CHE262

CHEMICAL PROCESSES AND

SUSTAINABILITY

PETROLEUM
 Introduction
• 1859 – first well was drilled in Penn
Sylvania, USA
• 1897 – first well was drilled offshore in
California, USA
• 1910 – first well was drilled in Malaysia
(well Miri No.1 in Sarawak)
 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) &
hydrogen (H) only
• Non-hydrocarbon = compound that contain some
sulphur, oxygen and nitrogen atoms besides C & H
• The principal forms of petroleum are:
- Crude oil
- Natural gas
- Condensate
- Asphalt
 Crude Oil
• A mixture of HC that exists in the liquid phase in
natural underground reservoirs and remains
liquid at 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 liquid
 Natural gas
• A mixture of HC compounds and small quantities of
various non-HC (eg. N2 and CO2) existing in the gaseous
phase or in solution with oil in natural underground
reservoirs at reservoir conditions
• Main HC component: methane (CH4)
• Dry gas contains 90-100% CH4
• Wet gas contains greater proportions of ethane,
propane, butane etc
• CO2, H2S & N2 also present
• Sweet and sour gases refer to the low and high content
of H2S respectively
• Application: power generation, industrial feedstock eg.
Fertilizers or liquefied into LNG for efficient
transportation
 Natural gas classification
• Associated gas:
- free natural gas, commonly known as gas-caps
which overlies and in contact with crude oil in the
reservoir
• Dissolved gas:
- Natural gas which is in solution with crude oil in
the reservoir at reservoir conditions
• Non – associated gas:
- Free natural gas not in contact with crude oil in
the reservoir
 Associated gas reservoir Gas

Oil

Water

Non - associated gas reservoir

Gas

Water
 Condensate
• HCs 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 conditions.
• Composed mainly of compounds in which
molecules contain at least 5 C atoms
• Colour: yellowish to colorless
 Asphalt
• Thick brownish or black substance derived from
the same crude oil which produces kerosene,
gasoline and vinyl.
• Composed of at least 80% carbon, which
explains its deep black color.
• Sulphur is another ingredient found in the tar-like
asphalt, as well as some trace minerals.
• Application: sealant for rooftops and a durable
surface for roads, airport runways, playgrounds
and parking lots.
 Origin of petroleum
In general, 2 theories exist:
1. Inorganic theories
- reaction of CO2 with H2O under suitable conditions
- assumes oil form from the reduction of primordial
carbon or its oxidized form at high temperatures deep in
the earth

2. Organic theories
- remains of plants and animals (most widely accepted)
- accumulation of HC from living things
- generation of HC by heat action on biogenically
formed organic matters
 Reservoir rock
• Most important types: sandstones and
carbonates
• A petroleum reservoir is the part of rock
that contains the pool of oil or gas
• Any rock with interconnected pores and
sufficient permeability to allow oil or gas
phase production
Sequence of activities in petroleum industry
Acquisition of Right

EXPLORATION

APPRAISAL

DEVELOPMENT

PRODUCTION

Export or Processing
• 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 determine commercial
significance of discovery & to shape the
field initial development plan
• Development – to formulate the field
development plan, install platforms, to drill
and complete the development wells
• 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
 Seismic data acquisition

