Hemendra

STUDY NOTES

by
HEMENDRA RAVAL
Industrial Health, Safety, Environment and Quality Management and Engineering Consultant
S-34, Second Floor, Yogeshwar Flat, High Tension Line Road, Subhanpura, Vadodara-390023
Mobile: +919825194168 email : hemendra_raval@[Link]

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SAFETY IN CEMENT INDUSTRY

CEMENT:

In the most general sense of the word, a cement is a binder, a substance that sets and hardens independently, and can
bind other materials together. The word "cement" traces to the Romans, who used the term opus caementicium to
describe masonry resembling modern concrete that was made from crushed rock with burnt lime as binder. The volcanic
ash and pulverized brick additives that were added to the burnt lime to obtain a hydraulic binder were later referred to as
cementum, cimentum, cäment and cement.

TYPES OF CEMENT :

Cement used in construction is classified as under.

CEMENT
HYDRAULIC CEMENTS NON-HYDRAULIC CEMENTS
(harden because of hydration, chemical reactions that occur
independently of the mixture's water content; they can
(Non-hydraulic cements must be kept dry in order to retain
harden even underwater or when constantly exposed to
their strength.
wet weather. The chemical reaction that results when the
anhydrous cement powder is mixed with water produces
hydrates that are not water-soluble.)
e.g. Portland Cement e.g. Lime and Gypsum plaster

The most important use of cement is the production of mortar and concrete—the bonding of natural or artificial
aggregates to form a strong building material that is durable in the face of normal environmental effects.

Concrete should not be confused with cement, because the term cement refers to the material used to bind the aggregate
materials of concrete. Concrete is a combination of a cement and aggregate.

Portland cement blends

Portland cement blends are often available as inter-ground mixtures from cement manufacturers, but similar formulations
are often also mixed from the ground components at the concrete mixing plant.

Portland blastfurnace cement contains up to 70 % ground granulated blast furnace slag, with the rest Portland clinker
and a little gypsum. All compositions produce high ultimate strength, but as slag content is increased, early strength is
reduced, while sulfate resistance increases and heat evolution diminishes. Used as an economic alternative to Portland
sulfate-resisting and low-heat cements.

Portland flyash cement contains up to 30 % fly ash. The fly ash is pozzolanic, so that ultimate strength is maintained.
Because fly ash addition allows a lower concrete water content, early strength can also be maintained. Where good quality
cheap fly ash is available, this can be an economic alternative to ordinary Portland cement.

Portland pozzolan cement includes fly ash cement, since fly ash is a pozzolan, but also includes cements made from
other natural or artificial pozzolans. In countries where volcanic ashes are available these cements are often the most
common form in use.

Portland silica fume cement. Addition of silica fume can yield exceptionally high strengths, and cements containing 5–
20 % silica fume are occasionally produced. However, silica fume is more usually added to Portland cement at the
concrete mixer.[15]

Masonry cements are used for preparing bricklaying mortars and stuccos, and must not be used in concrete. They are
usually complex proprietary formulations containing Portland clinker and a number of other ingredients that may include
limestone, hydrated lime, air entrainers, retarders, waterproofers and coloring agents. They are formulated to yield

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workable mortars that allow rapid and consistent masonry work. Subtle variations of Masonry cement in the US are Plastic
Cements and Stucco Cements. These are designed to produce controlled bond with masonry blocks.

Expansive cements contain, in addition to Portland clinker, expansive clinkers (usually sulfoaluminate clinkers), and are
designed to offset the effects of drying shrinkage that is normally encountered with hydraulic cements. This allows large
floor slabs (up to 60 m square) to be prepared without contraction joints.

White blended cements may be made using white clinker and white supplementary materials such as high-purity
metakaolin.

Colored cements are used for decorative purposes. In some standards, the addition of pigments to produce "colored
Portland cement" is allowed. In other standards (e.g. ASTM), pigments are not allowed constituents of Portland cement,
and colored cements are sold as "blended hydraulic cements".

Very finely ground cements are made from mixtures of cement with sand or with slag or other pozzolan type minerals
that are extremely finely ground together. Such cements can have the same physical characteristics as normal cement
but with 50% less cement particularly due to their increased surface area for the chemical reaction. Even with intensive
grinding they can use up to 50% less energy to fabricate than ordinary Portland cements.

Non-Portland hydraulic cements :

Pozzolan-lime cements. Mixtures of ground pozzolan and lime are the cements used by the Romans, and can be found
in Roman structures still standing. They develop strength slowly, but their ultimate strength can be very high. The
hydration products that produce strength are essentially the same as those produced by Portland cement.

Slag-lime cements. Ground granulated blast furnace slag is not hydraulic on its own, but is "activated" by addition of
alkalis, most economically using lime. They are similar to pozzolan lime cements in their properties. Only granulated slag
(i.e. water-quenched, glassy slag) is effective as a cement component.

Supersulfated cements. These contain about 80% ground granulated blast furnace slag, 15 % gypsum or anhydrite and
a little Portland clinker or lime as an activator. They produce strength by formation of ettringite, with strength growth
similar to a slow Portland cement. They exhibit good resistance to aggressive agents, including sulfate.

Calcium aluminate cements are hydraulic cements made primarily from limestone and bauxite. The active ingredients
are monocalcium aluminate CaAl2O4 (CaO · Al2O3 or CA in Cement chemist notation, CCN) and mayenite Ca12Al14O33 (12
CaO · 7 Al2O3, or C12A7 in CCN). Strength forms by hydration to calcium aluminate hydrates. They are well-adapted for use
in refractory (high-temperature resistant) concretes, e.g. for furnace linings.

Calcium sulfoaluminate cements are made from clinkers that include ye'elimite (Ca4(AlO2)6SO4 or C4A3 in Cement
chemist's notation) as a primary phase. They are used in expansive cements, in ultra-high early strength cements, and in
"low-energy" cements. Hydration produces ettringite, and specialized physical properties (such as expansion or rapid
reaction) are obtained by adjustment of the availability of calcium and sulfate ions. Their use as a low-energy alternative
to Portland cement has been pioneered in China, where several million tonnes per year are produced. Energy
requirements are lower because of the lower kiln temperatures required for reaction, and the lower amount of limestone
(which must be endothermically decarbonated) in the mix. In addition, the lower limestone content and lower fuel
consumption leads to a CO2 emission around half that associated with Portland clinker. However, SO2 emissions are
usually significantly higher.

"Natural" cements correspond to certain cements of the pre-Portland era, produced by burning argillaceous limestones
at moderate temperatures. The level of clay components in the limestone (around 30–35 %) is such that large amounts of
belite (the low-early strength, high-late strength mineral in Portland cement) are formed without the formation of
excessive amounts of free lime. As with any natural material, such cements have highly variable properties.

Geopolymer cements are made from mixtures of water-soluble alkali metal silicates and aluminosilicate mineral
powders such as fly ash and metakaolin.

CEMENT MANUFACTURING PROCESS :

Cement is made by heating limestone (calcium carbonate) with small quantities of other materials (such as clay) to
1450 °C in a kiln, in a process known as calcination, whereby a molecule of carbon dioxide is liberated from the calcium
carbonate to form calcium oxide, or quicklime, which is then blended with the other materials that have been included in
the mix. The resulting hard substance, called 'clinker', is then ground with a small amount of gypsum into a powder to
make 'Ordinary Portland Cement', the most commonly used type of cement (often referred to as OPC).

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MININING CRUSHING CALCINATION BLENDING

G
MINES CRUSHER CALCINATOR BLENDER

Portland cement is a basic ingredient of concrete, mortar and most non-speciality grout. The most common use for
Portland cement is in the production of concrete. Concrete is a composite material consisting of aggregate (gravel and
sand), cement, and water. As a construction material, concrete can be cast in almost any shape desired, and once
hardened, can become a structural (load bearing) element. Portland cement may be grey or white.

The setting of cement

Cement sets when mixed with water by way of a complex series of hydration chemical reactions still only partly
understood. The different constituents slowly hydrate and crystallise while the interlocking of their crystals gives to
cement its strength. After the initial setting, immersion in warm water will speed up setting. In Portland cement, gypsum
is added as a compound preventing cement flash setting. The time it takes for cement to set varies; and can take
anywhere from twenty minutes for initial set, to twenty-four hours, or more, for final set.

HAZARDS DUE TO BULK STORAGES OF RAW MATERIALS, CONVEYERS AND MACHINERY, ROTARY KILN,
MIXERS AND DRIERS, LOADING, UNLOADING AND PACKING ETC.
CONTROL MEASURES FOR DUST COLLECTION, NOISE, VIBRATIONS, HEAT EXPOSURE ETC.

Department/Area Hazards Control Measures

Mining Explosives Isolation

Restricted entry
Audio-visual signals
Dust, Silicosis, Pneumoconiosis, Silicosis Dust masks
Pre-employment & periodic medical examination
Loading of stones Injury Mechanical handling
Ergonomic issues in manual handling
Crushing Noise Isolation to remote location
Enclosures
Ear protectors
Pre-employment & periodic medical examination
Body trap Crusher guard
Tight clothing
Vibration, white finger Good foundation, shock absorbers

Conveying Body trap Pull cord

Audio-visual two end signals
Belt/chain slip Idlers
Spillage of crushed stone Idlers
Calcination CO2 exposure, global warming Stack, LEV, Gas masks
Heat (rotary kiln) Safety shower,
calcinator in open air
slow speed
Backfire in kiln NRVs
Asphyxia Calcinator in open air
Blending Dusting, Cement pneumoconiosis (mixers) LEV
Dust collectors
Dust mask
Pre-employment and periodical medical
examination
Packing Dusting, Cement pneumoconiosis Dust collectors
LEV
Dust Mask
Pre-employment and periodical medical
examination
Automation
Bagging, manual handling Mechanized packing and handling, small packs

HEALTH HAZARDS IN CEMENT INDUSTRY :

Cement Pneumoconiosis
Pneumocniosis
Silicosis

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Dermatitis
Noise induced deafness
White finger
Asphyxia

Control measures are described in the above table

Bags of cement routinely have health and safety warnings printed on them because not only is cement highly alkaline, but
the setting process is exothermic. As a result, wet cement is strongly caustic and can easily cause severe skin burns if not
promptly washed off with water. Similarly, dry cement powder in contact with mucous membranes can cause severe eye
or respiratory irritation. Cement users should wear protective clothing.

Environmental impacts

Cement manufacture causes environmental impacts at all stages of the process. These include emissions of airborne
pollution in the form of dust, gases, noise and vibration when operating machinery and during blasting in quarries, and
damage to countryside from quarrying. Equipment to reduce dust emissions during quarrying and manufacture of cement
is widely used, and equipment to trap and separate exhaust gases are coming into increased use. Environmental
protection also includes the re-integration of quarries into the countryside after they have been closed down by returning
them to nature or re-cultivating them.

CO2 emissions

Cement manufacturing releases CO2 in the atmosphere both directly when calcium carbonate is heated, producing lime
and carbon dioxide, and also indirectly through the use of energy if its production involves the emission of CO 2. The
cement industry is the second largest CO2 emitting industry behind power generation. The cement industry produces
about 5% of global man-made CO2 emissions, of which 50% is from the chemical process, and 40% from burning [Link]
amount of CO2 emitted by the cement industry is nearly 900 kg of CO2 for every 1000 kg of cement produced. The high
proportion of carbon dioxide produced in the chemical reaction leads to large decrease in mass in the conversion from
limestone to cement. So, to reduce the transport of heavier raw materials and to mimimize the associated costs, it is
more economical for cement plants to be closer to the limestone quarries rather than to the consumer centers.

