Petroleum Industry

in South Africa
SA Production Capacity
Location of Production Facilities
Contributors 2 SA’s Crude oil Imports
SA Convention Oil & Gas, &
Unconventional Gas
Location of
Reserves
Crude Oil Shipping Vessel at Harbour
MAIN POINT OF ENTRY FOR CRUDE OIL INTO SOUTH AFRICA
• Durban 76.42%
• Cape Town 22.06%
• Mosselbay 1.51%
Very Large Crude Carrier at Durban SBM
Schematic Layout of the SBM buoy &
pipeline to the refinery

Subsea pipeline 2.5km, 48” dia

Installed in 1999
SBM Inc Buoy installed 2009
330,000 dwt maximum tonnage
PLEM at depth 48m
Largest Worldwide Refineries
Crude Oil Origin and Properties
What is crude oil and what are petroleum
products?

• Crude oil is a mixture of hydrocarbons that

formed from plants and animals that lived
millions of years ago. Crude oil is a fossil fuel, and
it exists in liquid form in underground pools or
reservoirs, in tiny spaces within sedimentary
rocks, and near the surface in tar sands.
• Petroleum products are fuels made from crude
oil and other hydrocarbons contained in natural
gas.
• Petroleum products can also be made from coal,
natural gas, and biomass.
Crude Oil Characteristics
Crude Oil Characteristics: Gravity
Crude Oil
• Crude oil is made up of a wide range of
hydrocarbons.
• Hydrocarbons are molecules containing chains
of carbon and hydrogen.
• Length of chains vary from 1 carbon atom to
more than 70.
• Structures include straight and branched
chains and rings.
Crude Oil
• Combustion of hydrocarbons release a lot of
energy. Many of the products derived from
crude oil like gasoline, kerosene, diesel, take
advantage of this.
• By chemically cross-linking hydrocarbon
chains you can get a range of polymers
(“plastics”, synthetic rubber, nylon etc).
Hydrocarbon Names
Hydrocarbons
• The major classes of hydrocarbons in crude oils
include:
• Paraffins (or alkanes)
– general formula: CnH2n+2
– straight- or branched-chain molecules
– can be gas or liquid at room temperature depending
upon the molecule
– examples: methane, ethane, propane, butane,
isobutane, pentane, hexane
Hydrocarbon
C= Paraffins (or alkanes) H=

C1 METHANE CH4

C2 ETHANE C2H6

C3 PROPANE C3H8

C4 BUTANE C4H10

Also isoparaffins
Hydrocarbons
Olefins (Alkenes) C=
H=
C2 Ethylene
(ethene)
C2H4

C3 Proylene
C3H6
(propene)

C4 Butylene
(butene) C4H8
Hydrocarbons
• The major classes of hydrocarbons in crude oils
include:
• Napthenes (Cycloalkanes)
– general formula: CnH2n
– ringed structures with one or more rings
– rings contain only single bonds between the carbon
atoms
– typically liquids at room temperature
– examples: cyclohexane, methyl cyclopentane
Hydrocarbons
Naphthenes (Cycloalkenes)
HYDROGEN CARBON

CYCLOPENTANE C5H10
Hydrocarbons
• The major classes of hydrocarbons in crude oils
include:
• Aromatics
– general formula: C6H5 - RH (R is a chain that connects to
the benzene ring)
– ringed structures with one or more rings
– rings contain six carbon atoms, with alternating double
and single bonds between the carbons
– typically liquids
– examples: benzene, toluene, xylenes, ethylbenzene
Hydrocarbons
AROMATICS
CARBON HYDROGEN

Benzene C6H6
Hydrocarbons
• Other hydrocarbons
– Olefins (Alkenes)
• general formula: CnH2n
• linear or branched chain molecules containing one carbon-
carbon double-bond
• can be liquid or gas
• examples: propylene, butylene, isobutylene
– Dienes
• general formula: CnH2n-2
• linear or branched chain molecules containing two carbon-
carbon double-bonds
• can be liquid or gas
• examples: butadienes
Typical Composition of Crude
Refined Products

