CHEMICAL PROCESSES

& SUSTAINABILITY

PETROLEUM &
NATURAL GAS

Course Outcome:
CO1:

The ability to describe the process and

utility requirements in major chemical
engineering industries and identify its
importance.

Course Learning Outcome:

Define

petroleum, hydrocarbon and nonhydrocarbon

Discuss the principal forms of petroleum
Identify the major constituents of petroleum
Identify the activities in petroleum industry
Explain the purpose of refining
Identify the process of refining
Explain the purpose and the process of
petroleum refining
Identify the products of refining

HISTORY OF OIL AND GAS INDUSTRY

Development of energy sources:

From Industrial Revolution to todays
energy
What is the major energy source in the
world?

HISTORY OF OIL AND GAS INDUSTRY

Machineries
invented
Limiting
factor:
continual
power source
to run them

1700s

Late 1700s
Steam
engine
invented
major fuel
firewood
Power source
for
steamships,
locomotives
and textile
mills

Coal replace
firewood
Coal replace
firewood
Coal also used
for heating,
cooking,
industrial
process
Limiting factor:
Environmental
problem

Late 1800s
Invention of
internal
combustion
engine (cars)
Oil-well drilling

1940s
Fuel and
natural gas
dominant

Wind power
Hydroelectric
Solar enery
biofuels

Today

HISTORY OF OIL AND GAS INDUSTRY IN MALAYSIA

1909

Oil was first discovered by Shell

1974 - PETRONAS
1975 Petroleum Development Act

615,000 square km of available oil

36% are covered by production sharing contracts

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

H2, C

COMPOSITION

Hydrocarbon
(HC)

Organic
Compund

O2, N2, Sulphur

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

ORIGIN OF PETROLEUM
What is the process involve in formation of oil and gas?

THEORY

ORGANIC

INORGANIC

Principle form of petroleum

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.

Drill
Remain liquid
Atmosphere

under the sea

Principle form of petroleum

Natural gas
A mixture of hydrocarbon
compounds and small
quantities of various nonhydrocarbons existing in
the gaseous phase or in
solution with oil in natural
underground reservoirs at
reservoirs conditions.

NGV
CH4
Dry & Wet gas

Sweet & Sour gas

Principle form of petroleum

Natural gas
Associated

gas

Non-associated gas

Principle form of petroleum

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.
- gaseous at subsurface
temperature and become
liquid when cooled to
surface temperature

Drill
Liquid
Atmosphere

under the sea

Gas

Principle form of petroleum

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.

ALKANES

ISOALKANES

AROMATIC
CONSTITUENTS

CYCLO ALKANES

ALKENES

Activities in Petroleum Industries

Sequence of activities in petroleum industry.
Acquisition of Right
EXPLORATION
APPRAISAL
install the platform to
drill

commercial significance

DEVELOPMENT
PRODUCTION

TRANSPORTATION
Refining & Distribution

bring oil/gas from

subsurface to
surface

PETROLEUM REFINING
Petroleum

refineries - separate crude oil

into a wide array of petroleum products through a
series of physical and chemical separation
techniques.
Purpose of refining
The refinery is designed to process several
different types of crude oil to produce useful
petroleum product.

Cracking or breaking down

large HC molecules to
smaller molecules at
temperature higher than
distillation

CONVERSION
PROCESS

To remove
impurities

MAIN
STEPS
SEPARATION
PROCESS

To split the crude oil into groups of HC

Using distillation process

TREATMENT
POCESS

(1) Separation
- split the crude oil into groups of hydrocarbon
- size of different molecules - according to the number of carbon atom
- the larger the molecules, the higher the boiling point of the compound
and the higher the temperature it vaporizes.
- the lightest hydrocarbons boil first become vapours and 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).
- Inside fractionators, the column is divided at intervals by horizontal trays
(perforated or valve trays).
- Valve trays - common type since can accommodate a wider range of
loading
- 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.

Distillation Process:
Heating - boiling

Condense
Liquid

Vaporize rise up
through valve trays

Liquid
Condense change
back to liquid drawn
off

Crude oil

Heater

Vapor rise
up

 CONVERSION

PROCESS

a) Cracking,

reforming are conversion processes used to

break down large longer chain molecules into smaller ones
by heating or using catalysts.

b) These

processes allow refineries to break down the heavier

oil fractions into other light fractions to increase the
fraction of higher demand components such as gasoline,
diesel fuels or whatever may be more useful at the time.