In certain applications, lime mortar, reabsorbs the same amount of CO2 as was released in its manufacture, and has a
lower energy requirement in production than mainstream cement. Newly developed cement types from Novacem and Eco-
cement can absorb carbon dioxide from ambient air during hardening. Use of the Kalina cycle during production can also
increase energy efficiency.

Heavy metal emissions in the air

In some circumstances, mainly depending on the origin and the composition of the raw materials used, the high-
temperature calcination process of limestone and clay minerals can release in the atmosphere gases and dust rich in
volatile heavy metals, a.o, thallium, cadmium and mercury are the most toxic. Heavy metals (Tl, Cd, Hg, ...) are often
found as trace elements in common metal sulfides (pyrite (FeS2), zinc blende (ZnS), galena (PbS), ...) present as
secondary minerals in most of the raw materials. Environmental regulations exist in many countries to limit these
emissions.

Heavy metals present in the clinker

The presence of heavy metals in the clinker arises both from the natural raw materials and from the use of recycled by-
products or alternative fuels. The high pH prevailing in the cement porewater (12.5 < pH < 13.5) limits the mobility of
many heavy metals by decreasing their solubility and increasing their sorption onto the cement mineral phases. Nickel,
zinc and lead are commonly found in cement in non-negligible concentrations.

Use of alternative fuels and by-products materials

A cement plant consumes 3 to 6 GJ of fuel per tonne of clinker produced, depending on the raw materials and the process
used. Most cement kilns today use coal and petroleum coke as primary fuels, and to a lesser extent natural gas and fuel
oil. Selected waste and by-products with recoverable calorific value can be used as fuels in a cement kiln, replacing a
portion of conventional fossil fuels, like coal, if they meet strict specifications. Selected waste and by-products containing
useful minerals such as calcium, silica, alumina, and iron can be used as raw materials in the kiln, replacing raw materials
such as clay, shale, and limestone. Because some materials have both useful mineral content and recoverable calorific
value, the distinction between alternative fuels and raw materials is not always clear. For example, sewage sludge has a
low but significant calorific value, and burns to give ash containing minerals useful in the clinker matrix.

Bibliography :

- Engineering Material Science

- Metallurgy

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Exercise :

a) What is cement?
b) Classify cement.
c) Draw process flow diagram of cement manufacturing.
d) Explain cement manufacturing process.
e) What are the health hazards of cement industry?

Suggested Activities :

1. Visit any cement industry and observe the manufacturing.

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SAFETY IN FERTILIZER INDUSTRY

Fertilizer is any organic or inorganic material of natural or synthetic origin (other than liming materials) that is added to
a soil to supply one or more plant nutrients essential to the growth of plants.

Fertilizers typically provide, in varying proportions:

 six macronutrients: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and sulfur (S);
 seven micronutrients: boron (B), chlorine (Cl), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), and zinc
(Zn).

The macronutrients are consumed in larger quantities and are present in plant tissue in quantities from 0.15% to 6.0% on
a dry matter (0% moisture) basis (DM). Micronutrients are consumed in smaller quantities and are present in plant tissue
on the order of parts per million (ppm), ranging from 0.15 to 400 ppm DM, or less than 0.04% DM.

Only three other macronutrients are required by all plants: carbon, hydrogen, and oxygen. These nutrients are supplied
by water and carbon dioxide.

The nitrogen-rich fertilizer ammonium nitrate is also used as an oxidizing agent in improvised explosive devices,
sometimes called fertilizer bombs, leading to sale regulations

Mined inorganic fertilizers have been used for many centuries, whereas chemically synthesized inorganic fertilizers were
only widely developed during the industrial revolution. Increased understanding and use of fertilizers were important parts
of the pre-industrial British Agricultural Revolution and the industrial Green Revolution of the 20th century.

Inorganic fertilizer use has also significantly supported global population growth — it has been estimated that almost half
the people on the Earth are currently fed as a result of synthetic nitrogen fertilizer use.

TYPES OF FERTILIZER AND MANUFACTURING PROCESSES

Fertilizer Types

Soil amendments are made by adding fertilizer to the soil but there are different types of fertilizers. There is bulky
organic fertilizer such as cow manure, bat guano, bone meal, organic compost and green manure crops. And then there
is also chemical fertilizer which is also referred to as inorganic fertilizer and is made up with different formulations to
suit a variety of specified uses. Though many governments and agricultural departments go to great lengths to increase
the supply of organic fertilizers, such as bulky organic manures and composting materials, there is just not enough of
these fertilizers available to meet the existing and future fertilizer needs. Compared to organic compost, chemical or
inorganic fertilizers also have the added advantage of being less bulky. Being less bulky makes chemical fertilizer easier to
transport, both overland and from the soil into the plants itself, because they get to be available to the plant relatively
quickly when incorporated as part of the plant-food constituents. Chemical fertilizer usually comes in either granular or
powder form in bags and boxes, or in liquid formulations in bottles. The different types of chemical fertilizers are usually
classified according to the three principal elements, namely Nitrogen (N), Phosphorous (P) and Potassium (K), and
may, therefore, be included in more than one group.

ORGANIC AND INORGANIC CHEMICAL NITROGENOUS FERTILIZER TYPES

This type of fertilizer is divided into different groups according to the manner in which the Nitrogen combines with other
elements. These groups are:

 Sodium Nitrates,
 Ammonium Sulphate and ammonium salts,
 Chemical compounds that contains Nitrogen in amide form, and
 Animal and plant by products.

Sodium Nitrates

Sodium Nitrates are also known as Chilates or Chilean nitrate. The Nitrogen contained in Sodium Nitrate is refined and
amounts to 16%. This means that the Nitrogen is immediately available to plants and as such is a valuable source of
Nitrogen in a type of fertilizer. When one makes a soil amendment using Sodium Nitrates as a type of fertilizer in the
garden, it is usually as a top- and side-dressing. Particularly when nursing young plants and garden vegetables. In soil
that is acidic Sodium Nitrate is quite useful as a type of fertilizer. However, the excess use of Sodium Nitrate may cause
deflocculation.

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Ammonium Sulphate

This fertilizer type comes in a white crystalline salt form, containing 20 to 21% ammonia cal nitrogen. It is easy to
handle and it stores well under dry conditions. However, during the rainy season, it sometimes, forms lumps. (TIP: When
these lumps do occur you should grind them down to a powered form before use.) Though this fertilizer type is soluble in
water, its nitrogen is not readily lost in drainage, because the ammonium ion is retained by the soil particles. A note of
caution: Ammonium sulphate may have an acid effect on garden soil. Over time, the long-continued use of this type of
fertilizer will increase soil acidity and thus lower the yield. (TIP: It is advisable to use this fertilizer type together with
bulky organic manures to safeguard against the ill effects of continued application of ammonium sulphate.)

The application of Ammonium sulphate fertilizer can be done before sowing, at sowing time, or even as a top-dressing to
the growing crop. Do however take care NOT to apply it along with, or too close to, the seed, because in concentrated
form, it affects seed germination very adversely.

Ammonium Nitrate

This fertilizer type also comes in white crystalline salts. Ammonium Nitrate salts contains 33 to 35% nitrogen, of which
half is nitrate nitrogen and the other half in the ammonium form. As part of the ammonium form, this type of fertilizer
cannot be easily leached from the soil. This fertilizer is quick-acting, but highly hygroscopic thus making it unfit for
storage. (TIP: Coagulation and Granulation of this fertilizer can be combated with a light coating of the granules with oil.)
On a note of caution: Ammonium Nitrate also has an acid effect on the soil, in addition this type of fertilizer can be
explosive under certain conditions, and, should thus be handled with care.

'Nitro Chalk' is the trade name of a product formed by mixing ammonium nitrate with about 40% lime-stone or
dolomite. This fertilizer is granulated, non-hazardous and less hygroscopic. The lime content of this fertilizer type makes it
useful for application to acidic garden soils.

Ammonium Sulphate Nitrate

This fertilizer type is available as a mixture of ammonium nitrate and ammonium sulphate and is recognizable as a
white crystal or as dirty-white granules. This fertilizer contains 26% nitrogen, three-fourths of it in the ammoniac form
and the remainder (i.e. 6.5%) as nitrate nitrogen. Ammonium Sulphate Nitrate is non-explosive, readily soluble in water
and is very quick-acting. Because this type of fertilizer keeps well, it is very useful for all crops. Though it can also render
garden soil acidic, the acidifying effects is only one-half of that of ammonium sulphate on garden soil. Application of this
fertilizer type can be done before sowing, at sowing time or as a top-dressing, but it should not be applied along the seed.

Ammonium Chloride

This fertilizer type comes in a white crystalline compound, which contains a good physical condition and 26%
ammoniac nitrogen. In general, Ammonium Chloride is similar to ammonium sulphate in action. (TIP: Do not use this type
of fertilizer on crops such as tomatoes because the chorine may harm your crop.)

Urea

This type of fertilizer usually is available to the public in a white, crystalline, organic form. It is a highly concentrated
nitrogenous fertilizer and fairly hygroscopic. This also means that this fertilizer can be quite difficult to apply. Urea is also
produced in granular or pellet forms and is coated with a non-hygroscopic inert material. It is highly soluble in water and
therefore, subject to rapid leaching. It is, however, quick-acting and produces quick results. When applied to the soil, its
nitrogen is rapidly changed into ammonia. Similar to ammonium nitrate, urea supplies nothing but nitrogen and the
application of Urea as fertilizer can be done at sowing time or as a top-dressing, but should not be allowed to come into
contact with the seed.

Ammonia

This fertilizer type is a gas that is made up of about 80% of nitrogen and comes in a liquid form as well because under
the right conditions regarding temperature and pressure, Ammonia becomes liquid (anhydrous ammonia). Another form,
'aqueous ammonia', results from the absorption of Ammonia gas into water, in which it is soluble. Ammonia is used as a
fertilizer in both these forms. The anhydrous liquid form of Ammonia can be applied by introducing it into irrigation water,
or directly into the soil from special containers. Not really suitable for the home gardener as this renders the use of
ammonia as a fertilizer very expensive.

Organic Nitrogenous Fertilizers

Organic Nitrogenous fertilizer is the type of fertilizer that includes plant and animal by-products. These by-products
can be anything from oil cakes, to fish manure and even to dried blood. The Nitrogen available in organic nitrogenous
fertilizer types first has to be converted before the plants can use it. This conversion occurs through bacterial action and is
thus a slow process. The upside of this situation is that the supply of available nitrogen lasts so much longer AND the
amounts of this type of fertilizer may contain small amounts of organic stimulants that contain other minor elements that
might also be needed by the plants that are being fertilized. Furthermore, they may also small amounts of organic
stimulants that they may contain, or of some of the minor elements needed by plant. Oil-cakes contain not only nitrogen

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but also some phosphoric and potash, besides a large quantity of organic matter. This type of fertilizer is used in
conjunction with quicker-acting chemical fertilizers.

Then there is also blood meal which contains 10 to 12% highly available Nitrogen as well as 1 to 2% Phosphoric acid.
Blood meal, used in much the same way as oilcakes, makes for a quick remedy and can effectively be used on all types of
soil as a type of fertilizer.

Fish meal which can be dried fish, fish-meal or even powder is extracted in areas where fish oil is extracted. The resulting
residue is used as a fertilizer type. Obviously depending on the type of fish used, the available Nitrogen can be between 5
and 8% and the Phosphoric content can be from 4 to 6%. Fish meal also constitutes a fast-acting fertilizer type which is
suitable for most soil types and crops. (TIP: In powder form it is at its best.)

ORGANIC AND INORGANIC CHEMICAL PHOSPHATE FERTILIZER TYPES

The Phosphate fertilizers are categorized as natural phosphates, either treated or processed, and also by products of
phosphates and chemical phosphates.

