Industrial Safety

by

Omar Mustafa Hussein Al-Kubaisi

A lecture note
presented to the University of Anbar
in
Chemical and Petrochemical Engineering Department

Anabr, Iraq 2019

c Omar Mustafa Hussein Al-Kubaisi 2019

�
Chapter 2

Hazards in The Chemical Process

Industries

Introduction
The multitude of products and diversity of processes in the petrochemical industries
is vast, with numerous situations that may lead to high risk situations both for
workers and communities neighboring operations. Perhaps one of the worst chemical
disasters of the century was Bhopal, India, The city of Bhopal (1991 pop. 1,063,662),
central India, capital of Madhya Pradesh state, was founded in 1728. Bhopal is a
railway junction and industrial center, producing electrical equipment, textiles, and
jewelry. Landmarks include the old fort (built 1728) and the Taj-ul-Masajid mosque,
the largest in India. On Dec. 3, 1984, the worst industrial accident in history
occurred there when a toxic gas leak from a Union Carbide insecticide plant killed
over 6,400 people and seriously injured 30,000 to 40,000. The Indian government sued
on behalf of over 500,000 victims and in 1989 settled for $470 million in damages
and exempted company employees from criminal prosecution. The Indian judiciary
rejected that exemption in 1991, and the company’s Indian assets were seized (1992)
after its officials failed to appear to face charges.

2.1 General Terminology

The definitions provided are universally recognized, and in many cases the impor-
tance of the term in relation to a MSDS (Material Safety Data Sheet) is explained

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2.1.1 Acid:
There are several definitions for acid. The Arrhenius definition is a substance that
ionizes in water to product H+ ions. The Bronsted definition is a substance that is
a proton (H’) donor. This does not require the substances to be in aqueous (water)
solution.
An acidic solution is defined as one that has a pH less than 7.0. The following
are examples of strong acids, meaning that they completely dissociate into ions and
form H+ in aqueous (water) solution.
For example:

HCl −→ H+ +Cl-

All of these will cause severe burns upon skin contact: Perchloric acid (HCIO4 ),
Hydroiodic acid (HI), Hydrobromic acid (Hbr), Hydrochloric acid (HCl), Sulfuric
acid (H2 SO4 ), and Nitric acid (HNO3 ,). Weak acids do not dissociate completely
into ions.
The lower the pH, the greater the acidity of a solution. Just because an acid is
weak does not mean that it can’t be harmful. For example, HF, hydrofluoric acid, is
a weak acid. When you spill it on your hand it doesn’t burn, but over the course of
hours it migrates to the bones in your fingers and then begins to dissolve them from
the inside out (a painful process; amputation can be required).
Proposed Questions
What are the common properties of acids?

1 They have a sour taste.

2 They can react with metals such as magnesium, zinc or iron to corrode them and
produce explosive hydrogen gas. Do not store acids in metal containers;

3 Solutions of acids can conduct electricity.

Proposed Questions
Why its important to know the PH of substances?
It is important to know the pH of substances because they may be corrosive or
react with incompatible materials. For example, acids and bases should not be

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stored or used near each other as their accidental combination could generate a huge
amount of heat and energy, possibly resulting in an explosion. pH is also important
to know in case you spill the material on your skin or eyes.
Proposed Questions
What is required to do whenever a substance enters the eye?
Flush with water for 15 minutes and get prompt medical attention.

2.1.2 Acute toxicity:

Acute toxicity describes the adverse effects resulting from a single exposure to a
substance. Acute toxicity helps workers understand the health consequences from a
single exposure to a chemical. Acute toxicity differs from chronic toxicity, which de-
scribes the adverse health effects from repeated (lower level) exposures to a substance
over a longer period (months to years).
Proposed Questions
Define the acute toxicity, and what is difference of acute toxicity from
chronic toxicity?
(Answer: Paragraph above)

2.1.3 Alopecia
Alopecia is the loss of hair. Acute or chronic exposure to some chemicals may result
in the temporary or permanent loss of hair.

2.1.4 Ames Test

The Ames Test is a way of determining whether a compound causes genetic mu-
tations (changes). Animal liver cell extracts are combined with a special form of
salmonella bacteria. The mixture is then exposed to the test substance and exam-
ined for signs that the bacteria have mutated (a process called mutagenesis). The
Ames test does not directly indicate the carcinogenic (cancer- causing) potential of
the substance, however there is a good correlation between mutagen strength and
carcinogen strength in rodent studies.

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2.1.5 Anesthesia
Anesthesia is a loss of sensation or feeling. Anesthesia (or anaesthetic) is often
used deliberately by doctors and dentists to block pain and other sensations during
surgical procedures. Treatment for pre- or postoperative pain is called analgesia.