• Seismic method involves generation of

elastic vibration causing ground motion
which can be detected by geophones
Exploration drilling:
- Petroleum accumulations can only be
discovered by drilling i.e. there is no direct
method of locating a pool of petroleum
without first drilling test wells
- Drilling also serves as a source of
subsurface data
- Purpose of drilling – finding and producing
oil
 Questions to be answered
• Where, how deep is the reservoir?
• How thick is it?
• What kind of rock is it?
• What is the porosity of this rock?
• What does it contain (water, oil or gas)?
• What will it produce?
• What is its areal extent?
 What is a field development plan?
• Highlight the planned development activities in the field
• Addresses the following:
- geology of the field
- oil and gas original in place, reserve and production
forecast
- schedule of field development
- no. of platforms and wells
- methods for improving oil recovery
- well completion design
- production facilities aspects
- gas utilisation and conservation schemes
- project cost and project economic
Types Of Offshore Drilling Rigs
Oil Production System
• Tubing – a small pipe of diameter 3½ inch
installed in the well to handle the fluid flow from
the reservoir
• Christmas tree – assembly of valves on a final
casing to control the rate of oil production
• choke – a removable steel orifice device fitted to
a well flowline to restrict fluid flow
• Flowline – a pipeline that connects the well to
the separator
• Separator – vessel for separating mixtures of oil,
gas and water
• Storage tank – a tank in which oil is stored
 Purpose of refining
• The refinery is designed to process
several different types of crude oil to
produce useful petroleum products
Diff. prodts at diff. temp
Refining crude oil is carried out in 3 main
stages:
• separation – to split crude oil into groups
of HCs using distillation process
• conversion – breaking down of large HC
molecules into smaller ones at temp higher
than used in distillation
• treatment – to remove impurities
 Separation
- Process to split crude oil into groups of HCs according to size of diff
molecules
- Molecular size determined according to no. of carbon atoms present
- The larger and more complex molecules, the higher the boiling pt. and
temp. to vaporize
- When crude oil heated, lightest HC boil off first and heaviest last.
- As vap. cooled, they condensed back to liquids reverse order –
distillation process (to separate HCs into fractions or groups wt similar
boiling pts.
- In refinery, fractional distillation takes place in tower (fractionator) wt
temp 340oC at base
- Temp gradually decrease towards the top 110oC
- Column internals divided by intervals by horizontal trays: perforated or
valve trays
- Valve trays more common since they can accommodate wider vapor
load than perforated trays
- ↑ Vap load, no of valves open on each tray also increase
- Each tray cooler than the one below it providing temperature gradient
on which separate vapors can condense
• Crude oil first heated by furnace, then passed into the lower part of
the column
• Since most fractions in the oil is already boiling, they vaporize and
rise up column thru valve trays
• As each fraction condenses and chges back to liquid on separate
trays, they are drawn off
• This distillation proc. is continuous wt hot curde oil flowing in near
the base of column and separate fractions flowing out at each level
• 1st distillation carried out at atm. press. & separate crude oil into
gases, light distillates, middle distillates & residue
• The very lightest fraction: refinery gas in vap phase, used as fuel in
refinery
• 1st prodt fraction: LPG – C3 & C4
• Light distillates: gasoline & naphtha – major feedstock for
petrochemical industry
• Middle distillates: kerosene – aviation fuel, gas oil – heating fuel and
for blending in diesel fuels
• Residue used for fuel oil or further processed into lubricating oils,
waxes & bitumen
• Depending on crude oil being processed, a single atm. DC not
sufficient to separate out req. range of prodts. Efficiently
• Often a series of DC is used
 Conversion
• Dist. proc rarely yield prodts in proportions required
by market
• Hence, a variety of conversion techniques used to
enable yield of prodts to be reshaped to match
market demand
• Conversion processes depend on types of crude to
be processed & requirements of the market
 Cat-cracking Cracking alkylation
Breaking down
Cracking usg of large HC Linking or
catalyst Prod. molecules into changing
Components for smaller arrangement
Blending into high valuable ones of molecules to
octane motor at temp. obtain
gasoline, diesel Higher than in additional
fuel Components, DC quantities of
C3-C4 gases high octane
motor gasoline
hydrocracking
Catalyst and
hydrogen gas
present at high Conversion reforming
pressure Light distillates
containing HC
Steam molecules
cracking reformed by
Thermal cracking heat & P into
LPG or light Heat & pressure more useful
distillates visbreaking alone was the molecules of
broken down Used to original method same size and
in presence improve quality of obtaining boiling range
of steam at of heavy fuel greater amounts usg catalyst eg
high T and oils & to make of motor platinum
low P diesel fuel gasoline (Platformer)
components
 Treatment
• To remove impurities of prodts from distillation proc.,
feedstocks & prdts of conversion proc.
• Why? Reduce efficiency of conversion proc., prdts
become corrosive or unpleasant for customer to handle
• Main impurity: sulphur found in nearly all crude oils to
some extent
• Crude oils categorized by sulphur content
• Sweet crude: small amts of sulphur
• Sour crude: large amts of sulphur
• Mercaptans: organic sulphur compound
• How to remove sulphur? Pass the untreated prdts wt a
stream of H2 thru a bed of catalyst, converted to H2S gas
then addition of chemicals, extracted and converted to
liquid or solid sulphur for sale
• Others: N2, O2 and various metallic compds which
needed removal
 Blending
• Most fuels and lubricants are blends of
limited no. of basic grades fr refinery
• Contain additives designed for particular
uses
• Carried out in batching tanks complete wt
stirrer or circulating pumps or by in-line
blending
Major constituents of Petroleum

I. n-Parafin Series/alkanes, CnH2n+2

II. Iso-Parafin series/alkanes, CnH2n+2
III. Olefin or alkenes series, CnH2n
IV. Naphthene series or cycloalkanes, CnH2n
V. Aromatic/Benzoid Series, CnH2n-6