Rock Phosphate

As a type of fertilizer, rock phosphate occurs as natural deposits in some countries. This fertilizer type has its
advantages and disadvantages. The advantage is that with adequate rainfall this fertilizer results in a long growing period
which can enhance crops. Powdered phosphate fertilizer is an excellent remedy for soils that are acidic and has a
phosphorous deficiency and requires soil amendments.

However, the disadvantage is that although phosphate fertilizer such as rock phosphate contains 25 to 35% phosphoric
acid, the phosphorous is insoluble in water. It has to be pulverized to be used as a type of fertilizer before rendering
satisfactory results in garden soil. Thus it is not surprising that Rock Phosphate is used to manufacture superphosphate
which makes the Phosphoric acid water soluble.

Superphosphate

Superphosphate is a fertilizer type that most gardeners are familiar with. As a fertilizer type one can get superphosphate
in three different grades, depending on the manufacturing process. The following is a short description of the different
superphosphate fertilizer grades:

 Single superphosphate containing 16 to 20% phosphoric acid;

 Dicalcium phosphate containing 35 to 38% phosphoric acid; and
 Triple superphosphate containing 44 to 49% phosphoric acid.

Triple superphosphate is used mostly in the manufacture of concentrated mixed fertilizer types.

The greatest advantage to be had of using Superphosphate as a fertilizer is that the phosphoric acid is fully water soluble,
but when Superphosphate is applied to the soil, it is converted into soluble phosphate. This is due to precipitation as
calcium, iron or aluminum phosphate, which is dependent on the soil type to which the fertilizer is added, be it alkaline or
acidic garden soil. All garden soil types can benefit from the application of Superphosphate as a fertilizer. Used in
conjunction with an organic fertilizer, it should be applied at sowing or transplant time.

Slag

Basic slag is a by-product of steel mills and is used as a fertilizer to a lesser extent than Superphosphate. Slag is an
excellent fertilizer that can be used to amend soils that are acidic because of its alkaline reaction. For slag application to
be an effective fertilizer it has to be pulverized first.

Bonemeal

Bonemeal as a fertilizer type needs no introduction. Bone-meal is used as a phosphate fertilizer type and is available in
two types: raw and steamed. The raw bone-meal contains 4% organic Nitrogen that is slow acting, and 20 to 25%
phosphoric acid that is not soluble in water. The steamed bone-meal on the other hand has all the fats, greases,
nitrogen and glue-making substances removed as a result of high pressure steaming. But it is more brittle and can be
ground into a powder form. In powder form this fertilizer is of great advantage to the gardener in that the rate of
availability of the phosphoric acid depends on its pulverization. This fertilizer is particularly suitable as a soil amendment
for acid soil and should be applied either at sowing time or even a few days prior to sowing. (TIP: As a fertilizer type,
bone-meal is slow acting and should be incorporated into the soil and not as a top-dressing.)

ORGANIC AND INORGANIC CHEMICAL POTASSIUM FERTILIZER TYPES

Chemical Potassium fertilizer should only be added when there is absolute certainty that there is a Potassium deficiency
in your garden soil. Potassium fertilizers also work well in sandy garden soil that responds to their application. Crops such

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as chilies, potato and fruit trees all benefit from this type of fertilizer since it improves the quality and appearance of the
produce. There are basically two different types of potassium fertilizers:

 Muriate of potash (Potassium chloride) and

 Sulphate of potash (Potassium sulphate).

Both muriate of potash and sulphate of potash are salts that make up part of the waters of the oceans and inland seas as
well as inland saline deposits.

Muriate Of Potash

Muriate of potash is a gray crystal type of fertilizer that consists of 50 to 60% potash. All the potash in this fertilizer
type is readily available to plants because it is highly soluble in water. Even so, it does not leach away deep into the soil
since the potash is absorbed on the colloidal surfaces. (TIP: Apply muriate of potash at sowing time or prior to sowing.)

Sulphate Of Potash

Sulphate of potash is a fertilizer type manufactured when potassium chloride is treated with magnesium sulphate. It
dissolves readily in water and can be applied to the garden soil at any time up to sowing. Some gardeners prefer using
sulphate of potash over muriate of potash.

DIFFERENT TYPES OF FERTILIZERS

The different types of fertilizers with all its specifications and cautions that should be kept in mind should not detract us
from the joys of gardening. Thus to make it easier on most gardeners and since this website is dedicated to the home
gardener and growing our own gardens the following section is geared towards the home gardener.

The different types of chemical and organic fertilizers that are usually commercially available in most countries can be
categorized further into:

 Complete inorganic fertilizers: – these types of inorganic fertilizers contain all three major
macronutrients, Nitrogen (N), Phosphorous (P) and Potassium (K). On the containers you will find
that these macronutrients are depicted as a ratio, e.g. 2:3:2 (22). Complete inorganic fertilizers
are usually applied at a rate of 60g/m2 or roughly 4 tablespoons per square meter.
 Special purpose fertilizer: – these types of fertilizer are formulated especially to target certain
plants' requirements or certain soil deficiencies. Of the examples that come to mind here are the
Blue Hydrangea Food, and straight fertilizer that is made up of one particular plant nutrient for
example lawn fertilizer.
 Liquid fertilizers: – these types of fertilizer come in a variety of formulations and even include
organic fertilizer, complete fertilizer as well as special purpose fertilizer. Some examples of liquid
fertilizer are Nitrosol and African Violet Food.
 Slow-release fertilizer: – these types of fertilizer are formulated to release their nitrogen at a
steady pace. On the packs of this fertilizer that are available commercially it will usually be
depicted as 3:1:5 (SR) where the SR indicates slow-release.
 Fertilizer with insecticide: – these types of fertilizer that are prepared and combined with an
insecticide. One such example is Wonder 4:1:1 (21) + Karbaspray.

The reason why there are so many different types of chemical fertilizers in different formulations is because different
plants require different nutrients and different pH levels in the soil. However, organic fertilizers have more diversity,
and these types of fertilizers do not burn plant roots, get into ground water, or affect surrounding growth as is the case
when using the different types of chemical fertilizer and NPK amendments.

FLOW CHART AND SAFETY ASPECTS OF MACHINERY IN USE

HAZARDS DUE TO BULK STORAGES, PROCESSES, TRANSFER AND TRANSPORTATION OF CHEMICALS, DUST,
NOISE ETC. AND THEIR CONTROL MEASURES

RM Source & Process Machinery Hazards Safety Product Fertilizer Type

Features
Compost Agriculture machinery Infection Mechanized Natural
Vehicuar issues handling,
Vehicular
safety Organic
Biocompost Agriculture machinery Infection Mechanized
(Vermicompost) Vehicular issues handling,Ve
hicuar safety
Mine products Mining machinery Noise Silencer, ear
Vibration protectos,

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(white finger) shock
Dust absorber,
(pneumoconiosis, dust masks,
Dermatitis, barrier Inogrganic
Caission) cream,
retention
room, pre-
employment
and
periodical
medical
examination
Chemical compounds that Hyrdogenation & Explosion, Fire Process Organic
contains Nitrogen in amide Nitration reactors Toxic exposure automation, Nitorgenous
form and Pressure
Animal and plant relief
by-products. devices,
work place
environment
monitoring,
Pre-
employment
and
periodical
medical Synthetic
examination (Chemical)
PPEs
FFEs
Bone meal -- Biological Infection Mask, Organic
Pre- Phosphates
employment
and
periodical
medical
examination
Animal and plant -- Biological Infection -do- Organic
by-products Potash
Sodium Nitrates, Nitration, Sulphonation, Explosion, Fire, Process Inorganic
Ammonium Sulphate Chlorination and Toxic exposure, automation, Nitrogenous
and ammonium salts Carboxylation reactors, Noise in crackor Pressure
Ammonium chloride Naphtha crackor relief
Ammonia devices,
Urea work place
environment
monitoring,
Pre-
employment
and
periodical
medical
examination
Enclosure,
PPEs
FFEs
Rock Phosphate Steel mills Dusting Dust Inorganic
(pnemoconiosis) collector, Phosphates
Super Phosphates Burns LEV,
(Phosphoric acid) Radiation Shd 16
- Single (occupational glasses,
- Dicalcium phosphate cataract) Reflectors,
- Triple PPEs,
FFEs
Slag (steel mills) Pre-
employment
and
periodical
medical
examination
Muriate of Potash Chlorination and Explosion, Fire, Process Inorganic
(Potassium chloride) Sulphonation reactions Toxic exposure automation, Potash
Sulphate of Potash Pressure
(Potassium Suphate) relief
devices,
work place
environment
monitoring,

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Pre-
employment
and
periodical
medical
examination
Enclosure,
PPEs
FFEs

Bibliography :

- Unit Operations and Unit Processes

- Material Safety Data Sheets

Exercise :

1) What is fertilizer?
2) Classify fertilizers.
3) What are the health hazards of cement industry?

Suggested Activities :

1. Visit any fertilizer industry and observe the manufacturing.

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SAFETY IN PETROLEUM (REFINERY) INDUSTRY

PETROLEUM :

Petroleum (L. petroleum, from Greek: petra (rock) + Latin: oleum (oil)) or crude oil is a naturally occurring, flammable
liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds,
that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling. This
latter stage comes after the studies of structural geology (at the reservoir scale), sedimentary basin analysis, reservoir
characterization (mainly in terms of porosity and permeable structures). It is refined and separated, most easily by boiling
point, into a large number of consumer products, from petrol and kerosene to asphalt and chemical reagents used to
make plastics and pharmaceuticals. Petroleum is used in manufacturing a wide variety of materials.

PETROLEUM CLASSIFICATION AND HAZARDS DUE TO PETROLEUM PRODUCTS

Petroleum is a complex mixture of organic liquids called crude oil and natural gas, which occurs naturally in the ground
and was formed millions of years ago. Crude oil varies from oilfield to oilfield in colour and composition, from a pale yellow
low viscosity liquid to heavy black 'treacle' consistencies.

Crude oil and natural gas are extracted from the ground, on land or under the oceans, by sinking an oil well and are then
transported by pipeline and/or ship to refineries where their components are processed into refined products. Crude oil
and natural gas are of little use in their raw state; their value lies in what is created from them: fuels, lubricating oils,
waxes, asphalt, petrochemicals and pipeline quality natural gas.

An oil refinery is an organised and coordinated arrangement of manufacturing processes designed to produce physical and
chemical changes in crude oil to convert it into everyday products like petrol, diesel, lubricating oil, fuel oil and bitumen.
As crude oil comes from the well it contains a mixture of hydrocarbon compounds and relatively small quantities of other
materials such as oxygen, nitrogen, sulphur, salt and water. In the refinery, most of these non - hydrocarbon substances
are removed and the oil is broken down into its various components, and blended into useful products.
Natural gas from the well, while principally methane, contains quantities of other hydrocarbons - ethane, propane, butane,
pentane and also carbon dioxide and water. These components are separated from the methane at a gas fractionation
plant.

Petroleum hydrocarbon structures

Petroleum consists of three main hydrocarbon groups:

Paraffins
These consist of straight or branched carbon rings saturated with hydrogen atoms, the simplest of which is methane
(CH4) the main ingredient of natural gas. Others in this group include ethane (C2H6), and propane (C3H8).

Hydrocarbons
With very few carbon atoms (C1 to C4) are light in density and are gases under normal atmospheric pressure. Chemically
paraffins are very stable compounds.

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Naphthenes
Naphthenes consist of carbon rings, sometimes with side chains, saturated with hydrogen atoms. Naphthenes are
chemically stable, they occur naturally in crude oil and have properties similar to paraffins.

