COURSE OUTLINE

IMPORTANT OF CHEMICAL PROCESS

INDUSTRIES IN MALAYSIA
UTILITIES REQUIREMENT IN PROCESS
INDUSTRIES
INDUSTRIAL POLLUTION
SPECIAL TOPICS

IMPORTANT OF CHEMICAL
PROCESS INDUSTRIES IN MALAYSIA
PETROLEUM
NATURAL GAS
PALM OIL
SURFACE COATING INDUSTRIES
RUBBER INDUSTRIES
CEMENT INDUSTRIES

CHAP 1.1: PETROLEUM

Origin and Distribution
Petroleum Drilling Operation
Petroleum Refining Processes
Selected Petrochemicals Processing

OIL AND GAS INDUSTRY

1859 First well was drill in

Pennsylvania, USA
1897 First well was drilled
offshore in California, USA
1910 First well was drilled in
Malaysia (Well no. 1 is in Sarawak)

DEFINITION: PETROLEUM
Petroleum: A form of bitumen composed principally of
hydrocarbons which exists in the gaseous or liquid state in its
natural reservoirs.
Petroleum = Hydrocarbon Compound + Non-Hydrocarbon
Compound
Hydrocarbon = Organic Compounds of Carbon (C) and Hydrogen
(H)
only
Non-Hydrocarbon = Compound that contain some sulphur, oxygen
or
nitrogen atoms besides hydrogen and carbon
- Petroleum means oil (oleum) rock (petra).
- Petroleum is synonymous with hydrocarbon.

HYDROCARBON
Hydrocarbon can be found as:
(i) Natural gases. e.g. methane, ethane
(ii) Liquid. e.g. liquid crude, medium crude and heavy crude
(iii) Semi-solid. e.g. asphalts, waxes

Principal forms of petroleum are:

(i)
(ii)
(iii)
(iv)

Crude oil
Natural gas
Condensate
Asphalt

HYDROCARBON
(i) Crude oil

- A mixture of hydrocarbons that exists in the liquid phase in natural

underground reservoirs and remain liquid at the atmospheric
pressure after passing through surface separating facilities.
- Appearance: dark brown to yellowish brown.
- Density: ranges from very dense - denser than water - to very
light.
- Viscosity: ranges from solid to very thin liquid.

(ii) Natural gas

- A mixture of hydrocarbon compounds and small quantities of

various
non-hydrocarbons (e.g. nitrogen and carbon dioxide)
existing in the
gaseous phase or in solution with oil in natural
underground
reservoirs at reservoirs conditions.
- Main hydrocarbon component is methane (CH 4).
- Dry gas contain 90-100% CH4.
- Wet gas contain greater proportion of ethane (C 2H6), propane
C3H8),
butane (C4H10), etc.
- Carbon dioxide (CO2) and hydrogen sulphide (H2S) and nitrogen
may
also be present.

HYDROCARBON
- Sweet and sour gases refer to the low and high content of hydrogen
sulphide, respectively.
- Use in power generation, industrial feedstock like fertilizers and
liquefied into LNG for efficient transport.
(iii) Condensate
- The hydrocarbons which are in the gaseous state under reservoir
conditions but become liquid either in passage up the hole or at
surface due to the reduced pressure condition.
- Appearance: yellow to colourless.
- API gravity > 60 degrees
- Some hydrocarbons mixtures are gaseous at subsurface
temperature and become liquid when cooled to surface temperature.
- The fluid therefore condense and liquefy when produced
- There is no fundamental difference between wet gases and
condensate.
- Condensate are composed mainly of compounds in which
molecules contain at least 5 carbon atoms.
- Most gas field produce a lot of condensate which are measured in
barrels per day and treated like oil.

HYDROCARBON
(iv) Asphalt
- Hydrocarbon which is sticky, black and highly viscous liquid or
semi-solid
- Difficultly salable material, is by product of the refining process
- Difficult to dispose and relatively unprofitable
- The properties can be changed by heating it and partly
oxidizing it by blowing air through it.

ORIGIN OF PETROLEUM
What is the process involve in formation of oil and gas?
In general, 2 theories are exists for the origin of oil and gas.
(1)Inorganic theories reactions of carbon dioxide with water under

suitable conditions.
(2)Organic theories main source of petroleum is organic remains
of plants and animals.
Organic theory is the most widely accepted today.
-

The organic theory is based on accumulation of hydrocarbon

from lying things and the generation of hydrocarbon by heat
action on biogenically formed organic matters.
The inorganic hypothesis assumes oil form from the reduction of
primordial carbon or its oxidized form at high temperatures deep
in the earth.