Aviation fuel
Refinery Products
Product Quality

Gasoline –
RON 60 - 70

200 oC

300 oC

Gasoil Sulphur 0.5 – 2%wt

420 oC (5,000 – 20,000 ppm)
Octane Rating
• In the year 1972, Edger introduced a system of ranking of
fuel based on the efficiency of fuel.
• It has been found that n-heptane knocks very badly and
hence anti-knocking value of n-heptane has arbitrarily been
fixed as zero (0).
• On the other hand, iso-octane (2,2,4-trimethypentane) was
found to give little knocking and hence its anti-knocking
value was fixed as 100.

• 𝐶𝐶𝐶𝐶3 − 𝐶𝐶𝐶𝐶2 5 − 𝐶𝐶𝐶𝐶3

n-heptane
Octane No. = 0
Octane Number - Definition
Knocking and Chemical Structure
Diesel Engine Fuels
Cetane Rating
Cetane and Octane comparison
Petroleum Refining Industries
Petroleum refining is the physical, thermal and chemical separation
of crude oil into its major distillation fractions which are then further
processed through a series of separation and conversion steps into
finished petroleum products.
Petroleum refineries are a complex system of multiple operations and
the operations used at a given refinery depend upon the properties of
the crude oil to be refined and the desired products.
Petroleum Industry products
 The main products of this industry are divided into three categories:
CHEMICAL INDUSTRY FINISHED NON FUEL
FUELS FEEDSTOCKS PRODUCTS

motor gasoline, diesel and naphtha, ethane, propane, solvents, lubricating oils,
distillate fuel oil, jet fuel, residual butane, ethylene, propylene, greases, petroleum wax,
fuel oil, kerosene and coke butylenes, butadiene, benzene, petroleum jelly, asphalt and coke
toluene and xylene

These products are used as primary input to a vast number of products: fertilizers, pesticides, paints, waxes, thinners,
solvents cleaning fluids, detergents, refrigerants, anti-freeze, resins, sealants, insulations, latex, rubber compounds,
hard plastics, plastic sheeting and synthetic fibers.
Products From Crude Oil
• The problem is that crude oil contains hundreds of different
types of hydrocarbons all mixed together.
• You have to separate the different types of hydrocarbons to
have anything useful.
• Different hydrocarbon chain lengths have progressively higher
boiling points, so they can be separated by distillation.
• Distillation is the basis of oil refining.
• Crude oil is heated and the different chains are separated by
their vapourisation temperatures.
Products From Crude Oil
• Gas - used for heating, cooking, making plastics
– small alkanes (1 to 4 carbon atoms)
– commonly known by the names methane, ethane, propane, butane
– boiling range = less than 40 degrees Celsius
– often liquified under pressure (LPG, liquified petroleum gas, C3 & C4)
– or recently liquified at low temperatures (LNG, C1’s)
• Tops and light Virgin Naphtha - to make gasoline or chemicals
– 5 to 10 carbon atom
– boiling range = 65 to 185 degrees Celsius
• (Heavy Virgin Naphtha) Gasoline - motor fuel
– liquid
– 5 to 12 carbon atoms
– boiling range 40 to 205 degrees Celsius
• Kerosene - fuel for jet engines, and heating
– Liquid
– 10 to 18 carbons
– boiling range 175 to 325 degrees Celsius
Products From Crude Oil
• Gas oil or Diesel -
– liquid
– 12 or more carbon atoms
– boiling range about 250 to 420 degrees Celsius
• Lubricating oil - used for motor oil, grease, other lubricants
– liquid
– long chain (20 to 50 carbon atoms)
– boiling range = 300 to 370 degrees Celsius
• Fuel oil - used for industrial fuel
– liquid
– long chain (20 to 70 carbon atoms)
– boiling range = 370 to 600 degrees Celsius
• Residue – used to make bitumen, waxes, coke
– Solid at room temperature
– multiple-ringed compounds with 70 or more carbon atoms
– boiling range to greater than 600 degrees Celsius
BOILING
POINT Products From Crude Oil
-150 METHANE C1