Aromatics
aromatic hydrocarbons are compounds that contain a ring of six carbon atoms with alternating double and single bonds
and six attached hydrogen atoms. This type of structure is known as a benzene ring. They occur naturally in crude oil, and
can also be created by the refining process.

The more carbon atoms a hydrocarbon molecule has, the "heavier" it is (the higher is its molecular weight) and the higher
is its the boiling point.
Small quantities of a crude oil may be composed of compounds containing oxygen, nitrogen, sulphur and metals. Sulphur
content ranges from traces to more than 5 per cent. If a crude oil contains appreciable quantities of sulphur it is called a
sour crude; if it contains little or no sulphur it is called a sweet crude.

PROCESS FLOW DIAGRAM

OIL FIELD

GEOLOGICAL DRILLING STORAGE TRANSPORT

SURVEY

REFINERY

STORAGE DISTILLATION STORAGE TRANSPORT

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THE REFINING PROCESS (STAGES OF MANUFACTURING PROCESSES) :

Every refinery begins with the separation of crude oil into different fractions by distillation.

The fractions are further treated to convert them into mixtures of more useful saleable products by various methods such
as cracking, reforming, alkylation, polymerisation and isomerisation. These mixtures of new compounds are then
separated using methods such as fractionation and solvent extraction. Impurities are removed by various methods, e.g.
dehydration, desalting, sulphur removal and hydrotreating.

Refinery processes have developed in response to changing market demands for certain products. With the advent of the
internal combustion engine the main task of refineries became the production of petrol. The quantities of petrol available
from distillation alone was insufficient to satisfy consumer demand. Refineries began to look for ways to produce more
and better quality petrol. Two types of processes have been developed:
breaking down large, heavy hydrocarbon molecules
reshaping or rebuilding hydrocarbon molecules.

1 Crude Oil Pretreatment (Desalting)

2 Crude Oil Distillation (Fractionation)
3 Solvent Extraction and Dewaxing
4 Thermal Cracking
5 Fluid Catalytic Cracking
6 Hydrocracking
7 Catalytic Reforming
8 Catalytic Hydrotreating
9 Isomerization
10 Polymerization
11 Alkylation
12 Sweetening and Treating Processes
13 Unsaturated Gas Plants
14 Amine Plants
15 Saturate Gas Plants
16 Asphalt Production
17 Hydrogen Production
18 Blending
19 Lubricant, Wax, and Grease Manufacturing Processes

HAZARDS OF BULK STORAGES

Storages of Naphtha, propylene, ethylene, xylene, benzene, LPG, Petrol, diesel, kerosene etc. and their control measures
Testing of storage vessels and their safety fittings

Petroleum product Hazards Strage Safety Considerations

Naphtha Fire, Leak & Spill, Toxic exposure Dyke, restricted entry, floating roof, inerting, foam
pouring, gas detection, flameproof fitting, non-sparking
tools, no smoking, permit to work, separation distance,
electrical grounding, Level indication, Breather valve
Propylene, Ethylene Fire, Gas release, Toxic exposure Restricted entry, inerting, foam, gas detection, flameproof
fitting, non-sparking tools, no smking, permit to work,
separation distance, electrical grounding, Level indication,
pressure gauge, pressure relief devices, audio-visual
controls, spheres
Xylene, Benzene Fire, Leak & Spill, Toxic exposure Dyke, restricted entry, floating roof, inerting, foam
pouring, gas detection, flameproof fitting, non-sparking
tools, no smking, permit to work, separation distance,
electrical grounding, Level indication, Breather valve
LPG Fire, Explosion Restricted entry, inerting, foam, gas detection, flameproof
fitting, non-sparking tools, no smking, permit to work,
separation distance, electrical grounding, Level indication,
pressure gauge, pressure relief devices, audio-visual
controls, spheres
Petrol Fire, Leak & Spill, Toxic exposure Dyke, restricted entry, floating roof, inerting, foam
pouring, gas detection, flameproof fitting, non-sparking
tools, no smking, permit to work, separation distance,
electrical grounding, Level indication,
Diesel, Kerosene Fire, Leak & Spill, Toxic exposure Dyke, restricted entry, floating roof, inerting, foam
pouring, gas detection, flameproof fitting, non-sparking
tools, no smking, permit to work, separation distance,
electrical grounding, Level indication, Breather valve

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Safety in Pipeline transport

Hazards Control Measures

Fire Static grounding, low speed flow, periodic examination,

reliability study
Explosion Static grounding, low speed flow, periodic examination,
reliability study
Leak/Spill Jacketed pipes, inert in jackets, detection system
Toxic exposure Leak/spill control procedures, containment, monitoring,
barrier cream, gas masks and other PPEs
Theft Monitoring of flow, quantiry, audio-visual signals at ends

Hazards and controls during manufacturing process, Testing of pressure vessels

Hazards and controls : similar to as specified in pipeline transport.

Testing of pressure vessels : By a competent person
External – once in six months
Internal – once in year (thickness test)
Hydraulic – biannual (four years for non-accessible vessel)

DCS control rooms and instrumentation for safety

All process parameters like level, flow, pressure, temperature etc. should be monitored through instruments and
controlled through DCS. Human reliability should be avoilded.

All instruments should also have field indication. Limiting values should bemarked in red colour. Instruments should be
tested by a competent person every month.

All instruments and DCS system should take safe shutdown when pneumatic air is not availale.

Fire and gas detectors and fire fighting system.

Online fire and gas detectors should be provided in the field. High concentrations should give audio-visual alarm and
should activate fire protection system.

Foam pouring or injection should be installed. Fire/explosion suppression sytem should also be provided.

Fire hydrant, monitor and hydrant / trailer pump should be arranged.

PIPA software

It is pre-incident probability analysis software by Shell company that is engaged in oil refining business.
It is risk assessment software. The oil and petroleum material safety data and process parameters are fed in. For a given
condition, what can be risk is predicted by this software. Advanced refineries are assessing risk for all permit jobs.

FILLING OF ROAD AND RAIL TANKERS

Safety measures associated with filling of tankers

- Engine should be shut while filling
- Dip pipe with siphon breaking
- Double grounding with relays
- Parking log

Safety of workers employed for this purpose

- remotely operation
- antistatic shoes
- cotton clothing
- static dispensing

OISD norms for petroleum industries

OISD NORMS FOR PETROLEUM INDUSTRIES

Fuel : - Tanking
- Dyke

Oxygen : - Inerting
- Floating roof tanks
- Foam system

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Energy :
- No smoking
- No flame/energy sources
- Non-sparking tools
- Flameproof fittings
- Grounding
- Low flow speed
- Static dispensing

Other details :

Types of drilling fluid

Air
Air/polymer
Water
Water-based mud (WBM)
The clay (called "shale" in its rock form)
Oil-based mud (OBM
Synthetic-based fluid (SBM)

Function
The main functions of a drilling mud can be summarized as follows:

Remove cuttings from well

Suspend and release cuttings
Control formation pressures
Seal permeable formations
Maintain wellbore stability
Minimizing formation damage
Cool, lubricate, and support the bit and drilling assembly
Transmit hydraulic energy to tools and bit

Air core drilling

Cable tool drilling rig
Reverse circulation (RC) drilling
Track mounted Reverse Circulation rig
Diamond core drilling
Multi-combination drilling rig (capable of both diamond and reverse circulation drilling).
Direct push rigs
Cone Penetration Test rigs
Hydraulic rotary drilling
Sonic (vibratory) drilling

Rig equipment

Simple diagram of a drilling rig and its basic operation

Drilling rigs typically include at least some of the following items: See Drilling rig (petroleum) for a more detailed
description.
Blowout preventers: (BOPs)
The equipment associated with a rig is to some extent dependent on the type of rig but (#23 & #24) are devices installed
at the wellhead to prevent fluids and gases from unintentionally escaping from the borehole. #23 is the annular (often

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referred to as the "Hydril", which is one manufacturer) and #24 is the pipe rams and blind rams. In the place of #24
Variable bore rams or VBR's can be used, they offer the same pressure and sealing capacity found in standard pipe rams,
while offering the versatility of sealing on various sizes of drill pipe, production tubing and casing without changing
standard pipe rams. Normally VBR's are used when utilizing a tapered drill string (when different size drill pipe is used in
the complete drill string).
Centrifuge: an industrial version of the device that separates fine silt and sand from the drilling fluid.
Solids control: solids control equipments for preparing drilling mud for the drilling rig.
Chain tongs: wrench with a section of chain, that wraps around whatever is being tightened or loosened. Similar to a pipe
wrench.
Degasser: a device that separates air and/or gas from the drilling fluid.
Desander / desilter: contains a set of hydrocyclones that separate sand and silt from the drilling fluid.
Drawworks: (#7) is the mechanical section that contains the spool, whose main function is to reel in/out the drill line to
raise/lower the traveling block (#11).
Drill bit: (#26) device attached to the end of the drill string that breaks apart the rock being drilled. It contains jets
through which the drilling fluid exits.
Drill pipe: (#16) joints of hollow tubing used to connect the surface equipment to the bottom hole assembly (BHA) and
acts as a conduit for the drilling fluid. In the diagram, these are "stands" of drill pipe which are 2 or 3 joints of drill pipe
connected together and "stood" in the derrick vertically, usually to save time while tripping pipe.
Elevators: a gripping device that is used to latch to the drill pipe or casing to facilitate the lowering or lifting (of pipe or
casing) into or out of the borehole.
Mud motor: a hydraulically powered device positioned just above the drill bit used to spin the bit independently from the
rest of the drill string.
Mud pump: (#4) reciprocal type of pump used to circulate drilling fluid through the system.
Mud tanks: (#1) often called mud pits, provides a reserve store of drilling fluid until it is required down the wellbore.
Rotary table: (#20) rotates the drill string along with the attached tools and bit.
Shale shaker: (#2) separates drill cuttings from the drilling fluid before it is pumped back down the borehole.

An oil platform, also referred to as an offshore platform or, somewhat incorrectly, oil rig, is a lаrge structure with facilities
to drill wells, to extract and process oil and natural gas, and to temporarily store product until it can be brought to shore
for refining and marketing. In many cases, the platform contains facilities to house the workforce as well.
Depending on the circumstances, the platform may be fixed to the ocean floor, may consist of an artificial island, or may
float.

Remote subsea wells may also be connected to a platform by flow lines and by umbilical connections; these subsea
solutions may consist of single wells or of a manifold centre for multiple wells.

Offshore platform Drill Rig

1 Crude Oil Pretreatment (Desalting)

2 Crude Oil Distillation (Fractionation)
3 Solvent Extraction and Dewaxing
4 Thermal Cracking
5 Fluid Catalytic Cracking
6 Hydrocracking
7 Catalytic Reforming
8 Catalytic Hydrotreating
9 Isomerization
10 Polymerization
11 Alkylation
12 Sweetening and Treating Processes
13 Unsaturated Gas Plants
14 Amine Plants
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15 Saturate Gas Plants
16 Asphalt Production
17 Hydrogen Production
18 Blending
19 Lubricant, Wax, and Grease Manufacturing Processes

Crude Oil Pretreatment (Desalting)

Fire Prevention and Protection: The potential exists for a fire due to a leak or release of crude oil from heaters in the crude
desalting unit. Low boiling point components of crude may also be released if a leak occurs.
Safety: Inadequate desalting can cause fouling of heater tubes and heat exchangers throughout the refinery. Fouling
restricts product flow and heat transfer and leads to failures due to increased pressures and temperatures. Corrosion,
which occurs due to the presence of hydrogen sulfide, hydrogen chloride, naphthenic (organic) acids, and other
contaminants in the crude oil, also causes equipment failure. Neutralized salts (ammonium chlorides and sulfides), when
moistened by condensed water, can cause corrosion. Overpressuring the unit is another potential hazard that causes
failures.
Health: Because this is a closed process, there is little potential for exposure to crude oil unless a leak or release occurs.
Where elevated operating temperatures are used when desalting sour crudes, hydrogen sulfide will be present. There is
the possibility of exposure to ammonia, dry chemical demulsifiers, caustics, and/or acids during this operation. Safe work
practices and/or the use of appropriate personal protective equipment may be needed for exposures to chemicals and
other hazards such as heat, and during process sampling, inspection, maintenance, and turnaround activities.
Depending on the crude feedstock and the treatment chemicals used, the wastewater will contain varying amounts of
chlorides, sulfides, bicarbonates, ammonia, hydrocarbons, phenol, and suspended solids. If diatomaceous earth is used in
filtration, exposures should be minimized or controlled. Diatomaceous earth can contain silica in very fine particle size,
making this a potential respiratory hazard.

