Refinery Processes

PEOP1012 – INDUSTRIAL PROCESSES II

CERTIFICATE IN PROCESS OPERATIONS
Objectives
2
• Identify the different types of crude oil feedstocks based on the
categories of API Gravity, sulphur content, aromatics/aliphatics
content (crude oil assays).
• List the properties of various refinery products and critical
specifications: naphtha, kerosene, gasoline, gas oil, fuel oil,
lubricating oil, bitumen, LPG.
• Describe the purpose and operation of the Atmospheric
Distillation, Vacuum Distillation and Visbreaker units.
• Describe the purpose and operation of the Hydrogen Production,
Hydro-treating, Hydro-cracking and Caustic Treating units.
• Describe the purpose and operation of the Fluid Catalytic Cracking
and Alkylation unit.
• Describe the purpose and operation of the Catalytic Reforming
and Isomerization units.
• Describe the purpose and operation of the Sulphur Recovery unit.
Flow Diagram 3
4
 Introduction 5
1. Refining of crude oil to yield usable products is mainly
accomplished by fractional distillation, cracking, reforming and
other conversion processes.
2. Distillation of the crude oil is necessary to separate it into its
several different fractions (compounds). This is because the crude
oil comprises different compounds which all have different
boiling temperature ranges.
3. The fractions obtained from distillation are then subjected to
cracking processes whereby the long chain hydrocarbons are
converted to lighter compounds/products (shorter chains).
4. Reforming processes upgrade the octane ratings of the naphthas
to high octane products as reformates in gasoline.
5. Extraction, hydrotreating & sweetening processes downstream
then remove undesirable constituents and improve product
quality.
 6
Refinery Raw Materials & Products
Naphtha
 Colourless to reddish brown volatile, flammable, aromatic
compound that is insoluble in water.
 It is obtained as one of the intermediate products from the
distillation of crude oil; it is the liquid intermediate between
the light gases in the crude oil and kerosene.
 Naphtha refers to a mix of hydrocarbons (5 – 9 carbon
atoms), thus boiling points range from 30 - 200°C.
 It is used in the refineries to produce high octane gasoline; in
the petrochemical industries for producing alkenes in steam
crackers, and in chemical industries as solvents.
Kerosene
7
 Is obtained from the fractional distillation of crude oil between
150 - 275°C. It is a clear, combustible, hydrocarbon liquid
containing anywhere from 6 – 16 carbon atoms compounds.

 It is used as a home heating fuel in Japan for portable and

installed kerosene heaters. In the UK & Ireland, it is used as a
heating fuel in areas that are unconnected to a gas piping system.
In India, kerosene is used by the poor as a fuel for cooking in
kerosene stoves.
 Ultra-low sulfur kerosene is a custom-blended fuel used by the
New York City Transit to power its bus fleet.
 In jet engines today, kerosene is widely used as the fuel whereby
important properties such as freezing point and flash point must
be considered.
Gasoline
 Also known as petrol, is obtained from the distillation of8
crude oil and contains hydrocarbons between 4 – 12 carbon
atoms and has a boiling point of 100 – 400 °F.
 It has a clear or slightly yellowish colour. It is mainly used
as a fuel in internal combustion engines (motor gasoline),
enhanced with iso-octane or benzene compounds to improve
its octane rating.
 Gasohols (ethanol and gasoline blends of vehicular fuel) are
widely used presently as a more environmentally friendly
fuel.
Gas oil

 Also known as diesel distillate is an oily liquid 9

containing alkanes of 12 or more carbon atoms and is
obtained as the fraction of boiling point 250 – 350°C. It
is the lighter of the fuel oils produced. It is also used as
diesel fuel for good starting and combustion in engines.

Fuel Oil
 An oily liquid obtained in the fractional distillation of crude
oil, as distillate or residue at 370 - 600°C.
 Also called heavy gas oil or residual fuel, are long chain
hydrocarbons – 20-70 carbon atoms (alkanes, cycloalkanes,
aromatics). It is used as a heating oil in boilers and furnaces
& cotton or wool-wick burners; there must be a low sulphur
content for environmental control.
Lubricating oil
10
 Is the thick liquid obtained as the fraction between 300 -
370°C. It consists of long chain hydrocarbons (20 – 50
carbon atoms). Additives such as demulsifiers, antioxidants,
viscosity improvers are blended to give the characteristics
required for use as motor oil, greases, lubricants & cutting
oils.

