Petroleum Refinery and

Petrochemical Engineering
CH-416

Prof.Dr. SAUD HASHMI

Chairperson

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Recommended Books
Books:
1. Petroleum Refinery Engineering by W.L. Nelson.

2. Fundamentals of Petroleum Refining by Mohamed A. Fahim & Amal Elkilani.

3. Handbook of Petroleum Processing by DAVID S. J. “STAN” JONES and

PETER R. PUJAD´O

4. Petroleum Refinery Distillation by R.N Watkins, 2nd Edition.

5. Any other source that will be found helpful in this course we can use it.

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History of Petroleum Refining
 Petroleum and its derivatives such as asphalt have been known and used for
almost 6000 years and there is evidence of asphalt in building more than 600
years ago.

 Modern petroleum refining began in 1859 with discovery of petroleum in

pennsylvania (USA) and subsequent commercialization.

 The exploration of petroleum originated in the latter part of the nineteenth

century (speight,1999) .

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Course Objective
 Petroleum industries are the most prolific and dynamic industries all over the
world.

 The main objective of this course is to provide a thorough understanding in the

area of crude oil refining, hydrocarbon processing and trends in refinery
operations which is the current need of the country.

 The physical and chemical properties of petroleum and petroleum products will
be described, along with major refining processes.

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Talk outline

Part 2: Composition of Crude oil?

Part 3: Refining Processes

Physical & Chemical Processes

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Origin (1): Chemistry
en.wikipedia.org/wiki/Image:Petroleum.JPG en.wikipedia.org/wiki/Image:Octane_molecule_3D_model.png

Hydrocarbon

• Oil and gas are made of a mixture of

different hydrocarbons.

• As the name suggests these are large

molecules made up of hydrogen atoms
attached to a backbone of carbon.
Crude Oil
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Origin (2): Plankton
cache.eb.com/eb/image?id=93510

Plant plankton Animal plankton

would fit on a pinhead!
10,000 of these bugs

en.wikipedia.org/wiki/Image:Ceratium_hirundinella.jpg en.wikipedia.org/wiki/Image:Copepod.

• Most oil and gas starts life as microscopic plants and animals
that live in the ocean.

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Origin (4): On the sea bed
upload.wikimedia.org/wikipedia/en/0/04/Plankton.jpg When the plankton dies it rains
down on sea bed to form an
organic mush
If there are any animals on the
sea bed these will feed on the
organic particles
• However, if there is little or no
oxygen in the water then animals
can’t survive and the organic mush
accumulates
Where sediment contains
more than 5% organic matter,
it eventually forms a rock
known as a Black Shale

Sea bed

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Origin (6): Cooking

As Black Shale is buried, it is heated.

Organic matter is first changed by the

increase in temperature into kerogen,
Kerogen which is a solid form of hydrocarbon

Around 90°C, it is changed into a liquid

state, which we call oil
Oil

Around 150°C, it is changed into a gas

Gas

A rock that has produced oil and gas in

www.oilandgasgeology.com/oil_gas_window.jpg
this way is known as a Source Rock
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Origin (7): Migration
Oil on the move
 Hot oil and gas is less dense than the source
www.diveco.co.nz/img/gallery/2006/diver_bubbles.jpg
rock in which it occurs

 Oil and gas migrate upwards up through the

rock in much the same way that the air
bubbles of an underwater diver rise to the
surface.

 The rising oil and gas eventually gets trapped

in pockets in the rock called “Reservoirs”

Rising oil Department of chemical Engineering 10

Source Rocks
Organic Matter

• Sedimentary rocks rich in

organic matter
– 0.5 - 2% by weight
• Most commonly
microscopic marine
material, but it can be land
based material
• Organic material cannot
decay too much
– It has to keep its carbon

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5. Reservoir rocks
The oil needs to be trapped in a good place

• A good reservoir
rock is:
– Porous: holes
– Permeable: holes are
connected
– so that its fluids can
be produced
(removed from
them)
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Reading Assignment

Exploration and
Production –
How do we find oil and
gas and how is it
produced?

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Department of chemical Engineering
Composition of Crude Oils
 Crude oil is a complex liquid mixture made up of a vast number of hydrocarbon
compounds that consist mainly of carbon and hydrogen in differing proportions.

 In addition, small amounts of organic compounds containing sulfur, oxygen,

nitrogen and metals such as vanadium, nickel, iron and copper are also present
(See Table below).