Crude Oil Distillation (Fractionation)

Fire Prevention and Protection: Even though these are closed processes, heaters and exchangers in the atmospheric and
vacuum distillation units could provide a source of ignition, and the potential for a fire exists should a leak or release
occur.
Safety: An excursion in pressure, temperature, or liquid levels may occur if automatic control devices fail. Control of
temperature, pressure, and reflux within operating parameters is needed to prevent thermal cracking within the
distillation towers. Relief systems should be provided for overpressure and operations monitored to prevent crude from
entering the reformer charge.
The sections of the process susceptible to corrosion include (but may not be limited to) preheat exchanger (hydrogen
chloride (HCl) and hydrogen sulfide (H2S)), preheat furnace and bottoms exchanger (H2S and sulfur compounds),
atmospheric tower and vacuum furnace (H2S, sulfur compounds, and organic acids), vacuum tower (H2S and organic
acids), and overhead (H2S, HCl, and water). Where sour crudes are processed, severe corrosion can occur in furnace
tubing and in both atmospheric and vacuum towers where metal temperatures exceed 450° F. Wet H2S also will cause
cracks in steel. When processing high-nitrogen crudes, nitrogen oxides can form in the flue gases of furnaces. Nitrogen
oxides are corrosive to steel when cooled to low temperatures in the presence of water.
Chemicals are used to control corrosion by hydrochloric acid produced in distillation units. Ammonia may be injected into
the overhead stream prior to initial condensation and/or an alkaline solution may be carefully injected into the hot crude
oil feed. If sufficient wash-water is not injected, deposits of ammonium chloride can form and cause serious corrosion.
Crude feedstock may contain appreciable amounts of water in suspension which can separate during startup and, along
with water remaining in the tower from steam purging, settle in the bottom of the tower. This water can be heated to the
boiling point and create an instantaneous vaporization explosion upon contact with the oil in the unit.
Health: Atmospheric and vacuum distillation are closed processes and exposures are expected to be minimal. When sour
(high-sulfur) crudes are processed, there is potential for exposure to hydrogen sulfide in the preheat exchanger and
furnace, tower flash zone and overhead system, vacuum furnace and tower, and bottoms exchanger. Hydrogen chloride
may be present in the preheat exchanger, tower top zones, and overheads. Wastewater may contain water-soluble
sulfides in high concentrations and other water-soluble compounds such as ammonia, chlorides, phenol, mercaptans, etc.,
depending upon the crude feedstock and the treatment chemicals. Safe work practices and/or the use of appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as heat and noise, and
during sampling, inspection, maintenance, and turnaround activities.

Solvent Extraction and Dewaxing

Fire Prevention and Protection: Solvent treatment is essentially a closed process and, although operating pressures are
relatively low, the potential exists for fire from a leak or spill contacting a source of ignition such as the drier or extraction
heater. In solvent dewaxing, disruption of the vacuum will create a potential fire hazard by allowing air to enter the unit.
Health: Because solvent extraction is a closed process, exposures are expected to be minimal under normal operating
conditions. However, there is a potential for exposure to extraction solvents such as phenol, furfural, glycols, methyl ethyl
ketone, amines, and other process chemicals. Safe work practices and/or the use of appropriate personal protective
equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during repair,
inspection, maintenance, and turnaround activities.

Thermal Cracking
Fire Protection and Prevention: Because thermal cracking is a closed process, the primary potential for fire is from leaks or
releases of liquids, gases, or vapors reaching an ignition source such as a heater. The potential for fire is present in coking
operations due to vapor or product leaks. Should coking temperatures get out of control, an exothermic reaction could
occur within the coker.
Safety: In thermal cracking when sour crudes are processed, corrosion can occur where metal temperatures are between
450° and 900° F. Above 900° F coke forms a protective layer on the metal. The furnace, soaking drums, lower part of the
tower, and high-temperature exchangers are usually subject to corrosion. Hydrogen sulfide corrosion in coking can also
occur when temperatures are not properly controlled above 900° F.

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Continuous thermal changes can lead to bulging and cracking of coke drum shells. In coking, temperature control must
often be held within a 10°-20° F range, as high temperatures will produce coke that is too hard to cut out of the drum.
Conversely, temperatures that are too low will result in a high asphaltic-content slurry. Water or steam injection may be
used to prevent buildup of coke in delayed coker furnace tubes. Water must be completely drained from the coker, so as
not to cause an explosion upon recharging with hot coke. Provisions for alternate means of egress from the working
platform on top of coke drums are important in the event of an emergency.
Health: The potential exists for exposure to hazardous gases such as hydrogen sulfide and carbon monoxide, and trace
polynuclear aromatics (PNAs) associated with coking operations. When coke is moved as a slurry, oxygen depletion may
occur within confined spaces such as storage silos, since wet carbon will adsorb oxygen. Wastewater may be highly
alkaline and contain oil, sulfides, ammonia, and/or phenol. The potential exists in the coking process for exposure to
burns when handling hot coke or in the event of a steam-line leak, or from steam, hot water, hot coke, or hot slurry that
may be expelled when opening cokers. Safe work practices and/or the use of appropriate personal protective equipment
may be needed for exposures to chemicals and other hazards such as heat and noise, and during process sampling,
inspection, maintenance, and turnaround activities. (Note: coke produced from petroleum is a different product from that
generated in the steel-industry coking process.)

Fluid Catalytic Cracking

Fire Prevention and Protection: Liquid hydrocarbons in the catalyst or entering the heated combustion air stream should
be controlled to avoid exothermic reactions. Because of the presence of heaters in catalytic cracking units, the possibility
exists for fire due to a leak or vapor release. Fire protection including concrete or other insulation on columns and
supports, or fixed water spray or fog systems where insulation is not feasible and in areas where firewater hose streams
cannot reach, should be considered.
In some processes, caution must be taken to prevent explosive concentrations of catalyst dust during recharge or
disposal. When unloading any coked catalyst, the possibility exists for iron sulfide fires. Iron sulfide will ignite
spontaneously when exposed to air and therefore must be wetted with water to prevent it from igniting vapors. Coked
catalyst may be either cooled below 120° F before it is dumped from the reactor, or dumped into containers that have
been purged and inerted with nitrogen and then cooled before further handling.
Safety: Regular sampling and testing of the feedstock, product, and recycle streams should be performed to assure that
the cracking process is working as intended and that no contaminants have entered the process stream. Corrosives or
deposits in the feedstock can foul gas compressors. Inspections of critical equipment including pumps, compressors,
furnaces, and heat exchangers should be conducted as needed. When processing sour crude, corrosion may be expected
where temperatures are below 900° F. Corrosion takes place where both liquid and vapor phases exist, and at areas
subject to local cooling such as nozzles and platform supports.
When processing high-nitrogen feedstock, exposure to ammonia and cyanide may occur, subjecting carbon steel
equipment in the FCC overhead system to corrosion, cracking, or hydrogen blistering. These effects may be minimized by
water wash or corrosion inhibitors. Water wash may also be used to protect overhead condensers in the main column
subjected to fouling from ammonium hydrosulfide. Inspections should include checking for leaks due to erosion or other
malfunctions such as catalyst buildup on the expanders, coking in the overhead feeder lines from feedstock residues, and
other unusual operating conditions.
Health: Because the catalytic cracker is a closed system, there is normally little opportunity for exposure to hazardous
substances during normal operations. The possibility exists of exposure to extremely hot (700° F) hydrocarbon liquids or
vapors during process sampling or if a leak or release occurs. In addition, exposure to hydrogen sulfide and/or carbon
monoxide gas may occur during a release of product or vapor.
Catalyst regeneration involves steam stripping and decoking, and produces fluid waste streams that may contain varying
amounts of hydrocarbon, phenol, ammonia, hydrogen sulfide, mercaptan, and other materials depending upon the
feedstock, crudes, and processes. Inadvertent formation of nickel carbonyl may occur in cracking processes using nickel
catalysts, with resultant potential for hazardous exposures. Safe work practices and/or the use of appropriate personal
protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat; during
process sampling, inspection, maintenance and turnaround activities; and when handling spent catalyst, recharging
catalyst, or if leaks or releases occur.

Hydrocracking
Fire Prevention and Protection: Because this unit operates at very high pressures and temperatures, control of both
hydrocarbon leaks and hydrogen releases is important to prevent fires. In some processes, care is needed to ensure that
explosive concentrations of catalytic dust do not form during recharging.
Safety: Inspection and testing of safety relief devices are important due to the very high pressures in this unit. Proper
process control is needed to protect against plugging reactor beds. Unloading coked catalyst requires special precautions
to prevent iron sulfide-induced fires. The coked catalyst should either be cooled to below 120° F before dumping, or be
placed in nitrogen-inerted containers until cooled.
Because of the operating temperatures and presence of hydrogen, the hydrogen sulfide content of the feedstock must be
strictly controlled to a minimum to reduce the possibility of severe corrosion. Corrosion by wet carbon dioxide in areas of
condensation also must be considered. When processing high-nitrogen feedstock, the ammonia and hydrogen sulfide form
ammonium hydrosulfide, which causes serious corrosion at temperatures below the water dew point. Ammonium
hydrosulfide is also present in sour water stripping.
Health: Because this is a closed process, exposures are expected to be minimal under normal operating conditions. There
is a potential for exposure to hydrocarbon gas and vapor emissions, hydrogen and hydrogen sulfide gas due to high-
pressure leaks. Large quantities of carbon monoxide may be released during catalyst regeneration and changeover.
Catalyst steam stripping and regeneration create waste streams containing sour water and ammonia. Safe work practices
and/or the use of appropriate personal protective equipment may be needed for exposure to chemicals and other hazards
such as noise and heat, during process sampling, inspection, maintenance, and turnaround activities, and when handling
spent catalyst.

Catalytic Reforming
Fire Prevention and Protection: This is a closed system; however, the potential for fire exists should a leak or release of
reformate gas or hydrogen occur.

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Safety: Operating procedures should be developed to ensure control of hot spots during start-up. Safe catalyst handling is
very important. Care must be taken not to break or crush the catalyst when loading the beds, as the small fines will plug
up the reformer screens. Precautions against dust when regenerating or replacing catalyst should also be considered.
Also, water wash should be considered where stabilizer fouling has occurred due to the formation of ammonium chloride
and iron salts. Ammonium chloride may form in pretreater exchangers and cause corrosion and fouling. Hydrogen chloride
from the hydrogenation of chlorine compounds may form acid or ammonium chloride salt.
Health: Because this is a closed process, exposures are expected to be minimal under normal operating conditions. There
is potential for exposure to hydrogen sulfide and benzene should a leak or release occur.
Small emissions of carbon monoxide and hydrogen sulfide may occur during regeneration of catalyst. Safe work practices
and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as
noise and heat during testing, inspecting, maintenance and turnaround activities, and when handling regenerated or spent
catalyst.