Bitumen
 Is obtained as the residue or bottom fraction from the
distillation of crude oil (>600°C). Contains multiple-ringed
compounds greater than 70 carbon atoms. It is a semi-solid,
sticky, tar substance used for road surfacing and
waterproofing works.
LPG
 Liquefied Petroleum Gas is obtained from the pressurizing 11
of the light propane & butane gases obtained from the top
fraction (lightest fraction) at a boiling point of less than
40°C. It is used as a motor fuel and cooking gas & as an
intermediate in the manufacture of chemicals.
Electrostatic Desalting 12
 Is a pre-treatment process intended to remove
water, inorganic salts such as sodium, magnesium &
calcium chloride, suspended solids & water-soluble
trace metals from the crude oil.
 If not removed, problems arise during refining such
as formation of hydrochloric acid at downstream
high temperatures & thus corrosion of equipment,
impaired heat transfer and fluid flow in pipelines &
equipment due to fouling & deposition, and
catalyst de-activation and sintering due to the
metals such as sodium & arsenic.
Atmospheric Distillation 13
 Distillation is the separation of a mixture into its
many components based on the differences in their
respective boiling points.
 In the column/tower, the lighter (more volatile)
components are recovered at the top of the column
in gaseous form while the heavier (less volatile)
compounds are obtained at the bottom (residue) in
liquid form.
 The crude oil is distilled to yield fractions of
bitumen, fuel oil, lubricating oil, diesel oil,
kerosene, gasoline, naphtha and LPG.
14
Vacuum Distillation 15

 Vacuum distillation takes place at pressures lower

than atmospheric. It is an energy saving operation
because at reduced pressures, the boiling points of
heavy hydrocarbons and compounds are reduced
considerably, thus less energy is required for
boiling/separation.
 Heavy fractions from the previous column are sent
to this VD column to yield vacuum gas oil &
lubricating oils.
 Vacuum is obtained by the use of ejectors and
vacuum pumps.
Vis-breaking 16
 This is a mild form of thermal cracking as it lowers
the viscosity of heavy crude oil residue from the
vacuum tower which is to be used for blending with
lighter fuel oils.

 Products of vis-breaking include gasoline which are

sent for further treatment in Hydro-treating units,
and gases which proceed to the Gas plant.
Hydro-treating (Desulphurization) 17
 Removes 90% of contaminants such as nitrogen,
sulphur (hydrogen sulphide), oxygen and metals for
liquid petroleum fractions (petrol, jet fuel, kerosene,
diesel fuel) because if these are not removed, they can
have detrimental effects on downstream equipment,
catalysts and product quality.
 Also referred to as desulphurization since sulphur is
removed by a hydrogenation process.
 Hydro-treating also converts alkenes and aromatics to
saturated compounds.
 Hydro-treating upgrades middle-distillate crude oil
fractions such as kerosene, diesel fuel & heating fuel
oils.
 Hydrocarbon feed
18
Molybdenum based
H2 (g) catalyst
H2 (g)

260 - 370°C, >400psig

Hydrogen-rich gas H2S(g)
Amine
Contactor

Gas Separator
35°C, 3-5 atm sour gas sour gas Gas
Plant

Stripper
Liquid

desulfurized liquid product

Hydrogen Plant
19
 High purity hydrogen gas is required for
desulphurization, hydro-cracking & other
hydrogenation processes.
Step 1: Desulphurization of natural gas
 Sulphur must be removed as it is a poison to catalysts
in the reformer.
 Hydrogenation of sulphur compounds to H2S over a
cobalt molybdenum catalyst occurs first.
C2H4 S + 2H2 C2H6 + H2S
 The H2S is then absorbed by a bed of zinc oxide
catalyst while the purified natural gas proceeds to the
reformer.
ZnO + H2S ZnS + H2O
Step 2: Steam reforming of natural gas involves the
mixing of natural gas with superheated steam (700- 20
1000°C) with a nickel oxide catalyst. Main reaction is:
CH4 + H2O CO + 3H2

 The reformed gas, which consists of steam, hydrogen,

carbon monoxide, and carbon dioxide, is cooled and
passed through an extra reformer reactor stage
containing a copper based catalyst where the carbon
monoxide reacts with steam to form the less toxic
carbon dioxide, and more hydrogen. This is known as
the water gas shift reaction:
CO + H2O CO2 + H2