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Composition of Crude Oils
 There are three main classes of hydrocarbons. These are based on the type of
carbon–carbon bonds present. These classes are:

 Saturated hydrocarbons :contain only carbon–carbon single bonds. They are

known as paraffins (or alkanes) if they are acyclic, or naphthenes (or
cycloalkanes) if they are cyclic.

 Unsaturated hydrocarbons : contain carbon–carbon multiple bonds (double,

triple or both). These are unsaturated because they contain fewer hydrogens
per carbon than paraffins. Unsaturated hydrocarbons are known as olefins.
Those that contain a carbon–carbon double bond are called alkenes, while
those with carbon–carbon triple bond are alkyenes.

 Aromatic hydrocarbons : are special class of cyclic compounds related in

structure to benzene.

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Composition of Crude Oils
1- Paraffins:

 General formula: CnH2n+2 (n is a whole number, usually from 1 to 20), straight

or branched chain molecules, can be gasses or liquids at room temperature
depending upon the molecule. For example, methane, ethane, propane,
butane, isobutane, pentane, hexane

 They have similar chemical and physical properties, which change

gradually as carbon atoms are added to the chain.
 Isoparaffins (or isoalkanes) are branched-type hydrocarbons that exhibit
structural isomerization.
 The presence of isoparaffins in gasoline is essential for increasing the
octane number of gasoline fuels

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Composition of Crude Oils
2- Olefins (also known as alkenes)

 General formula: CnH2n (n is a whole number, usually from 1 to 20), linear or

branched chain molecules containing one carbon-carbon double-bond, can
be liquid or gas. For example: ethylene, butene, isobutene
 Olefins are not naturally present in crude oils but they are formed during
the conversion processes. They are more reactive than paraffins.

 The lightest alkenes are ethylene(C2H4) and propylene (C3H6), which

are important feed stocks for the petrochemical industry. The lightest
alkyne is acetylene

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Composition of Crude Oils
3- Naphthenes (cycloalkanes)

 General formula: CnH2n (n is a whole number usually from 1to 20), ringed
structures with one or more rings, rings contain only single bonds between the
carbon atoms, typically liquids at room temperature. For example:
cyclohexane, methyl cyclo pentane.
 The boiling point and densities of naphthenes are higher than those of
alkanes having the same number of carbon atoms. Naphthenes commonly
present in crude oil are rings with five or six carbon atoms. These rings
usually have alkyl substituents attached to them. Mutli-ring naphthenes are
present in the heavier parts of the crude oil.

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Composition of Crude Oils
4- Aromatics
 General formula: C6H5 - Y (Y is a longer, straight molecule 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. For examples benzene, naphthalene

 Crude oils from various origins contain different types of aromatic compounds in
different concentrations. Light petroleum fractions contain mono-aromatics, which
have one benzene ring with one or more of the hydrogen atoms substituted by
another atom or alkyl groups. Examples of these compounds are toluene and
xylene. Together with benzene, such compounds are important petrochemical
feedstocks, and their presence in gasoline increases the octane number.

Department of Polymer & Petrochemical

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Engineeirng
Composition of Crude Oils
poly nuclear aromatic compounds

 More complex aromatic compounds consist of a number of ‘‘fused’’ benzene

rings. They are found in the heavy petroleum cuts, and their presence is
undesirable because they cause catalyst deactivation and coke deposition
during processing,
 Causing environmental problems when they are present in diesel and fuel oils.
 The heaviest portion of the crude oil contains asphaltenes, which are
condensed polynuclear aromatic compounds of complex structure.
 Examples of polynuclear aromatic compounds are shown below

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Composition of Crude Oils
5- Sulfur Compounds
 The Sulfur content of crude oils varies from less than 0.05 to more than 10 wt%
but generally falls in the range 1–4 wt%.

 Crude oil with less than 1 wt % sulfur is referred to as low sulfur or sweet, and
that with more than 1 wt% sulfur is referred to as high sulfur or sour.

 Crude oils contain sulfur heteroatoms in the form of elemental sulfur S, dissolved
hydrogen sulphide H2S, carbonyl sulphide COS, inorganic forms and most
importantly organic forms, in which sulfur atoms are positioned within the organic
hydrocarbon molecules.

 Sulfur compounds lead to environmental pollution, decreases the life of

machinery, corrodes of pipes, machines and equipment, affecting the additives
used for the purpose of increasing the octane number, reduce the activity of Tetra
Ethyl Lead (TEL) added to gasoline. As a result, the engine metal will erode and
leads to destruct the metallic parts.

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Composition of Crude Oils
5- Sulfur Compounds

 Their emissions are very dangerous to human safety and environment.


 In addition, these impurities cause catalyst poisoning and reduce the catalyst
activity.