Catalytic Hydrotreating
Fire Prevention and Protection: The potential exists for fire in the event of a leak or release of product or hydrogen gas.
Safety: Many processes require hydrogen generation to provide for a continuous supply. Because of the operating
temperatures and presence of hydrogen, the hydrogen sulfide content of the feedstock must be strictly controlled to a
minimum to reduce corrosion. Hydrogen chloride may form and condense as hydrochloric acid in the lower-temperature
parts of the unit. Ammonium hydrosulfide may form in high-temperature, high-pressure units. Excessive contact time
and/or temperature will create coking. Precautions need to be taken when unloading coked catalyst from the unit to
prevent iron sulfide fires. The coked catalyst should be cooled to below 120° F before removal, or dumped into nitrogen-
inerted bins where it can be cooled before further handling. Special antifoam additives may be used to prevent catalyst
poisoning from silicone carryover in the coker feedstock.
Health: Because this is a closed process, exposures are expected to be minimal under normal operating conditions. There
is a potential for exposure to hydrogen sulfide or hydrogen gas in the event of a release, or to ammonia should a sour-
water leak or spill occur. Phenol also may be present if high-boiling point feedstocks are processed. Safe work practices
and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as
noise and heat; during process sampling, inspection, maintenance, and turnaround activities; and when handling amine or
exposed to catalyst.

Isomerization
Fire Protection and Prevention: Although this is a closed process, the potential for a fire exists should a release or leak
contact a source of ignition such as the heater.
Safety: If the feedstock is not completely dried and desulfurized, the potential exists for acid formation leading to catalyst
poisoning and metal corrosion. Water or steam must not be allowed to enter areas where hydrogen chloride (HCl) is
present. Precautions are needed to prevent HCl from entering sewers and drains.
Health: Because this is a closed process, exposures are expected to be minimal during normal operating conditions. There
is a potential for exposure to hydrogen gas, hydrochloric acid, and hydrogen chloride and to dust when solid catalyst is
used. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals
and other hazards such as heat and noise, and during process sampling, inspection, maintenance, and turnaround
activities.

Polymerization
Fire prevention and Protection: Polymerization is a closed process where the potential for a fire exists due to leaks or
releases reaching a source of ignition.
Safety: The potential for an uncontrolled exothermic reaction exists should loss of cooling water occur. Severe corrosion
leading to equipment failure will occur should water make contact with the phosphoric acid, such as during water washing
at shutdowns. Corrosion may also occur in piping manifolds, reboilers, exchangers, and other locations where acid may
settle out.
Health: Because this is a closed system, exposures are expected to be minimal under normal operating conditions. There
is a potential for exposure to caustic wash (sodium hydroxide), to phosphoric acid used in the process or washed out
during turnarounds, and to catalyst dust. Safe work practices and/or appropriate personal protective equipment may be
needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection,
maintenance, and turnaround activities.

Alkylation
Fire Protection and Prevention: Alkylation units are closed processes; however, the potential exists for fire should a leak
or release occur that allows product or vapor to reach a source of ignition.
Safety: Sulfuric acid and hydrofluoric acid are potentially hazardous chemicals. Loss of coolant water, which is needed to
maintain process temperatures, could result in an upset. Precautions are necessary to ensure that equipment and
materials that have been in contact with acid are handled carefully and are thoroughly cleaned before they leave the
process area or refinery. Immersion wash vats are often provided for neutralization of equipment that has come into
contact with hydrofluoric acid. Hydrofluoric acid units should be thoroughly drained and chemically cleaned prior to
turnarounds and entry to remove all traces of iron fluoride and hydrofluoric acid. Following shutdown, where water has
been used the unit should be thoroughly dried before hydrofluoric acid is introduced.
Leaks, spills, or releases involving hydrofluoric acid or hydrocarbons containing hydrofluoric acid can be extremely
hazardous. Care during delivery and unloading of acid is essential. Process unit containment by curbs, drainage, and
isolation so that effluent can be neutralized before release to the sewer system is considered. Vents can be routed to
soda-ash scrubbers to neutralize hydrogen fluoride gas or hydrofluoric acid vapors before release. Pressure on the cooling
water and steam side of exchangers should be kept below the minimum pressure on the acid service side to prevent water
contamination.
Some corrosion and fouling in sulfuric acid units may occur from the breakdown of sulfuric acid esters or where caustic is
added for neutralization. These esters can be removed by fresh acid treating and hot-water washing. To prevent corrosion
from hydrofluoric acid, the acid concentration inside the process unit should be maintained above 65% and moisture
below 4%.

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Health: Because this is a closed process, exposures are expected to be minimal during normal operations. There is a
potential for exposure should leaks, spills, or releases occur. Sulfuric acid and (particularly) hydrofluoric acid are
potentially hazardous chemicals. Special precautionary emergency preparedness measures and protection appropriate to
the potential hazard and areas possibly affected need to be provided. Safe work practices and appropriate skin and
respiratory personal protective equipment are needed for potential exposures to hydrofluoric and sulfuric acids during
normal operations such as reading gauges, inspecting, and process sampling, as well as during emergency response,
maintenance, and turnaround activities. Procedures should be in place to ensure that protective equipment and clothing
worn in hydrofluoric acid activities are decontaminated and inspected before reissue. Appropriate personal protection for
exposure to heat and noise also may be required.

Sweetening and Treating Processes

Fire Protection and Prevention: The potential exists for fire from a leak or release of feedstock or product. Sweetening
processes use air or oxygen. If excess oxygen enters these processes, it is possible for a fire to occur in the settler due to
the generation of static electricity, which acts as the ignition source.
Health: Because these are closed processes, exposures are expected to be minimal under normal operating conditions.
There is a potential for exposure to hydrogen sulfide, caustic (sodium hydroxide), spent caustic, spent catalyst (Merox),
catalyst dust and sweetening agents (sodium carbonate and sodium bicarbonate). Safe work practices and/or appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and
during process sampling, inspection, maintenance, and turnaround activities.
Unsaturated Gas Plants
Fire Prevention and Protection: The potential of a fire exists should spills, releases, or vapors reach a source of ignition.
Safety: In unsat gas plants handling FCC feedstock, the potential exists for corrosion from moist hydrogen sulfide and
cyanides. When feedstocks are from the delayed coker or the TCC, corrosion from hydrogen sulfide and deposits in the
high pressure sections of gas compressors from ammonium compounds is possible.
Health: Because these are closed processes, exposures are expected to be minimal under normal operating conditions.
There is a potential for exposures to amine compounds such as monoethanolamine (MEA), diethanolamine (DEA) and
methyldiethanolamine (MDEA) and hydrocarbons. Safe work practices and/or appropriate personal protective equipment
may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling,
inspection, maintenance, and turnaround activities.

Amine Plants
Fire Protection and Prevention: The potential for fire exists where a spill or leak could reach a source of ignition.
Safety: To minimize corrosion, proper operating practices should be established and regenerator bottom and reboiler
temperatures controlled. Oxygen should be kept out of the system to prevent amine oxidation.
Health: Because this is a closed process, exposures are expected to be minimal during normal operations. There is
potential for exposure to amine compounds (i.e. monoethanolamine, diethanolamine, methyldiethanolamine), hydrogen
sulfide and carbon dioxide. Safe work practices and/or appropriate personal protective equipment may be needed for
exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance
and turnaround activities.

Saturate Gas Plants

Fire Protection and Prevention: There is potential for fire if a leak or release reaches a source of ignition such as the unit
reboiler.
Safety: Corrosion could occur from the presence of hydrogen sulfide, carbon dioxide, and other compounds as a result of
prior treating. Streams containing ammonia should be dried before processing. Antifouling additives may be used in
absorption oil to protect heat exchangers. Corrosion inhibitors may be used to control corrosion in overhead systems.
Health: Because this is a closed process, exposures are expected to be minimal during normal operations. There is
potential for exposure to hydrogen sulfide, carbon dioxide, and other products such as diethanolamine or sodium
hydroxide carried over from prior treating. Safe work practices and/or appropriate personal protective equipment may be
needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection,
maintenance, and turnaround activities.

Asphalt Production
Fire Protection and Prevention: The potential for a fire exists if a product leak or release contacts a source of ignition such
as the process heater. Condensed steam from the various asphalt and deasphalting processes will contain trace amounts
of hydrocarbons. Any disruption of the vacuum can result in the entry of atmospheric air and subsequent fire. In addition,
raising the temperature of the vacuum tower bottom to improve efficiency can generate methane by thermal cracking.
This can create vapors in asphalt storage tanks that are not detectable by flash testing but are high enough to be
flammable.
Safety: Deasphalting requires exact temperature and pressure control. In addition, moisture, excess solvent, or a drop in
operating temperature may cause foaming, which affects the product temperature control and may create an upset.
Health: Because these are closed processes, exposures are expected to be minimal during normal operations. Should a
spill or release occur, there is a potential for exposure to residuals and asphalt. Air blowing can create some polynuclear
aromatics. Condensed steam from the air-blowing asphalt process may also contain contaminants. The potential for
exposure to hydrogen sulfide and sulfur dioxide exists in the production of asphalt. Safe work practices and/or appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and
during process sampling, inspection, maintenance, and turnaround activities.

Hydrogen Production
Fire Protection and Prevention: The possibility of fire exists should a leak or release occur and reach an ignition source.
Safety: The potential exists for burns from hot gases and superheated steam should a release occur. Inspections and
testing should be considered where the possibility exists for valve failure due to contaminants in the hydrogen. Carryover
from caustic scrubbers should be controlled to prevent corrosion in preheaters. Chlorides from the feedstock or steam
system should be prevented from entering reformer tubes and contaminating the catalyst.
Health: Because these are closed processes, exposures are expected to be minimal during normal operating conditions.
There is a potential for exposure to excess hydrogen, carbon monoxide, and/or carbon dioxide. Condensate can be

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contaminated by process materials such as caustics and amine compounds, with resultant exposures. Depending on the
specific process used, safe work practices and/or appropriate personal protective equipment may be needed for exposures
to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance, and
turnaround activities.

Blending
Fire Prevention and Protection: Ignition sources in the area need to be controlled in the event of a leak or release.
Health: Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals
and other hazards such as noise and heat; when handling additives; and during inspection, maintenance, and turnaround
activities.

Lubricant, Wax, and Grease Manufacturing Processes

Fire Protection and Prevention: The potential for fire exists if a product or vapor leak or release in the lube blending and
wax processing areas reaches a source of ignition. Storage of finished products, both bulk and packaged, should be in
accordance with recognized practices.
While the potential for fire is reduced in lube oil blending, care must be taken when making metal-working oils and
compounding greases due to the use of higher blending and compounding temperatures and lower flash point products.
Safety: Control of treater temperature is important as phenol can cause corrosion above 400° F. Batch and in-line
blending operations require strict controls to maintain desired product quality. Spills should be cleaned and leaks repaired
to avoid slips and falls. Additives in drums and bags need to be handled properly to avoid strain. Wax can clog sewer or oil
drainage systems and interfere with wastewater treatment.
Health: When blending, sampling, and compounding, personal protection from steam, dusts, mists, vapors, metallic salts,
and other additives is appropriate. Skin contact with any formulated grease or lubricant should be avoided. Safe work
practices and/or appropriate personal protection may be needed for exposures to chemicals and other hazards such as
noise and heat; during inspection, maintenance, and turnaround activities; and while sampling and handling hydrocarbons
and chemicals during the production of lubricating oil and wax.