2.1.6 Anhydride
An anhydride is a compound that gives an acid or a base when combined with
water. Many substances are not themselves acids or bases, but will become such
when exposed to water. This does not necessarily require the addition of water (such
as from a fire hose). Many anhydrides will react readily with ambient humidity and
even the water present in your skin or lungs. The reaction of anhydrides with water
is often very violent and exothermic (giving off a great deal of heat energy). The
reaction to form sulfuric acid is one step in the reaction of sulfur oxide emissions to
form ”acid rain”. The reaction to form acetic acid is used in certain silicone caulks,
leading to the familiar smell of vinegar (vinegar is a 5 % solution of acetic acid in
water), while the caulk cures.

2.1.7 Anhydrous
Anhydrous: An anhydrous material does not contain any water molecules. Many
substances occur naturally as hydrates, compounds that have a specific number of
water molecules attached to them. This water can often be removed by heating
and/or vacuum to give the anhydrous material. Anhydrous materials can absorb
water from their surroundings and find use as dessicants. Examples include those
packets of silica gel you find in some consumer goods, as well as dehumidifying sachets
used in clothes closets. When an anhydrous material reacts with water, this could
release a large amount of heat, possibly leading to a heat or pressure buildup that
could result in an explosion.

2.1.8 ANSI-American National Standards Institute

American National Standards Institute, ANSI, is a private, nonprofit membership
organization representing organizations, businesses and government over 1,000 public
and private agencies. They seek to develop technical, political and policy consensus

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among various groups. Their web site is http://www.ansi.org/. ANSI does not
develop American National Standards (ANSs), but they accredit qualified groups to
do so in their area(s) of technical expertise. There are over 14,000 ANSI-approved
standards in use today.
ANSI format is likely to be consistent from country to country, possibly permit-
ting one to use the same MSDS in different markets without modification. Most
businesses that issue new MSDSs today use the ANSI standard format.

2.1.9 Combustible
A combustible material can be a solid or liquid. The U. S. Occupational Health and
Safety Administration (OSHA) defines a combustible liquid as ”any liquid having
a flash point at or above 100 O F (37.8 ”C), but below 200 O F (93.3 ”C), except
any mixture having components with flashpoints of 200O F (93.3 ”C), or higher, the
total volume of which make up 99 percent or more of the total volume of the mixture.
” Compare this definition to flammable, which indicates a liquid that is even easier
to ignite (flash point below 100 OF). OSHA divides combustible (and flammable)
liquids into several classes. Combustible solids are those capable of igniting and
burning. Wood and paper are examples of such materials.
Proposed Questions
How we can store combustible materials in a Lab. or others?
Proper storage and use of combustible materials is absolutely critical in maintaining
a safe work place. Avoid placing or using combustible materials near sources of heat
or flame.

2.2 Chemical Process

2.2.1 Polymer Production

A polymer or resin can be defined as a solid or semisolid, water-insoluble, organic
substance, with little or no tendency to crystallize. Resins are the basic components
of plastics and are important components of surface-coating formulations. There are
two types of resins – natural and synthetic. The natural resins are obtained directly
from sources such as fossil remains and tree sap.
Synthetic resins can be classified by physical properties as:

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1- Thermoplastic: Thermoplastic resins undergo no permanent change upon heat-
ing.They can be softened, melted, and molded into shapes they retain upon
cooling, without change in their physical properties.
2- Thermosetting: Thermosetting resins can be softened, melted, and molded
upon heating, but upon continued heating, they harden or set to a perma-
nent, rigid state and cannot be remolded.

Proposed Questions
What are the difference between the thermoplastic and thermosetting
synthetic polymeric resins?

Manufacturing Equipment and Inhalation Exposures in Polymer Industry

Most resins are polymerized or otherwise reacted in a stainless steel, jacketed, indi-
rectly heated vessel, which is completely enclosed, equipped with a stirring mecha-
nism, and generally contains an integral reflux condenser. Since most of the reactions
previously described are exothermic, cooling coils are usually required. Some resins,
such as the phenolics, require that the kettle be under vacuum during part of the
cycle. This can be supplied either by a vacuum pump or by a steam or water jet
ejector. Moreover, for some reactions, that of polyvinyl chloride for example, the
vessel must be capable of being operated under pressure. This is necessary to keep
the normally gaseous monomer in a liquid state.
The size of the reactor vessels varies from a few hundred to several thousand
gallons capacity. Because of the many types of raw materials, ranging from gases to
solids, storage facilities vary accordingly: ethylene, a gas, is handled as such; vinyl
chloride, a gas at standard conditions, is liquefied easily under pressure. It is stored,
therefore, as a liquid in a pressurized vessel. Most of the other liquid monomers do
not present any particular storage problems. Some, such as styrene, must be stored
under an inert atmosphere to prevent premature polymerization. Some of the more
volatile materials are stored in cooled tanks to prevent excessive vapor loss.
Some of the materials have strong odors, and care must be taken to prevent
emission of odors to the atmosphere. Solids, such as phthalic anhydride, are usually
packaged and stored in bags or fiber drums. Treatment of the resin after polymer-
ization varies with the proposed use.
The major sources of possible air contamination are the emissions of raw mate-
rials or monomer to the atmosphere, emissions of solvent or other volatile liquids