CONSITUENT OF PETROLEUM
Crude petroleum is made up of thousands of different chemical
substances including gases, liquids and solids and ranging from
methane to asphalt. Most constituents are hydrocarbons but there are
significant amounts of compounds containing nitrogen (0-0.5%), sulfur
(0-6%) and oxygen (0-3.5%).
Below is list of major constituents of petroleum.
a)

n-Parafin Series or Alkanes, CnH2n+2

b)

iso-Parafin Series or iso-Alkanes, CnH2n+2

c)

Olefin or Alkene Series, CnH2n

d)

Naphthene Series or Cycloalkanes, CnH2n

e)

Aromatic or Benzoid Series, CnH2n-6

Aliphatic or
open chain
hydrocarbons

Ring
compounds

CONSITUENT OF PETROLEUM
a) n-Parafin Series or Alkanes, CnH2n+2
- Comprise a larger fraction of most crude than any other
- Most straight-run (distilled directly from crude) gasolines a
predominantly n-paraffin
- Poor antiknock properties
- e.g. n-hexane, n-heptane
b) iso-Parafin Series or iso-Alkanes, CnH2n+2
- Perform better in internal-combustion engines than n-paraffin, more
desirable
- Formed by catalytic reforming, alkylation, polymerization or
isomerization
- e.g. 2- and 3-methylpentanes, 2,3-dimethylhexane
c) Olefin or Alkene Series, CnH2n
- Generally absent in crudes but produce in refining process (crackingmaking smaller molecules from large one)
- Unstable molecules improve the antiknock quality of gasoline (not as
effective a iso-paraffin)

CONSITUENT OF PETROLEUM
- On storage, they polymerize and oxidize, undesirable, very tendency
to react but useful for forming other compounds, petrochemicals by
additional chemical reactions. e.g. ethylene, propylene, butylene
d) Naphthene Series or Cycloalkanes, CnH2n
- Different from naphthalene
- Having same chemical formula as olefins
- Lower members of this group are good fuels
- Higher molecular weight are predominant in gas oil and lubricationg oil
- e.g. methylcyclopentane, cyclohexane, dimethylcyclopentanes,
methylcyclohexane
e) Aromatic or Benzoid Series, CnH2n-6
- Only small amounts of this series occur in most common crudes but they
are very desirable in gasoline since they have high antiknock value
- Only special crude (Borneo Sumatra) has relatively high amount
- Good storage stability and many uses besides fuel
- Many aromatic are formed by refining processes
- e.g. benzene, toluene, ethylbenzene, xylene

ACTIVITIES IN PETROLEUM INDUSTRY

Sequence of activities in petroleum industry.
Acquisition of Right
EXPLORATION
APPRAISAL
DEVELOPEMENT
PRODUCTION

Export or Processing

ACTIVITIES IN PETROLEUM INDUSTRY

Activities:

Acquisition of Right: To obtain permission from government or

relevant agency before drilling of exploration well.
Exploration: To search for oil and gas
Appraisal: To determined the commercial significance of the
discovery and to shape the initial development plan for the field.
Development: to formulate the field development plan of the field, to
install the platform to drill and complete the development well.
Production: To bring oil/gas from subsurface to surface and to
separate between gas/oil/water before the oil is stored and gas is
processed.
Transportation: To bring oil from storage to refinery and gas to gas
processing plant either by pipeline or floating tanker.
Refining/gas processing: To manufacture petroleum products from
crude oil.
Marketing: To distribute the petroleum products to customers.

PETROLEUM REFINING
Purpose of refining
- The refinery is designed to process several different types of
crude oil to produce useful petroleum product.
Refining crude oil is carried out in 3 main stages.
(1) Separation

To split the crude oil into groups of hydrocarbon using

distillation process.
(2) Conversion

Cracking or breaking down of large hydrocarbon molecules.

Smaller at temperature higher than used in distillation.
(3) Treatment

To remove impurities

PETROLEUM REFINING - SEPARATION

(1) Separation
- Process to split the crude oil into groups of hydrocarbon
- Done according to the size of different molecules, normal
practice is to define the molecular size according to the
number of carbon atom present
- Generally, the larger and more complex the molecules, the
higher tends to be the boiling point of the compound and
consequently the temperature at which it vaporizes.

PETROLEUM REFINING - SEPARATION

- When crude oil is heated, the lightest

hydrocarbons boil first. As the vapours are

cooled, they then condense back to liquid in
reverse order; this technique known as
distillation (used to separate the
hydrocarbons into fractions or groups
having similar boiling points).
Fractional distillation of fractionation takes
place in a tower known as a fractionators,
temperature of ~340C at its base and
gradually decrease towards the top, ~110C
Inside fractionator, the column is divided at
intervals by horizontal trays (perforated or
valve trays).

PETROLEUM REFINING - SEPARATION

- Valve trays are more common type since they can
accommodate a wider range of loading than perforated
trays.
- As the vapour load in the column increases, so does the
number of valves which open on each tray.
- Each tray is cooler than the one below it, thus providing a
temperature gradient on which separate vapours can
condense.
- The crude oil is first heated by a furnace and then passes
into the lower part of the column. Since most of the fractions
in the oil are already boiling, they vaporize and rise up the
column through the valve trays. As each fraction condense
and change back into liquid.

PETROLEUM REFINING - SEPARATION

As the fraction condenses on their separate

trays, they are drawn off.