-100 ETHANE C2 GAS

-50
PROPANE C3
L.P.G.
0 BUTANE C4
100
OCTANE C8 PETROL

200
DECANE C10 JET
DIESEL
C15
300
C20
FUEL OIL
400 C24
L
U
500 C36 B
E
O BITUMEN
I
600 L

0 2 4 6 8 10 12 14 16 18 20 24 28 32 36 40 44 48 52 56 CARBON NO.
Fractions of Crude Oil & Their Properties
Number of Boiling Point
Name Uses
Carbon Atoms (°C)
Bottled Gas
Refinery Gas 3 or 4 below 30
(propane or butane).
Fuel for car
Gasoline 7 to 9 100 to 150
engines.
Solvents
Naphtha 6 to 11 70 to 200
and used in gasoline.
Fuel for aircraft
Kerosene (paraffin) 11 to 18 200 to 300
and stoves.
Fuel for road vehicles
Diesel Oil 11 to 18 200 to 300
and trains.
Lubricant for engines
Lubricating Oil 18 to 25 300 to 400
and machines.
Fuel for ships
Fuel Oil 20 to 27 350 to 450
and heating.
Lubricants
Greases and Wax 25 to 30 400 to 500
and candles.
Road surface
Bitumen above 35 above 500
and roofing.
Yields from Crude Oil
100%
80%
60%

40%
20%

0%

V
XL

H
L

RI
Y
AN
AB

AN
AB

NN
AB

S
CA
IR
AR

IR
AR

AS
BO
AR

BR
FO

S RES W DIST GAS OIL KERO L NAP TOPS GAS

Crude Oil Yield vs Product Demands
100
90
80
GAS
70 SOLVENTS
60 MOGAS
KERO
50
AGO
40 FUEL OIL
30 LUBES
20 BITUMEN

10
0
TYPICAL CRUDE TYPICAL MARKET
COMPOSITION DEMAND
How do we do it?
INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY

The process of oil refining involves five major processes which are briefly described:

SEPARATION CONVERSION TREATING BLENDING AUXILIARY

SEPARATION PROCESSES ASSOCIATED OPERATIONS

These processes involve

separating the different fractions of
hydrocarbon compounds that make • Atmospheric distillation
up crude oil base on their boiling • Vacuum distillation
point differences. Additional • Light ends recovery (gas processing)
processing of these fractions is
usually needed to produce final
products to be sold within the
market.
Atmospheric Crude Distillation Unit
Fractional Distillation Column
Vacuum Distillation Unit
INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY

SEPARATION CONVERSION TREATING BLENDING AUXILIARY

ASSOCIATED OPERATIONS

CONVERSION PROCESSES
• Cracking (thermal and catalytic)
• Reforming
Include processes used to bread
• Alkylation
down large longer chain molecules
• Polymerization
into smaller ones by heating using
• Isomerization
catalysts.
• Coking
• Visbreaking
Refinery Processes
• Fractionation / Distillation
• Conversion Processes:-
– Changing hydrocarbon structures
– Treating – removing sulphur from products
– Treating – removing sulphur from emissions
Conversion Processes
To improve gasoline octane:-
• Catalytic Reforming
• Isomerisation
To convert LPG fraction to gasoline fraction:-
• Alkyation and polymerisation (C4’s 
gasoline)
To convert heavy molecules to smaller ones:-
• FCC and Hydrocracking
• Visbreaking
Conversion Processes
Treating – removing sulphur from products:-
• Hydrotreating
• Hydrodesulphurisation
• Caustic and Merox Treating
Treating – removing sulphur from emissions:-
• Amine Treating
• Sulphur Recovery (Claus and Incineration)
• Off gas treating (SCOT)
INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY

SEPARATION CONVERSION TREATING BLENDING AUXILIARY

ASSOCIATED OPERATIONS

TREATING PROCESSES

Petroleum-treating processes are • Hydrodesulfurization

used to separate the undesirable • Hydrotreating
components and impurities such as • Chemical sweetening
sulfur, nitrogen and heavy metals • Acid gas removal
from the products.
• Deasphalting
INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY

SEPARATION CONVERSION TREATING BLENDING AUXILIARY

ASSOCIATED OPERATIONS

BLENDING/COMBINATION
PROCESSES

• Storage
These are used to create mixtures with • Blending
the various problem fractions to produce a • Loading
desired final product, some examples of • Unloading
this are lubricating oils, asphalt, or
gasoline with different octane ratings.
2.2.3 INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY

SEPARATION CONVERSION TREATING BLENDING AUXILIARY

AUXILIARY PROCESSES
ASSOCIATED OPERATIONS
Processes that are vital to operations
by providing power, waste treatment • Boilers
and other utility services. Products • Waste water treatment
from these facilities are usually • Hydrogen production
recycled and used in other processes • Sulfur recovery plant
within the refinery and are also
important in regards to minimizing
water and air pollution.
Processing units used in refineries
• Crude Oil Distillation unit:
Distills the incoming crude oil into various fractions for further
processing in other units.
• Vacuum distillation unit:
Further distills the residue oil from the bottom of the crude oil
distillation unit. The vacuum distillation is performed at a pressure
well below atmospheric pressure.
• Naphtha hydrotreater unit:
Uses hydrogen to desulfurize the naphtha fraction from the crude oil
distillation or other units within the refinery.
• Catalytic reforming unit:
Converts the desulfurized naphtha molecules into higher-octane
molecules to produce reformate, which is a component of the end-
product gasoline or petrol.
• Alkylation unit:
Converts isobutane and butylenes into alkylate, which is a very high-
octane component of the end-product gasoline or petrol.
• Isomerization unit:
Converts linear molecules such as normal pentane into higher-
octane branched molecules for blending into the end-product
gasoline. Also used to convert linear normal butane into isobutane
for use in the alkylation unit.
• Distillate hydrotreater unit:
Uses hydrogen to desulfurize some of the other distilled fractions
from the crude oil distillation unit (such as diesel oil).
• Desulphurization unit:
Desulfurize LPG, kerosene or jet fuel by oxidizing
undesired mercaptans to organic disulfides.
• Amine gas treater, Claus unit, and tail gas treatment
For converting hydrogen sulfide gas from the hydrotreaters into end-
product elemental sulfur.
• Fluid catalytic cracking (FCC) unit:
Upgrades the heavier, higher-boiling fractions from the crude oil
distillation by converting them into lighter and lower boiling, more
valuable products.
• Hydrocracker unit:
Uses hydrogen to upgrade heavier fractions from the crude oil
distillation and the vacuum distillation units into lighter, more
valuable products.
• Visbreaker unit:
Upgrades heavy residual oils from the vacuum distillation unit by
thermally cracking them into lighter, more valuable reduced viscosity
products.
• Delayed coking and fluid coker units:
Convert very heavy residual oils into end-product petroleum coke
as well as naphtha and diesel oil by-products.
• Steam reforming unit:
Converts natural gas into hydrogen for the hydrotreaters and/or the
hydrocracker.
• Sour water stripper unit:
Uses steam to remove hydrogen sulfide gas from various wastewater
streams for subsequent conversion into end-product sulfur in the
Claus unit.
• Utility units such as cooling towers for furnishing circulating cooling
water, steam generators, compressors and an electrical substation.
• Wastewater collection and treating systems consisting of API
separators, dissolved air flotation (DAF) units and some type of further
treatment (such as an activated sludge biotreater) to make the
wastewaters suitable for reuse or for disposal.
• Liquified gas (LPG) storage vessels for propane and similar gaseous fuels at
a pressure sufficient to maintain them in liquid form.
• Storage tanks for crude oil and finished products, usually vertical,
cylindrical vessels with some sort of vapour emission control and
surrounded by an earthen berm to contain liquid spills.
HURDLES