 Sulfur containing constituents of crude oils vary from simple mercaptans, also
known as thiols, to sulphides and polycyclic sulphides (Mercaptans (R–SH),
sulphides (R–S–R'), disulphides (R–S–S–R'), Thiophenes)

Department of Polymer & Petrochemical

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Engineeirng
Composition of Crude Oils
6-Nitrogen Compounds

 Crude oils contain very low amounts of nitrogen compounds, less than 1%.
 Basic nitrogen compounds consist of pyridines.

 The decomposition of nitrogen compounds in catalytic cracking and hydrocracking

processes forms ammonia and cyanides that can cause corrosion.

 Nitrogen compounds are more stable than sulphur compounds and therefore are
harder to remove.

 Even though they are present at very low concentrations, nitrogen compounds
have great significance in refinery operations. They can be responsible for the
poisoning of a cracking catalyst , and they also contribute to gum formation in
finished products.

Department of Polymer & Petrochemical

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Engineeirng
Composition of Crude Oils
7-Oxygen Compounds

 The oxygen content of crude oil is usually less than 2 wt%.

 Phenomenally high oxygen content indicates that the oil has suffered
prolonged exposure to the atmosphere.

 Oxygen in crude oil can occur in a variety of forms. These include alcohols,
ethers, carboxylic acids, phenolic compounds, ketones, esters and
anhydrides.

 The presence of such compounds causes the crude to be acidic with

consequent processing problems such as corrosion.

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Engineeirng
Composition of Crude Oils
Total acid number (TAN)

 It is a measurement of acidity that is determined by the amount of potassium

hydroxide in milligrams that is needed to neutralize the acids in one gram of
oil.
 It is an important quality measurement of crude oil.

 The TAN value indicates to the crude oil refinery the potential
of corrosion problems. It is usually the naphthenic acids in the crude oil that
cause corrosion problems.

 This type of corrosion is referred to as naphthenic acid corrosion (NAC).

 TAN values may also be useful in other industries where oils are used as
lubricants to determine oxidation and the subsequent corrosion risk to
machinery.

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Composition of Crude Oils
7-Oxygen Compounds

 Alcohols have the general formula R–OH and are structurally similar to water
but with one of the hydrogen atoms replaced by an alkyl group.

 Alcohols such as methyl alcohols generally do not have any effect on refining
operations, but they are effect the waste water treatment plant.

 They effect the BOD and COD requirements at effluent treatment plant.

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Composition of Crude Oils
7-Oxygen Compounds

 Ketones are compounds responsible for color formation.

 They give rise color to kerosene.

 They are responsible in reducing the market value of the kerosene, as it do

not effect any other property of kerosene.

 Kerosene serve as a raw materials for many products such as medicines,

solvents for paints and varnishes, insecticides etc.

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Composition of Crude Oils
8- Metals Compounds

 Metallic compounds exist in all crude oil types in very small amounts.

 Their concentration must be reduced to avoid operational problems and to

prevent them from contaminating the products.

 Metals affect many upgrading processes. They cause poisoning to the

catalysts used for hydroprocessing and cracking.

 Even minute amounts of metals (iron, nickel and vanadium) in the

feedstock to the catalytic cracker affect the activity of the catalyst and
result in increased gas and coke formation and reduced gasoline yields.

 Burning heavy fuel oils in refinery furnaces and boilers can leave deposits
of vanadium oxide and nickel oxide in furnace boxes, ducts, and tubes.

 It is also desirable to remove trace amounts of arsenic, vanadium, and

nickel prior to processing as they can poison certain catalysts.
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Composition of Crude Oils
9- Asphaltenes and Resins Compounds

 Asphaltenes are dark brown friable solids that have no definite melting point
and usually leave carbonaceous residue on heating.

 They are made up of condensed polynuclear aromatic layers linked by

saturated links.

 The presence of high amounts of asphaltenes in crude oil can create

tremendous problems in production because they tend to precipitate inside the
pores of rock formations, well heads and surface processing equipments.

 They may also lead to transportation problems because they contribute to

gravity and viscosity increases of crude oils.

 Resins are polar molecules have high molecular weight, which are insoluble in
liquid propane but soluble in n-heptane.

 It is believed that the resins are responsible for dissolving and stabilizing the
solid asphaltene molecules in petroleum.
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Composition of Crude Oils
9- Salt Content

 Salt is another type of impurity that might present in the crude oil.

 Salt usually present in a dissolve state.

 Salt such as chlorates and sulfates are present in the crude oil.