This distillation process is continuous, with hot
crude oil flowing near the base of the column
and separate fraction flowing at each level.
The first distillation is carried out at
essentially atmospheric pressure and
separates crude oil into gasses, light
distillates, middle distillates and residue.
The very lightest fraction is termed refinery
gas which remain as a vapour and is used as a
fuel in the refinery.

PETROLEUM REFINING - SEPARATION

- Depending upon the crude oil being processed, a single

atmospheric distillation process will not necessarily separate
out the required range of product efficiently, and often a
series of distillation columns is used.
- e.g. the naphtha may be further split into a light and heavy
naphtha stream, the heavy stream typically goes on for
treatment and reforming whereas the light stream may be
further distillated to provide petrochemical feedstock stream.

PETROLEUM REFINING - CONVERSION

(2) Conversion
- Conversion technique is used to enable the yield of products to be reshaped to match market demand.
- Main conversion process is cracking, the breaking down of large
hydrocarbon molecules of heavy fractions into smaller more valuable
molecules at temperature higher than those used in distillation.

PETROLEUM REFINING - CONVERSION

Types of cracking process

(1) Catalyst cracking

Produce components for blending into highoctane motor gasoline, diesel components
and C3 - C4, gasses used largely as raw
material
for petrochemical industry.
Gasoline and kerosene can be produced
from the heavier fractions
if the cracking
process is carried out in the presence of
catalyst and hydrogen at high pressure.
This hydrocracking process is supplement
to other cracking process.

PETROLEUM REFINING - CONVERSION

(2) Thermal cracking

Using heat and pressure alone, original method of obtaining
greater
amounts of motor gasoline. e.g. visbreaking used
to improve the
quality of heavy fuel oils and to make diesel
oil components, production of coke for industrial carbon
electrodes.
(3) Steam cracking
Process in which LPG or light distillates are broken down
in the
presence of steam at high temperature and low
pressure.

PETROLEUM REFINING - CONVERSION

(4) Reforming
Light distillate (usually naphtha) containing
hydrocarbon
molecules smaller than those
found in cracking feedstock are reformed by
heat
and pressure into more useful molecules
of the same size and boiling range.
A catalyst improve catalytic process (platinum)
and the process
known as platformer
(platinum catalytic reformer).
Its product include components for motor
gasoline and jet fuel and
aromatic (cyclic)
hydorcarbons for petro-chemical feedstock.
Also produce large quantities of hydrogen which
in an integrated
refinery, is used in treating
processes and for hydrocraking.

PETROLEUM REFINING - CONVERSION

(5) Other conversion process

Linking or changing the arrangement of molecules to
obtain additional quantities of high-octane motor gasoline
Alkylation: combines the lightest fractions by using
sulphuric acid as a catalyst.
The heaviest residue (after vacuum distillation) is
converted by blowing air through it at high temperature, to
give a variety of grades of bitumen for industrial uses.

PETROLEUM REFINING - TREATMENT

(3) Treatment
- The products of the conversion have to be treated to remove
impurities.
- Impurities reduce the efficiency of conversion process, make
product corrosive or unpleasant fro customer to handle.
- Major impurity: SULPHUR
Sweet crude oil, small amount of sulphur
Sour crude oil, large amount of sulphur

PETROLEUM REFINING - TREATMENT

The most common are a group of organic sulphur

called mercaptants.
Hydrogen sulphide gas is also found dissolved in
crude oil and is produces by the thermal
decomposition of some mercaptants.
Remove sulphur by passing the untreated product
with a stream of hydrogen through a bed of
catalyst. Sulphur converted to hydrogen sulphide
which the aid of chemicals, is extracted and
converted into liquid or solid sulphur for sale to
chemical industry.
Other impurities: nitrogen, oxygen and various
metallic compounds, all which have to be removed
at a certain extent.

PRODUCT OF REFINING
Crude oil distillation is the first stage of a series of complex
petroleum processing process. The distillation consists of light,
intermediate, heavy distillates and residue. Below are the list of
the distillate (product obtain from the condensation of vapour in
a distillation column).
(i)
Light Distillate
Aviation gasoline, motor gasoline (automobile), naphtha,
petroleum solvents, jet fuel and kerosene.
(ii) Intermediate Distillate
Gas oil, light and heavy domestic furnace oils, diesel fuel and
distillate used for cracking to produce more gasoline. Used
mainly for transportation fuels in heavy trucks, railroads, small
commercial boats.

PRODUCT OF REFINING
(iii) Heavy Distillate
These are converted into lubricating oils, heavy oils for a
variety of
fuel uses, waxes and cracking stock. Lubricating oils of
high quality can readily be made from paraffin-base oils
but most oils are mixed or naphtene base and solvent.
(iv) Residue
The residue including asphalt, residue fuel oil, coke and
petrolatum. Asphalt used as road-paving material, for
water proofing structures and roofing material. Petroleum
coke commercially used in making electrodes,
manufacture of calcium carbide, paint and ceramics.