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REFINING OF PETROLEUM

Distillation (Fractionation)
Because crude oil is a mixture of hydrocarbons with different boiling temperatures, it can be separated by distillation into
groups of hydrocarbons that boil between two specified boiling points. Two types of distillation are performed:
atmospheric and vacuum.
Atmospheric distillation takes place in a distilling column at or near atmospheric pressure. The crude oil is heated to 350 -
400oC and the vapour and liquid are piped into the distilling column. The liquid falls to the bottom and the vapour rises,
passing through a series of perforated trays (sieve trays). Heavier hydrocarbons condense more quickly and settle on
lower trays and lighter hydrocarbons remain as a vapour longer and condense on higher trays.
Liquid fractions are drawn from the trays and removed. In this way the light gases, methane, ethane, propane and butane
pass out the top of the column, petrol is formed in the top trays, kerosene and gas oils in the middle, and fuel oils at the
bottom. Residue drawn of the bottom may be burned as fuel, processed into lubricating oils, waxes and bitumen or used
as feedstock for cracking units.
To recover additional heavy distillates from this residue, it may be piped to a second distillation column where the process
is repeated under vacuum, called vacuum distillation. This allows heavy hydrocarbons with boiling points of 450oC and
higher to be separated without them partly cracking into unwanted products such as coke and gas.
The heavy distillates recovered by vacuum distillation can be converted into lubricating oils by a variety of processes. The
most common of these is called solvent extraction. In one version of this process the heavy distillate is washed with a
liquid which does not dissolve in it but which dissolves (and so extracts) the non-lubricating oil components out of it.
Another version uses a liquid which does not dissolve in it but which causes the non-lubricating oil components to
precipitate (as an extract) from it. Other processes exist which remove impurities by adsorption onto a highly porous solid
or which remove any waxes that may be present by causing them to crystallise and precipitate out.

Reforming
Reforming is a process which uses heat, pressure and a catalyst (usually containing platinum) to bring about chemical
reactions which upgrade naphthas into high octane petrol and petrochemical feedstock. The naphthas are hydrocarbon
mixtures containing many paraffins and naphthenes. In Australia, this naphtha feedstock comes from the crudes oil
distillation or catalytic cracking processes, but overseas it also comes from thermal cracking and hydrocracking processes.
Reforming converts a portion of these compounds to isoparaffins and aromatics, which are used to blend higher octane
petrol.
paraffins are converted to isoparaffins
paraffins are converted to naphthenes
naphthenes are converted to aromatics
e.g.
catalyst
heptane -> toluene + hydrogen
C7H16 -> C7H8 + 4H2

catalyst

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cyclohexane -> benzene + hydrogen
C6H12 -> C6H6 + 3H2

Cracking
Cracking processes break down heavier hydrocarbon molecules (high boiling point oils) into lighter products such as petrol
and diesel. These processes include catalytic cracking, thermal cracking and hydrocracking.
e.g.
A typical reaction:
catalyst
C16H34 -> C8H18 + C8H16
Catalytic cracking is used to convert heavy hydrocarbon fractions obtained by vacuum distillation into a mixture of more
useful products such as petrol and light fuel oil. In this process, the feedstock undergoes a chemical breakdown, under
controlled heat (450 - 500oC) and pressure, in the presence of a catalyst - a substance which promotes the reaction
without itself being chemically changed. Small pellets of silica - alumina or silica - magnesia have proved to be the most
effective catalysts.
The cracking reaction yields petrol, LPG, unsaturated olefin compounds, cracked gas oils, a liquid residue called cycle oil,
light gases and a solid coke residue. Cycle oil is recycled to cause further breakdown and the coke, which forms a layer on
the catalyst, is removed by burning. The other products are passed through a fractionator to be separated and separately
processed.
Fluid catalytic cracking uses a catalyst in the form of a very fine powder which flows like a liquid when agitated by steam,
air or vapour. Feedstock entering the process immediately meets a stream of very hot catalyst and vaporises. The
resulting vapours keep the catalyst fluidised as it passes into the reactor, where the cracking takes place and where it is
fluidised by the hydrocarbon vapour. The catalyst next passes to a steam stripping section where most of the volatile
hydrocarbons are removed. It then passes to a regenerator vessel where it is fluidised by a mixture of air and the
products of combustion which are produced as the coke on the catalyst is burnt off. The catalyst then flows back to the
reactor. The catalyst thus undergoes a continuous circulation between the reactor, stripper and regenerator sections.
The catalyst is usually a mixture of aluminium oxide and silica. Most recently, the introduction of synthetic zeolite
catalysts has allowed much shorter reaction times and improved yields and octane numbers of the cracked gasolines.
Thermal cracking uses heat to break down the residue from vacuum distillation. The lighter elements produced from this
process can be made into distillate fuels and petrol. Cracked gases are converted to petrol blending components by
alkylation or polymerisation. Naphtha is upgraded to high quality petrol by reforming. Gas oil can be used as diesel fuel or
can be converted to petrol by hydrocracking. The heavy residue is converted into residual oil or coke which is used in the
manufacture of electrodes, graphite and carbides.
This process is the oldest technology and is not used in Australia.
Hydrocracking can increase the yield of petrol components, as well as being used to produce light distillates. It produces
no residues, only light oils. Hydrocracking is catalytic cracking in the presence of hydrogen. The extra hydrogen saturates,
or hydrogenates, the chemical bonds of the cracked hydrocarbons and creates isomers with the desired characteristics.
Hydrocracking is also a treating process, because the hydrogen combines with contaminants such as sulphur and
nitrogen, allowing them to be removed.
Gas oil feed is mixed with hydrogen, heated, and sent to a reactor vessel with a fixed bed catalyst, where cracking and
hydrogenation take place. Products are sent to a fractionator to be separated. The hydrogen is recycled. Residue from this
reaction is mixed again with hydrogen, reheated, and sent to a second reactor for further cracking under higher
temperatures and pressures.
In addition to cracked naphtha for making petrol, hydrocracking yields light gases useful for refinery fuel, or alkylation as
well as components for high quality fuel oils, lube oils and petrochemical feedstocks.
Following the cracking processes it is necessary to build or rearrange some of the lighter hydrocarbon molecules into high
quality petrol or jet fuel blending components or into petrochemicals. The former can be achieved by several chemical
process such as alkylation and isomerisation.

Alkylation
Olefins such as propylene and butylene are produced by catalytic and thermal cracking. Alkylation refers to the chemical
bonding of these light molecules with isobutane to form larger branched-chain molecules (isoparaffins) that make high
octane petrol.
Olefins and isobutane are mixed with an acid catalyst and cooled. They react to form alkylate, plus some normal butane,
isobutane and propane. The resulting liquid is neutralised and separated in a series of distillation columns. Isobutane is
recycled as feed and butane and propane sold as liquid petroleum gas (LPG).
e.g.
catalyst
isobutane + butylene -> isooctane
C4H10 + C4H8 -> C8H18

Isomerisation
Isomerisation refers to chemical rearrangement of straight-chain hydrocarbons (paraffins), so that they contain branches
attached to the main chain (isoparaffins). This is done for two reasons:
they create extra isobutane feed for alkylation
they improve the octane of straight run pentanes and hexanes and hence make them into better petrol blending
components.
Isomerisation is achieved by mixing normal butane with a little hydrogen and chloride and allowed to react in the
presence of a catalyst to form isobutane, plus a small amount of normal butane and some lighter gases. Products are
separated in a fractionator. The lighter gases are used as refinery fuel and the butane recycled as feed.
Pentanes and hexanes are the lighter components of petrol. Isomerisation can be used to improve petrol quality by
converting these hydrocarbons to higher octane isomers. The process is the same as for butane isomerisation.

Polymerisation
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Under pressure and temperature, over an acidic catalyst, light unsaturated hydrocarbon molecules react and combine with
each other to form larger hydrocarbon molecules. Such process can be used to react butenes (olefin molecules with four
carbon atoms) with iso-butane (branched paraffin molecules, or isoparaffins, with four carbon atoms) to obtain a high
octane olefinic petrol blending component called polymer gasoline.

Hydrotreating and sulphur plants

A number of contaminants are found in crude oil. As the fractions travel through the refinery processing units, these
impurities can damage the equipment, the catalysts and the quality of the products. There are also legal limits on the
contents of some impurities, like sulphur, in products.
Hydrotreating is one way of removing many of the contaminants from many of the intermediate or final products. In the
hydrotreating process, the entering feedstock is mixed with hydrogen and heated to 300 - 380oC. The oil combined with
the hydrogen then enters a reactor loaded with a catalyst which promotes several reactions:
hydrogen combines with sulphur to form hydrogen sulphide (H2S)
nitrogen compounds are converted to ammonia
any metals contained in the oil are deposited on the catalyst
some of the olefins, aromatics or naphthenes become saturated with hydrogen to become paraffins and some cracking
takes place, causing the creation of some methane, ethane, propane and butanes.

Sulphur recovery plants

The hydrogen sulphide created from hydrotreating is a toxic gas that needs further treatment. The usual process involves
two steps:
the removal of the hydrogen sulphide gas from the hydrocarbon stream
the conversion of hydrogen sulphide to elemental sulphur, a non-toxic and useful chemical.
Solvent extraction, using a solution of diethanolamine (DEA) dissolved in water, is applied to separate the hydrogen
sulphide gas from the process stream. The hydrocarbon gas stream containing the hydrogen sulphide is bubbled through
a solution of diethanolamine solution (DEA) under high pressure, such that the hydrogen sulphide gas dissolves in the
DEA. The DEA and hydrogen mixture is the heated at a low pressure and the dissolved hydrogen sulphide is released as a
concentrated gas stream which is sent to another plant for conversion into sulphur.
Conversion of the concentrated hydrogen sulphide gas into sulphur occurs in two stages.
Combustion of part of the H2S stream in a furnace, producing sulphur dioxide (SO2) water (H2O) and sulphur (S).
2H2S + 2O2 -> SO2 + S + 2H2O
Reaction of the remainder of the H2S with the combustion products in the presence of a catalyst. The H2S reacts with the
SO2 to form sulphur.
2H2S + 2O2 -> 3S + 2H2O
As the reaction products are cooled the sulphur drops out of the reaction vessel in a molten state. Sulphur can be stored
and shipped in either a molten or solid state.
Click here to view a flow chart of a refinery .

Refineries and the environment

Air, water and land can all be affected by refinery operations. Refineries are well aware of their responsibility to the
community and employ a variety of processes to safeguard the environment.
The processes described below are those used by the Shell refinery at Geelong in Victoria, but all refineries employ similar
techniques in managing the environmental aspects of refining.

Air
Preserving air quality around a refinery involves controlling the following emissions:
sulphur oxides
hydrocarbon vapours
smoke
smells
Sulphur enters the refinery in crude oil feed. Gippsland and most other Australian crude oils have a low sulphur content
but other crude's may contain up to 5 per cent sulphur. To deal with this refineries incorporate a sulphur recovery unit
which operates on the principles described above.
Many of the products used in a refinery produce hydrocarbon vapours. The escape of vapours to atmosphere are
prevented by various means. Floating roofs are installed in tanks to prevent evaporation and so that there is no space for
vapour to gather in the tanks. Where floating roofs cannot be used, the vapours from the tanks are collected in a vapour
recovery system and absorbed back into the product stream. In addition, pumps and valves are routinely checked for
vapour emissions and repaired if a leakage is found.
Smoke is formed when the burning mixture contains insufficient oxygen or is not sufficiently mixed. Modern furnace
control systems prevent this from happening during normal operation.
Smells are the most difficult emission to control and the easiest to detect. Refinery smells are generally associated with
compounds containing sulphur, where even tiny losses are sufficient to cause a noticeable odour.