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during the reaction, emissions of sublimed solids such as phthalic anhydride in alkyd
production, emissions of solvents during thinning of some resins, and emissions of
solvents during storage and handling of thinned resins.
In the formulation of polyurethane foam, a slight excess of tolylene diisocyanate
is usually added. Some of this is vaporized and emitted along with carbon dioxide
during the reaction. The TDI fumes are extremely irritating to the eyes and respira-
tory system and are a source of local air pollution. Since the vapor pressure of TDI is
small, the fumes are minute in quantity and, if exhausted from the immediate work
area and discharged to the outside atmosphere, are soon diluted to a nondetectible
concentration. No specific controls have been needed to prevent emission of TDI
fumes to the atmosphere.
There are a variety of air pollution control equipment that are used to minimize
emissions, however, not all are effective, depending upon the problem. Scrubbing and
condensing equipment is not capable of controlling some odors adequately because
some of the objectionable material is in the form of noncondensable or insoluble gas
or vapor, or is particulate matter of very small size. Scrubbers are, however, valuable
adjuncts when used as precleaners. The scrubbing equipment used upstream from
the final collection device is generally a spray tower, a plate tower, a chamber or
tower with a series of baffles and water curtains, an agitated tank, or a water jet
scrubber. The spray tower is probably the most efficient because the high degree of
atomization that can be obtained in the scrubbing liquid by the sprays allows for
maximum contact between the scrubbing water and particulate matter. A major
disadvantage of the spray tower, however, is the excessive maintenance required to
keep the spray nozzle free from clogging and in proper operation if the scrubbing
media are recirculated. From an economic point of view, the baffled water curtain
scrubber is better but is less efficient.

2.2.2 Sulfuric Acid Manufacturing

Sulfuric acid is used as a basic raw material in an extremely wide range of industrial
processes and manufacturing operations. Table 4 lists the properties and chemical
hazards of sulfuric acid. Basically, the production of sulfuric acid involves the gener-
ation of sulfur dioxide (SO2 ), its oxidation to sulfur trioxide (SO3 ), and the hydration
of the SO3 to form sulfuric acid. The two main processes are the chamber process
and the contact process. The chamber process uses the reduction of nitrogen dioxide
to nitric oxide as the oxidizing mechanism to convert the SO2 to SO3 . The contact

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process, using a catalyst to oxidize the SO2 to SO3 , is the more modern and the more
commonly encountered.
A contact process plant, intended mainly for use with various concentrations of
hydrogen sulfide (H2 S) as a feed material, is known as a wet-gas plant. The wet-
gas plant’s combustion furnace is also used for burning sulfur or dissociating spent
sulfuric acid.
A common procedure for wet-gas plants located near petroleum refineries is to
sulfuric acid from the burn simultaneously H2 S, molten sulfur, and spent alkylation
processes at the refineries. In some instances a plant of this type may produce sulfuric
acid by using only H2 S or spent acid. In a wet-gas plant, the H2 S gas, saturated with
water vapor, is charged to the combustion furnace along with atmospheric air. The
SO2 formed, together with the other combustion products, is then cooled and treated
for mist removal. Gas may be cooled by a waste-heat boiler or by a quench tower
followed by updraft coolers. Mist formed is removed by an electrostatic precipitator.
Moisture is removed from the SO2 and air stream with concentrated sulfuric acid in a
drying tower. A centrifugal blower takes suction on the drying tower and discharges
the dried SO2 and air to the converters. The balance of the wet-gas process is
essentially the same as that of the previously discussed sulfur-burning process.
The most significant source of air contaminant discharge from a contact sulfuric
acid plant is the tail gas discharge from the SO3 absorber. While these tail gases
consist primarily of innocuous nitrogen, oxygen, and some carbon dioxide, they also
contain small concentrations of SO2 and smaller amounts of SO3 and sulfuric acid
mist. Tail gases that contain SO3 , owing to incomplete absorption in the absorber
stack, hydrate and form a finely divided mist upon contact with atmospheric mois-
ture. The optimum acid concentration in the absorbing tower is 98. 5 percent. This
concentration has the lowest SO3 vapor pressure. The partial pressure of SO3 in-
creases, if the absorbing acid is too strong, and SO3 passes out with the tail gases.
If a concentration of absorbing acid less than 98.5 percent is used, the beta phase
of SO3 , which is less easily absorbed, is produced. A mist may also form, when the
process gases are cooled before final absorption, as in the manufacture of oleum.
Water scrubbing of the SO3 absorber tail gases can remove 50 to 75 percent of
the SO2 content. Scrubbing towers using 3-inch or larger stacked rings are often
employed. On startups, when SO2 concentrations are large, soda ash solution is
usually used in place of straight water. Water scrubbing is feasible, where disposal
of the acidic waste water does not present a problem. Tail gases may be scrubbed with
soda ash solution to produce marketable sodium bisulfite. The traditional process
for removal of SO2 from a gas stream is scrubbing with ammonia solution. Single-