Catalyst cracking
Method of operation: carried out in presence of catalyst and H 2
at high pressure. Also called as hydrocracking
Products: high-octane motor gasoline, gases used as raw
material in petrochemical industry

Thermal cracking
Method of operation: Using heat and pressure alone
Products: heavy fuel oils, coke, diesel oil components

Steam cracking
Method of operation: Presence of steam at high temperature and
low pressure
Products: LPG and other light distillates

Reforming
Method of operation: reformed by heat and pressure into more
useful molecules of the same size and boiling range, use of catalyst
(platinum)
Products: motor gasoline, jet fuel

Reforming
use 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 HC mixtures containing many paraffins and naphthenes. It
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

isoparaffins

paraffins

naphthenes

naphthenes

aromatics

Other conversion process

Alkylation
refers to the chemical bonding of light molecules with isobutane to form
larger branched-chain molecules (isoparaffins) that make high octane petrol.
Olefins (propylene and butylene) 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).
Isomerisation
chemical rearrangement of straight-chain HC, so that they contain branches
attached to the main chain. This is done for two reasons:
they create extra isobutane feed for alkylation
they improve the octane of straight-chain HC.
Isomerisation can be used to improve petrol quality by converting HC to
higher octane isomers.

TREATMENT PROCESS

a)

Purpose: remove impurities.

Why?- can damage the equipment, the catalysts and
the quality of the products.
Major impurities: SULPHUR MERCAPTANTS
Other impurities: nitrogen, oxygen and various metallic
compounds, all which have to be removed at a certain
extent.
Hydrogen sulphide gas is also found dissolved in crude
oil and is produces by the thermal decomposition of
some mercaptants.
How to remove? - 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.

b)
c)
d)

MAJOR PRODUCTS OF OIL

REFINERIES

Crude oil distillation is the first stage of series of complex

petroleum processing process

Example of the product:

Liquid petroleum gas (LPG) mixture of mostly propane and butane

Gasoline (petrol) liquid mixture consists most of aliphatic hydrocarbon with isobutane
Naphtha
Kerosene and related jet aircraft fuels is a combustible hydrocarbon liquid.
Diesel fuel
Fuel oils
Lubricating oils
Paraffin wax
Asphalt and Tar
Petroleum coke

Most products of oil processing are usually grouped into three categories:
light distillates, middle distillates, and heavy distillates and residuum.

Light
distillate

residuum

PRODUCT
OF OIL
REFINING
Heavy
distillate

Middle
distillate

Light distillate
consists liquid petroleum gas(LPG), gasoline(petrol), motor gasoline
(automobile), naphtha, jet fuel and kerosene.

Middle distillate
form such as gas oil, light and heavy domestic furnace oils, diesel fuel
and distillate that used for cracking to produce more gasoline.

converted into lubricating oils, heavy oils for a variety of uses, waxes and
crackingHeavy
stock. distillate

includes asphalt, residue fuel oil, coke and petroleum.

residue

detergent

Product
using
petroleum

Plastic

Vaseline

Recap:
What

is petroleum, hydrocarbon and nonhydrocarbon?

What are the principal forms of
petroleum?
List the major constituents of petroleum.
State the purpose of appraisal in
petroleum industrys activities
Identify the process of refining
Explain the purpose
Explain the process of petroleum refining
Identify the products of refining

NATURAL GAS
What is 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.
Natural gas may be classified as:
i. Associated Gas: Free natural gas commonly known as gascaps
which overlies and in contact with crude oil in the reservoir
ii. Dissolved Gas: Natural gas which is in solution with crude oil in
the reservoir at the reservoir condition.
iii. Non-associated Gas: Free natural gas not in contact with crude
oil in the reservoir.

NATURAL GAS- terminologies

LNG = Liquefied Natural Gas

LPG = Liquefied Petroleum Gas
NGL = Natural Gas Liquids

NATURAL GAS- terminologies

NATURAL GAS PROCESSING

LNG PROCESS CHAIN:

NATURAL GAS PROCESSING

Block Scheme - LNG Plant
EXTRACTION
CO2, H2S

ACID GAS REMOVAL

DEHYRATION

Water

MERCURY REMOVAL
SCRUBBING

Hg on sorbent
Liquid

FRACTIONATION

Gas

LIQUEFACTION
TRANSPORTATION

C2, C3, C4
RE-INJECTION

C2, C3 Refrigerant
C3, C4 LPG
C5+ Gasoline

PETRONAS MLNG

NATURAL GAS PROCESSING

Natural gas is processed through the following stages.
Extraction : Natural gas is gather at the main production platform
which is located offshore. It is then piped via trunk lines and enters
the processing plant onshore

NATURAL GAS PROCESSING

Acid gas removal : To remove the main contaminants, carbon dioxide
(CO2) together with traces of sulphur compounds.
2 methods of removal process: solvent absorption & adsorption
Solvent absorption: acid gas dissolve in the liquid followed by
chemical reaction with alkali compound to produce soluble salt
Adsorption: physical adsorption on synthetic zeolites (solids)

NATURAL GAS PROCESSING

Dehydration Unit : Moisture is taken down to reduce pipeline corrosion
and eliminate pipe blockage caused by hydrate formation. The water
dew point should be below the lowest pipeline temperature to prevent
free water formation.
Methods: Physical absorption & physical adsorption
Physical Absorption process:
In physical absorption process, the gas containing water is contacted
with a liquid that absorbs the water vapour.
Physical Adsorption process:
Physical adsorption is an equilibrium process in which the water is
adsorbed onto a solid phase by means of adsorbent. In this process,
the wet gas is passed through two-bed adsorbers system. One bed
dries the gas while the other one, the gas goes through regeneration
cycle. Regeneration involves heating the bed, removing the water and
cooling.