Step 3: The hydrogen gas is then purified by a pressure

swing adsorption process.
Alkylation 21
 The reaction of low molecular weight alkenes with
isoparaffins to form a high molecular weight
isoparaffin, termed an alkylate.
 Alkylates are premium grade blending ingredients
because of anti-knock properties, and they burn
clean.
 The typical alkylation reaction is the combination
of isobutane with n-butene in the presence of
sulphuric acid as catalyst.
C4H10 + C4H8 C8H18
 Characteristics of Alkylates: 22
 High octane number
 Low Reid Vapor Pressure
 No olefins
 No aromatics
 100% Paraffinic
Catalytic Reforming
23
 Aims at upgrading low octane naphthas (low-octane
gasoline) to produce high octane components
(reformates) for motor gasoline use (high octane
gasoline).
 The naphtha molecules are re-arranged or re-
structured, and some molecules are broken down to
smaller molecules.
 The product reformate contains hydrocarbons with
more complex molecular shapes having higher octane
values.
 Most common forms of the reforming process used
are:-
 Platforming
 Rheniforming
 Powerforming
 The reactions take place with a catalyst and hydrogen.
24
 Temperatures range from 495 - 525 °C and pressures of 5 -
45 atm.
 A series of reactions take place:
1. De-hydrogenation of naphthenes to produce aromatics
methylcyclohexane toluene + H2(g)
2. Isomerization of naphthenes /paraffins to yield isoparaffins
methylcyclopentane cyclohexane
3. De-hydrocyclization of paraffins to aromatics.
n-heptane toluene + H2(g)
4. Hydro-cracking of paraffins into smaller molecules.
Decane + H2(g) iso-hexane + n-butane
Reforming Unit 25
Fluid Catalytic Cracking 26
 Complex hydrocarbons are broken down to simpler
molecules in order to increase the quality and quantity
of lighter, more desirable products such as kerosene,
gasoline, LPG, heating oil & petrochemical feedstock.

 The unit consists of 3 sections:-

1. Reaction – feedstock reacts with catalyst and
cracks into different hydrocarbons.
2. Regeneration – catalyst is reactivated by burning
off coke (a carbon based material)
3. Fractionation – cracked hydrocarbon stream is
separated into various products.
• Typical temperatures are from 850 - 950°F at
pressures of 10-20 psi. Catalysts used are 27
aluminium-based solid materials such as zeolite,
aluminium hydrosilicate, bauxite, in the form of
powders, beads, pellets.

• The fluid cracker unit consists of a catalyst section

which consists of the reactor and regenerator, and
the fractionation section.

• The catalyst is maintained in a fluidized state by oil

vapours, air and steam.
• The spent catalyst is regenerated by getting rid
28
of coke that collects during the process. The
coke is burnt off by preheated air.

• It is important that regenerator temperatures

(by proper air flow control) are carefully
controlled to prevent catalyst deactivation by
overheating and to ensure the desired coke burn
off.
29
 The primary reactions that occur:- 30
1. Paraffin paraffin + olefin
2. Alkyl naphthene naphthene + olefin
3. Alkyl aromatic aromatic + olefin

 The secondary reactions involve isomerization of

olefins, followed by saturation and aromatization.
Catalytic Hydro-cracking
31
 Is used for its advantages of giving a greater yield
of gasoline and improved gasoline quality (octane),
as well as high yields of jet fuel and diesel.
Feed Products
Kerosene Naphtha
Straight-run diesel Naphtha, jet fuel
Atmospheric gas oil Naphtha, jet fuel, diesel
Vacuum gas oil Naphtha, jet fuel, diesel, lube oil

 There are two main chemical reactions occurring in

the hydrocracker: catalytic cracking of heavy
hydrocarbons into lighter unsaturated
hydrocarbons and the saturation of these newly
formed hydrocarbons with hydrogen.
• The feed to the hydrocracker comes from 32
the atmospheric and vacuum distillation
unit, and the FCC unit.
Isomerization 33
 Aims at converting n-pentane, n-butane, n-hexane
into their respective isoparaffins of higher octane
number.
 Isobutane isomerized from n-butane provides
feedstock for the alkylation unit.
 The products of the isomerization of n-pentane and
n-hexane are used in gasoline blending.
 Isomerization is similar to catalytic reforming
because the hydrocarbon molecules are re-arranged,
but different at the same time since only
isoparaffins are produced.
 Catalysts used are chloride based.
Isomerization of n-Butane 34
 Low temperatures are associated (230-340°F).
 The butane stream is fed with hydrogen to inhibit olefin
formation.
 The feed goes to a reactor operating at 200-300 psi.
 Hydrogen is flashed off in a high-pressure separator and the
chloride (catalysts) are removed in a distillation column.
 The resultant butane mixture is sent to a fractionator (de-
isobutanizer) to separate any n-butanes from the isobutane
product.
35
Isomerization of n-pentane, n-hexane
 Dried and de-sulphurized feedstock is mixed with a small36
amount of organic chloride and recycled hydrogen and heated
to reactor temperature.
 It is then passed through the first reactor which uses a
platinum or other metal catalyst where benzene and other
alkenes are hydrogenated.
 The feed then goes to the isomerization reactor where the
paraffins are catalytically isomerized to isoparaffins.
 The reactor effluent is cooled and then separated in the
product separator into 2 streams – the liquid product
(isomerate) and a recycle hydrogen-gas stream.
 The product is washed, stripped of acid and stabilized before
going to storage.
Classification of Crude Oils
 Crude oils range in consistency from liquid to tar-like solids, 37
and
in color from clear to black.
 Composition of an average crude oil:-
• 84% carbon, 14% hydrogen, 1-3% Sulphur, less than 1% each
of nitrogen, oxygen, metals and salts

