like Benzene and
Cyclohexane which are highly volatile.
2. Heat Transfer:

For safe operation,

 Prevent mixing.

 Provide different surface, for cleaning, insulation, expansion.

 Prevent flame travel in furnace.

 Use safety over design factor of 15 – 20 %.

3. Mass Transfer:

Safe guards are,

 Prevent liquid injection and vigorous flashing in hot column.

 Provide both pressure and vacuum relief.

 Use detection and warning devices for build up of hazardous material.

 Provide thermal expansion in system.

4. Pressure Vessels:

It includes,

 Corrosion allowance must be provided.

 Take care weld joint efficiency. Design pressure is maximum operating

pressure plus static pressure plus 5 %.

 Design temperature is 25-30 ºC above maximum operating temperature.

  Use safety over design factor of 15 – 20 %.

5. Instrumentation and Safety devices:

 Thermocouple burnout, stem or cooling water failure.

 Fusible plugs to relive pressure above design value.

 Combustible gas monitor with alarms for flammable.

 Over temperature switch.

ENVIRONMENTAL ASPECTS

Industrial waste is produced by industrial activity which includes any material

that is rendered useless during a manufacturing process such as that of
factories, industries, mills, and mining operations. Some examples of industrial
wastes are chemical solvents, sludge, metals, ash, industrial by-products,
metals, and wastes. Toxic waste, chemical waste, industrial solid waste and
municipal solid waste are designations of industrial wastes. Sewage treatment
plants can treat some industrial wastes, i.e. those consisting of conventional
pollutants such as biochemical oxygen demand (BOD). Industrial wastes
containing toxic pollutants require specialized treatment systems.

WATER RECLAMATION

The usage of water reclamation decreases the pollution sent to sensitive

environments. It can also enhance wetlands, which benefits the wildlife
depending on that eco-system. It also helps to stop the chances of drought as
recycling of water reduces the use of fresh water supply from underground
sources. Distillation of used automobile and heavy duty engine coolant under
reduced pressure has been assessed to be an acceptable technology for
recycling ethylene glycol in terms of economic potential, waste reduction
potential, and product quality.

The main potential risks that are associated with reclaimed wastewater reuse
for irrigation purposes, when the treatment is not adequate are the following.

 Contamination of the food chain with micro contaminants, pathogens.

 Soil salinization and accumulation of various unknown constituents.

  Distribution of the indigenous soil microbial communities.

 Alteration of the physicochemical and microbiological properties of the

soil and contribution to the accumulation of chemical/biological
contaminants (e.g. metals, chemicals).

 Excessive growth of algae and vegetation in canals carrying wastewater

(i.e. eutrophication).

 Groundwater quality degradation by the various reclaimed water

contaminants, migrating and accumulating in the soil and aquifers.

WASTE WATER TREATMENT

Wastewaters generated from petrochemical processes contain a large number

of pollutants at high concentrations and have adverse environmental impacts. A
certain type of wastewaters, such as those produced from Ethylene
Oxide/Ethylene Glycol (EO/EG) plants; contain high chemical oxygen demand
(COD) in accordance with mono ethylene glycol and its derivatives as well as
aldehydes. The concentration of pollutants may reach up to 20000mg/L as
COD and 90 mg/L as aldehydes, respectively.

DISPOSAL

Two promising methods for the complete (>99%) destruction of ethylene

glycol in waste water are ultraviolet (UV) light-catalyzed oxidation and
supercritical oxidation.

 In the UV light-catalyzed oxidation method, ethylene glycol-containing

waste water in the presence of 10% hydrogen peroxide is oxidized by
UV irradiation (200–250 nm) with light from a mercury lamp. The
UV/hydrogen peroxide undergoes photochemical decomposition to
produce OH radicals that are strong oxidants capable of oxidizing most
 organic compounds stepwise to complete mineralization (e.g., carbon
dioxide and water).

 In the supercritical water oxidation method, the waste water is

subjected to oxidation at >550 °C and 4,000 psi pressure with a
residence time of treatment technology) has shown potential for the
remediation of soil

contaminated with ethylene glycol. During the in situ vitrification process,

contaminated soil is transformed into silicate glass using large amounts of
electrical energy and a crystalline product similar to obsidian is formed.

 Another approach involving an encapsulated bio-oxidation method

proposes that sodium percarbonate encapsulated in polyvinylidene
chloride be inserted in subsurface soil by a method called hydraulic
fracturing. Oxygen slowly released from the encapsulated sodium
percarbonate increases the number of glycol-degrading organisms. This
method is expected to remediate soils contaminated with glycols via
enhanced aerobic biodegradation in subsurface soils.