 These salts are potential candidates for the causing corrosion in the distillation
column.

 Desalting methods has been employed to remove these dissolve salt contents.

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Some crude oils of Pakistan

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Engineeirng
Department of Polymer & Petrochemical
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Engineeirng
WHAT DOES A REFINERY DO?

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Engineeirng
Refining facility in Pakistan
Byco Refinery 35,000 bbl/day
ARL Refinery 40,000 bbl/day
PRL Refinery 50,000 bbl/day
NRL Refinery 65,000 bbl/day
PARCO Refinery 100,000 bbl/day

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Physical Separation Processes
Refining Processes
Crude Distillation
Crude oils are first desalted and then introduced with steam to an atmospheric
distillation column. The atmospheric residue is then introduced to a vacuum
distillation tower

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Physical Separation Processes
Solvent Deasphalting
 This is the only physical process where carbon is rejected from heavy petroleum
fraction such as vacuum residue. Propane in liquid form (at moderate pressure) is
usually used to dissolve the whole oil, leaving asphaltene to precipitate. The
deasphalted oil (DAO) has low sulphur and metal contents since these are removed
with asphaltene.

Solvent Extraction
 In this process, lube oil stock is treated by a solvent, such as N-methyl pyrrolidone
(NMP), which can dissolve the aromatic components in one phase (extract) and the
rest of the oil in another phase (raffinate). The solvent is removed from both phases
and the raffinate is dewaxed.
Solvent Dewaxing
 The raffinate is dissolved in a solvent (methyl ethyl ketone, MEK) and the solution is
gradually chilled, during which high molecular weight paraffin (wax) is crystallized, and
the remaining solution is filtered. The extracted and dewaxed resulting oil is called
‘‘lube oil’’. In some modern refineries removal of aromatics and waxes is carried out by
catalytic processes in ‘‘all hydrogenation process’’.

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Chemical Catalytic Conversion Processes
Catalytic Reforming
 In this process a special catalyst (platinum metal supported on silica or silica base
alumina) is used to restructure naphtha fraction (C6–C10) into aromatics and
isoparaffins.

Hydrotreating
 This is one of the major processes for the cleaning of petroleum fractions from
impurities such as sulphur, nitrogen, oxy-compounds, chlorocompounds, aromatics,
waxes and metals using hydrogen. Catalysts , such as cobalt and molybdenum oxides
on alumina matrix, are commonly used.

Catalytic Hydrocracking
 For higher molecular weight fractions such as atmospheric residues (AR) and
vacuum gas oils (VGOs), cracking in the presence of hydrogen is required to get light
products. In this case a dual function catalyst is used. It is composed of a zeolite catalyst for
the cracking function and rare earth metals supported on alumina for the hydrogenation
function. The main products are kerosene, jet fuel, diesel and fuel oil.

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Chemical Catalytic Conversion Processes
Catalytic Cracking
Fluid catalytic cracking (FCC) is the main player for the production of gasoline. The
catalyst in this case is a zeolite base for the cracking function. The main feed to FCC is VGO and
the product is gasoline, but some gas oil and refinery gases are also
Produced.

Alkylation
Alkylation is the process in which isobutane reacts with olefins such as butylene (C4 ) to produce
a gasoline range alkylate. The catalyst in this case is either sulphuric acid or hydrofluoric acid.
The hydrocarbons and acid react in liquid phase. Isobutane and olefins are collected mainly from
FCC and delayed coker.

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Thermal Chemical Conversion Processes
These processes are considered as upgrading processes for vacuum residue.
Delayed Coking
 This process is based on the thermal cracking of vacuum residue by carbon rejection
forming coke and lighter products such as gases, gasoline and gas oils. Three types of
coke can be produced: sponge, shot and needle. The vacuum residue is heated in a
furnace and flashed into large drums where coke is deposited on the walls of these
drums, and the rest of the products are separated by distillation.
Flexicoking
 In this thermal process, most of the coke is gasified into fuel gas using steam and air.
The burning of coke by air will provide the heat required for thermal cracking. The
products are gases, gasoline and gas oils with very little coke.
Visbreaking
 This is a mild thermal cracking process used to break the high viscosity and pour
points of vacuum residue to the level which can be used in further downstream
processes. In this case, the residue is either broken in the furnace coil (coil
visbreaking) or soaked in a reactor for a few minutes (soaker visbreaker). The
products are gases, gasoline, gas oil and the unconverted residue.

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Reading Assignment
 Go through these topics from the books for getting better understanding.

 Read details of the topics as I have mentioned in the slides above or those
topics which I left purposely.

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