NATURAL GAS PROCESSING

Physical Adsorption process:

NATURAL GAS PROCESSING

Mercury Removal Unit : To remove mercury in order to prevent
corrosion of pipe work and equipment made from Aluminium.
Removal process: Generative and non-generative process
Nongenerative process:
Utilizes sulphur sulphur-impregnated carbon for mercury removal. The
mercury reacts with the sulphur to form a stable compound on the
adsorbent surface.
Regenerative process:
Utilizes silver on molecular sieve to chemisorb mercury while providing
dehydration at the same time. The silver-impregnated sieve is added to
the standard molecular sieve dehydration bed, and the basic
dehydration process remains unchanged. Consequently, the mercury
condenses with the water on regeneration and forms a separate phase,
which easily can be decanted and sold.

NATURAL GAS PROCESSING

Scrubbing :To remove heavy hydrocarbons (liquid phase) by partial
condensation and fed to the fractionation unit. Lighter components
(gaseous phase) fed into liquefaction unit.
Fractionation Unit : Pentane and heavier hydrocarbons is separated
and run down as gasoline, the butanes and lighter components are
re-injected into the liquefaction unit as make up.
MERCURY REMOVAL
SCRUBBING

Hg on sorbent
Liquid

FRACTIONATION

Gas

LIQUEFACTION
TRANSPORTATION

C2, C3, C4
RE-INJECTION

C2, C3 Refrigerant
C3, C4 LPG
C5+ Gasoline

NATURAL GAS PROCESSING

Liquefaction: One common method in engineering practices to
produce low temperature is Joule-Thomson liquefaction cycle:

NATURAL GAS PROCESSING

Liquefaction:
The liquefaction cycles begins with natural
gas being compressed and sent through the
heat exchangers and expansion valve. Upon
expansion, the gas cools (approximately
47C) if the gas is principally methane and
the expansion is from 101 to 1 bar.

NATURAL GAS PROCESSING

Liquefaction:
Thus, all of the chilled low-pressure gas is
recycled through the heat exchanger for
recompression. This cold low-pressure gas
lowers the temperature of the high-pressure
gas stream ahead of the expansion valve,
which result in a lower temperature upon
expansion.

NATURAL GAS PROCESSING

Liquefaction: continued:
As long as all of the gas being expanded is recycled through the
counterflow heat exchanger to cool the high-pressure gas stream,
temperatures will be progressively lower upon expansion.
The process continues until liquid is formed during the expansion
from high to low pressure. The liquid formed is separated from
the low-pressure gas stream in the liquid receiver.
The liquid is withdrawn as LNG.

NATURAL GAS PROCESSING

Transportation:
The LNG product is stored at temperature of -162C and
atmospheric pressure at the tank farm. The LNG is transported by
three options:
Truck transport
LNG Pipelines
Marine carriers

NATURAL GAS: PRODUCT & APPLICATION

Methane (CH4)
- Fuel for residential, commercial and industrial heating
- Chemical feedstock, ammonia, fertilizer, methanol
- For export as LNG or by pipeline as fuel or feedstock application
Ethane (C2H6)
- Conversion material to ethylene (end product is plastic goods,
packaging, synthetic fibre, cloth)
Propane (C3H8) and Butane (C4H10)
- Fuel for residential, commercial and industrial heating, automotive
fuel
- Chemical feedstock for plastic and synthetic material
- Export as LPG for fuel and feedstock
Condensate (C5~C10)
- Fuel for industrial heating
- Chemical feedstock for plastic and synthetic material
- Refinery feedstock for fuel

ENVIRONMENTAL IMPACTS

Environmental Hazards of
Petroleum Refineries
Refineries-a

major source of pollutant in

areaswhere they are located and are regulated
by a number of environmental laws related to
air,land & water.

Effect to the environment

a)

Air pollution hazards

-petroleum refineries are a major source of
hazardous and toxic air pollutant
-major sources of criteria air pollutant
-release less toxic hydrocarbon and other light
volatile fuel
-health effect: -asthma
-cough

b) WATER POLLUTION HAZARDS

-potential major contributors to ground water
and surface water contamination
-wastes are regulated under the safe drinking
water act
-wastewater in refineries may be highly
contaminated during the refinery process
c) SOIL POLLUTION HAZARDS
-include hazardous waste and sludges from the
treatment processes can occur from leaks

Impact of oil spills

Marine life
>include the type and amount of oil and its
behaviour once spilled
>effects on marine organisms
Eg: birds mortality occurs
seabirds vulnerable inhabitant
productivity of plankton is less

Economic

- directly damage the boats and gear

used for catching or cultivating marine
species
- economic loss to fishermen is
interruption to their activities