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and two-stage absorber systems reduce SO2 concentrations in tail gases. Two-stage
systems are designed to handle SO2 gas concentrations as great as 0.9 percent. Large
SO2 concentrations resulting from acid plant startups and upsets could be handled
adequately by a system, such as this.
Electrostatic precipitators are widely used for removal of sulfuric acid mist from
the cold SO2 gas stream of wet-purification systems. The wet-lead-tube type is
used extensively in this service. Tube-type and plate-type precipitators have also
been used for treating tail gases from SO3 absorber towers. Dry gas containing
SO2 , carbon dioxide, oxygen, nitrogen, and acid mist enters two inlet ducts to the
precipitator.
Corrosion possibilities from concentrated sulfuric acid must be considered in se-
lecting wire mesh material. The initial cost of wire mesh equipment is modest.
Porous ceramic filter tubes have proved successful in removing acid mist. The filter
tubes are usually several feet in length and several inches in diameter with a wall
thickness of about 3/8 inch. The tubes are mounted in a horizontal tube sheet, with
the tops open and the bottoms closed. The tail gases flow downward into the tubes
and pass out through porous walls. Appreciably more filtering area is required for
the ceramic filter than for the wire mesh type.
The porous ceramic filter is composed of small particles of alumina or similar
refractory material fused with a binder. The maintenance costs for ceramic tubes is
considerably higher, than those for wire mesh filters because of tube breakage. Initial
installation costs are also considerably higher, than those for wire mesh. A pressure
drop of 8 to 10 inches water column is required to effect mist removal equivalent to
that of a wire mesh filter. Thus, operating costs would also be appreciable. Another
approach is sonic agglomeration. The principle of sonic agglomeration is also used to
remove acid particles from waste-gas streams. Sound waves cause smaller particles in
an aerosol to vibrate and thereby coalesce into larger particles. Conventional cyclone
separators can then be used for removal of these larger particles. A nuisance factor
must be taken into consideration, however, since some of the sound frequencies are in
the audible range. Simple baffles and cyclone separators are not effective in collecting
particles smaller than 5 microns in size.
Next Lecture will be ”INHALATION AND FIRE HAZARDS IN REFINERIES”,
Good luck Dr. Omar

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Chapter 3

20
Chapter 4

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Chapter 5

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Chapter 6

Home work and Assignment

Example

(H.W) A Tanker carrying toluene is unloaded, using the ships pump, to an onshore
storage tank, The pipeline is 225 mm internal diameter and 900 m long. Miscella-
neous loss due to fittings, valves, etc. , amount to 600 equivalent pipe diameters.
The maximum liquid level in the storage tank is 30 m above the lowest level in the
ship’s tank. The ships tanks are nitrogen blanketed and maintained at pressure 1.05
bar. The storage tank has a floating roof, which exerts a pressure of 1.1 bar on the
liquid.
The ship must unload 1000 metric tons within 5 hours to avoid demurrage charges.
Estimate the power required by the pump. Take the pump efficiency 70%.
Physical properties of toluene: density 874 kg/m3 , viscosity 0.62 mN·m2
Extra information: Absolute roughness commercial steel pipes=0.046mm, friction
factor f=0.0019 Solution

Example

(H.W) Estimate the safe working pressure for a 4 in(100 mm)dia, Schedule 40 pipe,
SA53 carbon steel welded, working temperature 100 o C. The maximum allowable
stress for butt welded steel pipe up to 120 o C is 11700 lb/in2 (79.6 N/mm2 ) ?
Solution:

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