One of the problems of a generation line, is the destruction of the MEG at a

high temperature, and in the presence of oxygen, it causes the formation of
carboxylic acids (formic acid, acetic acid and so on) which can decrease the pH
and cause corrosion of carbon steel tanks. Therefore, it is recommended that
the amount of dissolved oxygen for carbon steel systems be kept below 20
ppm. Oxygen scavengers are used to keep the amount of dissolved oxygen low.
Other organic compounds are usually lower than 100 ppm.

A major source of glycol wastage is generated from defrost excess fluids.

Wastewater treatment plants, consider a concentration of 1-5% as the
maximum concentration for an effective microbial degradation with an
acceptable oxygen demand. There are many methods to recycle the ethylene
glycol existing in the wastage of this industrial unit such as: reverse osmosis,
membrane distillation, pervaporation, vacuum distillation, ozonization, use of
activated carbon adsorption, aldehyde separation through stripping, and ion
exchange. These methods have some advantages and disadvantages, and the
two methods with the best performances are ion exchange and aldehyde
separation through stripping. In this study, ion exchange with anion resin
modified with sodium bisulfite were used to decrease the aldehyde and
recirculate the wastage towards the ethylene glycol treatment unit in 1atm and
three different discharges.

ENVIRONMENTAL IMPACT ASSESSMENT

 Screening often results in a categorization of the project and from this a

decision is made on whether or not a full EIA is to be carried out.

 Scoping is the process of determining which are the most critical issues
to study and will involve community participation to some degree. It is
at this early stage that EIA can most strongly influence the outline
proposal.

 Detailed prediction and mitigation studies follow scoping and are

carried out in parallel with feasibility studies.

 The main output report is called an Environmental Impact Statement,

and contains a detailed plan for managing and monitoring
environmental impacts both during and after implementation.

 Finally, an audit of the EIA process is carried out some time after
implementation. The audit serves a useful feedback and learning
function.
HAZOP GUIDE OF: primary
TABLE esterification reactor

GUIDE POSSIBLE CONSEQUENC ACTION

WORD DEVIATION CAUSES ES REQUIRED

-Higher level in
MORE FLOW - Pump racing the reactor - High level alarm

-Increased duty
of heating
system

- Lower level in
LESS FLOW - Pump failure the reactor - Low level alarm

- Line breakage

- Sediment

- Lower level in
NO FLOW - Pump failure the reactor - Low level alarm

- Line breakage

- Line blockage

REVERSE FLOW - Pump failure - Low level alarm

- Lower level in
 the reactor

- Reactor
pressure higher
than delivery

- Partial
blockage of - Check design
MORE PRESSURE vessel or line - Line burst pressure of line

- Reverse flow - Regular operator

LESS PRESSURE - Pump failure from the reactor patrol of all lines.

- Reduced - Warning should be

- Line leakage throughput installed upstream

- Control
problem or
TEMPERATU faulty - Overheating - Regulate steam flow
MORE RE temperature will occur with heat duty

signal (reads
low)

TEMPERATU - Winter - Lower heating - Regulate steam flow

LESS RE condition will occur with heat duty

- Control
problem or
 faulty
temperature

signal (reads
high)

GUIDE OF: primary esterification

HAZOP TABLE NR: 2 / 3 reactor (R-200)

CONSEQUENCE
GUIDE WORD DEVIATION POSSIBLE CAUSES S ACTION REQUIRED

- Failure of reactor - Lower reactor

MORE FLOW level control level - Low level alarm

- Partial failure or - Higher reactor

LESS FLOW blockage of valve level - High level alarm

- Higher reactor
NO FLOW - Failure of valve level - High level alarm

- Partial blockage in -Increased liquid

MORE PRESSURE line level in the reactor - High level alarm

- Check design pressur

- Line burst of line
 - Reduced - Warning should b
LESS PRESSURE - Line leakage throughput installed upstream

- Failure of - Increased reactor - Regulate steam flow

MORE TEMPERATURE temperature control temperature rate with heat duty

- Technical
problems in PV-
400

- Failure of - decreased reactor - Regulate steam flow

LESS TEMPERATURE temperature control temperature rate with heat duty
HAZOP GUIDE OF: primary esterification reactor
TABLE (R-200)

GUIDE ACTION
WORD DEVIATION POSSIBLE CAUSES CONSEQUENCES REQUIRED

-Failure of control - Higher reactor

MORE FLOW valve temperature - Alarm acuted

-Trap frozen

- Partial failure or -Reduced reactor

LESS FLOW blockage of temperature - Alarm acuted

valve

- Failure of control -Reduced reactor

NO FLOW valve temperature - Alarm acuted