Crude oils are classified as follows:-

 Paraffinic – The alkane composition of crude oil whether
straight-chained or branched chain (saturated compounds). The
light, straight-chain molecules are found in gases and paraffin
waxes. The branched chain molecules are found in the heavier
fractions of crude oil.
 Aromatics – Are the unsaturated ring-type compounds which are
reactive. All aromatics have at least one benzene ring structure.
 Naphthenes – Are the cyclic saturated hydrocarbons with the
general formula CnH2n. They are found in all fractions of the oil,
except the lightest.
API Gravity 38

 Crude oils are also classified based on their API gravity. If

the API gravity of the crude oil is of 20 degrees or less, it is
graded as 'heavy', those with an API gravity of 40.1 degrees
or greater is known as 'light', and if the oil ranges between
20 and 40.1 degrees, it is graded as 'medium’. The higher the
API gravity, the lighter the crude oil.

 Crude oils with low carbon, high hydrogen, and high API
gravity are rich in paraffins and tend to give greater
proportions of gasoline and light petroleum products. Those
with high carbon, low hydrogen, and low API gravities are
rich in aromatics.
Sweet & Sour Crude Oil 39

 Crude oils are also deemed ‘sweet’ or ‘sour’.

‘Sour’ crude oils contain a certain quantity of
hydrogen sulphide or other reactive sulphur
compounds (>0.5%) eg. Dubai crude. Those
with lesser quantities (<0.5% sulphur) are
‘sweet’ eg. Brent crude, West Texas
Intermediate.
Sulphur Recovery Unit
40

 Major sulphur impurity obtained in hydrocarbon

gases is H2S.
 We need to ensure this gas is not let into the
atmosphere to result in pollution.
 There is need to convert this gas to a more stable,
non toxic form.
 The most stable form is elemental S.
 The Claus process utilizes this process where H2S
is converted to elemental S.
The Claus Process 41
 Gases containing hydrogen sulphide is mixed with
a stoichiometric amount of air.
 This is introduced into the top of a reactor.
 The result mixture is passed through a catalytic
converter containing bauxite or Aluminium oxide
catalyst .
 H2S is converted to S and cooled from a vapour
phase to a liquid phase.
Claus Process Reactions
42
 1/3 of the H2S reacts with oxygen to form SO2. This is the
oxidation reaction in the furnace.
2H2S + 3O2 2 SO2 + 2H2O + Heat

 A side reaction also occurring.

2H2S + O2 2S + 2H2O + Heat

 Major reaction occurring in the converter (The Claus

Reaction):
2H2S + SO2 3S + 2H2O + Heat
In this converter the reactions occur over a bauxite
(Aluminium oxide) catalyst, where the remaining 2/3 of the
H2S reacts.
43
Methods used for Tail Gas Clean
44
up
1. There are methods which extend the Claus reaction
further under more favourable conditions (Sulphreen
process).
2. Other methods convert sulphur compounds in the
tail gas to hydrogen sulphide which then react to form
elemental sulphur (SCOT process).
 Tail gas clean up has to be done to ensure the
environmental standards are met since the sulphur
Claus process is not efficient in meeting the
standards required by the environmental bodies.
Reference 45

 file:///C:/Users/keesha/Downloads/Impact%20of%
20low%20crude%20prices%20on%20refining%20Co
B.pdf
 https://www.britannica.com/technology/petroleu
m-refining/Refinery-plant-and-facilities
 https://www.youtube.com/watch?v=MdLVzXf7v5
E
 https://www.youtube.com/watch?v=GYRwWyG3
Qqw