Water
Aqueous effluent's consist of cooling water, surface water and process water.
The majority of the water discharged from the refinery has been used for cooling the various process streams. The cooling
water does not actually come into contact with the process material and so has very little contamination. The cooling
water passes through large "interceptors" which separate any oil from minute leaks etc., prior to discharge. The cooling
water system at Geelong Refinery is a once-through system with no recirculation.
Rainwater falling on the refinery site must be treated before discharge to ensure no oily material washed off process
equipment leaves the refinery. This is done first by passing the water through smaller "plant oil catchers", which each
treat rainwater from separate areas on the site, and then all the streams pass to large "interceptors" similar to those used
for cooling water. The rainwater from the production areas is further treated in a Dissolved Air Flotation (DAF) unit. This
unit cleans the water by using a flocculation agent to collect any remaining particles or oil droplets and floating the

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resulting flock to the surface with millions of tiny air bubbles. At the surface the flock is skimmed off and the clean water
discharged.
Process water has actually come into contact with the process streams and so can contain significant contamination. This
water is treated in the "sour water treater" where the contaminants (mostly ammonia and hydrogen sulphide) are
removed and then recovered or destroyed in a downstream plant. The process water, when treated in this way, can be
reused in parts of the refinery and discharged through the process area rainwater treatment system and the DAF unit.
Any treated process water that is not reused is discharged as Trade Waste to the sewerage system. This trade waste also
includes the effluent from the refinery sewage treatment plant and a portion of treated water from the DAF unit.
As most refineries import and export many feed materials and products by ship, the refinery and harbour authorities are
prepared for spillage from the ship or pier. In the event of such a spill, equipment is always on standby at the refinery and
it is supported by the facilities of the Australian Marine Oil Spill Centre at Geelong, Victoria.

Land
The refinery safeguards the land environment by ensuring the appropriate disposal of all wastes.
Within the refinery, all hydrocarbon wastes are recycled through the refinery slops system. This system consists of a
network of collection pipes and a series of dewatering tanks. The recovered hydrocarbon is reprocessed through the
distillation units.
Wastes that cannot be reprocessed are either recycled to manufacturers (e.g. some spent catalysts can be reprocessed),
disposed of in EPA-approved facilities off-site, or chemically treated on-site to form inert materials which can be disposed
to land-fill within the refinery.
Waste movements within the refinery require a "Process liquid, Sludge and Solid waste disposal permit". Wastes that go
off-site must have an EPA "Waste Transport Permit".

Bibliography :

- API Handbook
- Processing Petroleum

Exercise :

1. What do you mean by Petroleum?

2. Classify Petroleum.
3. Draw Process flow diagram for Petroleum Industry.
4. What are the hazards and control measures with Petroleum Industry?
5. Draw sketch of Flaoting roof tank.
6. What are the hazards and safety measures in loading and unloading petroleum tankers.

Suggested activities :
1. Visit an oil field and observe safety systems.
2. Visit an oil refinery and observe tanking, processes and dispatch of products.

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SAFETY IN PETROCHEMICAL INDUSTRY

Petrochemical

Petrochemicals are chemical products derived from petroleum. Some chemical compounds made from petroleum are
also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as corn or sugar cane. The
prefix "petro-" is an arbitrary abbreviation of the word "petroleum"; since "petro-" is Ancient Greek for "rock" and "oleum"
means "oil". Therefore, the etymologically correct term would be "oleochemicals". However, the term oleochemical is used
to describe chemicals derived from plant and animal fats.

Two petrochemical classes are olefins including ethylene and propylene, and aromatics including benzene, toluene and
xylene isomers. Oil refineries produce olefins and aromatics by fluid catalytic cracking of petroleum fractions. Chemical
plants produce olefins by steam cracking of natural gas liquids like ethane and propane. Aromatics are produced by
catalytic reforming of naphtha. Olefins and aromatics are the building blocks for a wide range of materials such as
solvents, detergents, and adhesives. Olefins are the basis for polymers and oligomers used in plastics, resins, fibers,
elastomers, lubricants, and gels.

Primary petrochemicals are divided into three groups depending on their chemical structure:

 Olefins includes ethylene, propylene, and butadiene. Ethylene and propylene are important sources of industrial
chemicals and plastics products. Butadiene is used in making synthetic rubber.
 Aromatics includes benzene, toluene, and xylenes. Benzene is a raw material for dyes and synthetic detergents,
and benzene and toluene for isocyanates MDI and TDI used in making polyurethanes. Manufacturers use xylenes to
produce plastics and synthetic fibers.
 Synthesis gas is a mixture of carbon monoxide and hydrogen used to make ammonia and methanol. Ammonia is
used to make the fertilizer urea and methanol is used as a solvent and chemical intermediate.

List of significant petrochemicals and their derivatives

The following is a partial list of the major commercial petrochemicals and their derivatives:

Chemicals produced from ethylene

 ethylene - the simplest olefin; used as a chemical feedstock and ripening hormone
o polyethylene - polymerized ethylene
o ethanol - via ethylene hydration (chemical reaction adding water) of ethylene
o ethylene oxide - via ethylene oxidation
 ethylene glycol - via ethylene oxide hydration
 engine coolant - ethylene glycol, water and inhibitor mixture
 polyesters - any of several polymers with ester linkages in the backbone chain
 glycol ethers - via glycol condensation
 ethoxylates
o vinyl acetate
o 1,2-dichloroethane
 trichloroethylene
 tetrachloroethylene - also called perchloroethylene; used as a dry cleaning solvent and
degreaser
 vinyl chloride - monomer for polyvinyl chloride
 polyvinyl chloride (PVC) - type of plastic used for piping, tubing, other things

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Chemicals produced from propylene

 propylene - used as a monomer and a chemical feedstock

o isopropyl alcohol - 2-propanol; often used as a solvent or rubbing alcohol
o acrylonitrile - useful as a monomer in forming Orlon, ABS
o polypropylene - polymerized propylene
o propylene oxide
 polyol - used in the production of polyurethanes
 propylene glycol - used in engine coolant and aircraft deicer fluid
 glycol ethers - from condensation of glycols
o acrylic acid
 acrylic polymers
o allyl chloride -
 epichlorohydrin - chloro-oxirane; used in epoxy resin formation
 epoxy resins - a type of polymerizing glue from bisphenol A, epichlorohydrin, and
some amine
 C4 hydrocarbons - a mixture consisting of butanes, butylenes and butadienes
o isomers of butylene - useful as monomers or co-monomers
 isobutylene - feed for making methyl tert-butyl ether (MTBE) or monomer for copolymerization
with a low percentage of isoprene to make butyl rubber
o 1,3-butadiene (or buta-1,3-diene) - a diene often used as a monomer or co-monomer for polymerization
to elastomers such as polybutadiene, styrene-butadiene rubber, or a plastic such as acrylonitrile-butadiene-
styrene (ABS)
 synthetic rubbers - synthetic elastomers made of any one or more of several petrochemical
(usually) monomers such as 1,3-butadiene, styrene, isobutylene, isoprene, chloroprene; elastomeric
polymers are often made with a high percentage of conjugated diene monomers such as 1,3-butadiene,
isoprene, or chloroprene
 higher olefins
o polyolefins such poly-alpha-olefins which are used as lubricants
o alpha-olefins - used as monomers, co-monomers, and other chemical precursors. For example, a small
amount of 1-hexene can be copolymerized with ethylene into a more flexible form of polyethylene.
o other higher olefins
o detergent alcohols

Chemicals produced from benzene

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 benzene - the simplest aromatic hydrocarbon
o ethylbenzene - made from benzene and ethylene
 styrene made by dehydrogenation of ethylbenzene; used as a monomer
 polystyrenes - polymers with styrene as a monomer
o cumene - isopropylbenzene; a feedstock in the cumene process
 phenol - hydroxybenzene; often made by the cumene process
 acetone - dimethyl ketone; also often made by the cumene process
 bisphenol A - a type of "double" phenol used in polymerization in epoxy resins and making a
common type of polycarbonate
 epoxy resins - a type of polymerizing glue from bisphenol A, epichlorohydrin, and
some amine
 polycarbonate - a plastic polymer made from bisphenol A and phosgene (carbonyl
dichloride)
 solvents - liquids used for dissolving materials; examples often made from petrochemicals
include ethanol, isopropyl alcohol, acetone, benzene, toluene, xylenes
o cyclohexane - a 6-carbon aliphatic cyclic hydrocarbon sometimes used as a non-polar solvent
 adipic acid - a 6-carbon dicarboxylic acid which can be a precursor used as a co-monomer
together with a diamine to form an alternating copolymer form of nylon.
 nylons - types of polyamides, some are alternating copolymers formed from
copolymerizing dicarboxylic acid or derivatives with diamines
 caprolactam - a 6-carbon cyclic amide
 nylons - types of polyamides, some are from polymerizing caprolactam
o nitrobenzene - can be made by single nitration of benzene
 aniline - aminobenzene
 methylene diphenyl diisocyanate (MDI) - used as a co-monomer with diols or polyols
to form polyurethanes or with di- or polyamines to form polyureas
 polyurethanes
o alkylbenzene - a general type of aromatic hydrocarbon which can be used as a presursor for a sulfonate
surfactant (detergent)
 detergents - often include surfactants types such as alkylbenzenesulfonates and nonylphenol
ethoxylates
o chlorobenzene

Chemicals produced from toluene

 toluene - methylbenzene; can be a solvent or precursor for other chemicals

o benzene
o toluene diisocyanate (TDI) - used as co-monomers with diols or polyols to form polyurethanes or with
di- or polyamines to form polyureas
 polyurethanes - a polymer formed from diisocyanates and diols or polyols
o benzoic acid - carboxybenzene
 caprolactam
 nylon

Chemicals produced from xylenes

 mixed xylenes - any of three dimethylbenzene isomers, could be a solvent but more often precursor chemicals
o ortho-xylene - both methyl groups can be oxidized to form (ortho-)phthalic acid

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 phthalic anhydride
o para-xylene - both methyl groups can be oxidized to form terephthalic acid
 dimethyl terephthalate - can be copolymerized to form certain polyesters
 polyesters - although there can be many types, polyethylene terephthalate is made
from petrochemical products and is very widely used.
 purified terephthalic acid - often copolymerized to form polyethylene terephthalate
 polyesters

meta-xylene

Important Processes :

Processes Hazards Safety Features

Chlorination - Chlorine hazards – toxic - Automation-DCS, PLC
- Lowering of Flash point of petroleum - Audit-visual alarm and controls
- Widening of flammable range of the petroleum - Dew point maintenance
- Exothermic, can be runaway - Pressure relief devices
- Corrosion - FFE
- PPE
- Flameproof fitting

Nitration - NOX hazards – adverse effects on CNS - Pipeline reactor

- Exothermic, fire and explosion - Automation-DCS, PLC
- Audit-visual alarm and controls
- Pressure relief devices
- FFE
- PPE
- Blowdown vessel
- Flameproof fiting
- Non-sparking tools

Sulphonation - Exothermicm runaway - Automation-DCS, PLC

- Solidification of mass - Audit-visual alarm and controls
- Solid mass is sensitive to water, - Pressure relief devices
impact andstatic - FFE
- PPE
- Blowdown vessel
- Flameproof fitting
- Non-sparking tools

Hydrogenation - low MIE of Hydrogen - Low flows speed

- Exothermic - Inerting
- Fire and explosion - Geared valve in venting

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- Presure relief devices
- FFE
- PPE
- Flameproof fittings
- Non-soarking tools

Bibliography :

- API Manual
- Safe Handling of Chlorine\
- Process Safety
- Risk Assessment

Exercise :

1. What do you mean by ―Petrochemical‖.?

2. Classify Petrochemicals.
3. What are the hazards of various petrochemical processes and their safety measures?

Suggested activities :

1. Make a chart of Petrochemicals.

2. Visit a petrochemical factory.

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