Volatile crude prices

Crude quality variability

The petroleum industry has been dramatically

impacted over the last three decades by
geopolitical disruptions and volatile world oil
prices. Today refiners must deal with:

Low marketing and

transport profit margins

Increasing capital and operating costs

of environmental compliance.
ENVIRONMENTAL DISCHARGES

Now, that we have seen an overview of the Refinery Process,

we can make some questions:

What is this industry discharging?

How is it discharged?
Where does it come from?

In order to answer these questions, this section will show:

Air emission sources

Wastewater sources
Residuals
Environmental discharges by process
98
REFINERY AIR EMISSIONS SOURCES

COMBUSTION EMISSIONS: associated with the burning of

fuels in the refinery, including fuels used in the generation of
electricity.

EQUIPMENT LEAK EMISSIONS (fugitive emissions): released

through leaking valves, pumps, or other process devices. They
are primarily composed of volatile compounds such as ammonia,
benzene, toluene, propylene, xylene, and others.

WASTEWATER SYSTEM EMISSIONS from tanks, ponds and

sewer system drains.

PROCESS VENT EMISSIONS: typically include emissions

generated during the refining process itself. Gas streams from all
refinery processes contain varying amounts of refinery fuel gas ,
hydrogen sulfide and ammonia.

STORAGE TAND EMISSIONS released when product is

transferred to and from storage tanks.
TYPES OF WASTEWATER PRODUCED IN REFINERIES

COOLING WATER which normally does not come into contact with oil
streams and contains less contaminants than process wastewater. It may
contain chemical additives used to prevent scaling and biological growth in
heat exchanger pipes.

SURFACE WATER RUNOFF is generated intermittently and

may contain constituents from spills to the surface, leaks in
equipment and materials in drains.

PROCESS WASTEWATER that has been contaminated by

direct contact with oil accounts for a significant portion of total
refinery wastewater. Many of these are sour water streams and
are also subjected to treatment to remove hydrogen sulfide and
ammonia.
REFINERY RESIDUALS
Most refinery residuals are in the form of sludge, spend caustics, spend process catalysts,
filter clay, and incinerator ash.

These residuals could be classified as follows:

NON-HAZARDOUS RESIDUALS are incinerated, landfilled or regenerated to provide

products that can be sold off-site or returned for re-use at a refinery.

HAZARDOUS WASTES are regulated under the NEMA Act. Listed hazardous wastes
include oily sludge, slop oil emulsion solids, dissolved air flotation floats, leads tank bottom
corrosion solids and waster from the cleaning of heat exchanger bundles.

TOXIC CHEMICALS are also use in large quantities by refineries. These are monitored
through the Toxic Release Inventory (TRI).
DISCHARGES

AIR EMISSIONS LIQUID EFFLUENTS

Approximately 3.5-5 cubic meters of

Average rate wastewater per ton of crude are
Po llutant
k g/t o f c rude generated when cooling water is recycled.
Particulate matter 0.8
Sulfur oxides 1.3 Average rate
Nitrogen oxides 0.3 Po llutant m g/l of
Benzene, toluene was tewater
and xylene (BTX) 0.0025 BOD 150-250
VOC 1 COD 300-600
Phenols 20-200
Oil 100-300
300 kg CO2 /ton crude Benzene 1-100
Benzopyrene 1-100
SOLID WASTES Heavy metals 0.1-100
Chrome 0.2-10
Refineries generate solid wastes and sludges
ranging from 3 to 5 kg per ton of crude
processed, 80% of this sludges may be
considered hazardous because or the
presence of toxic organics and heavy metals.