LIQUID FUELS

Petroleum
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• Introduction
• Composition of Petroleum
• Petroleum (World Data)
• Uses of Petroleum
• Petroleum Refining
• Processing units used in refineries
• Petroleum Refining Processes
• Thermal Properties (Empirical Relations)
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Introduction
• Petroleum is a naturally occurring, yellow-to-black liquid
found in geologic formations beneath the Earth's surface

• Petroleum is formed when large quantities of dead

organisms, usually zooplankton and algae, are buried
underneath sedimentary rock and subjected to intense heat
and pressure.
– It consists of hydrocarbons of various molecular weights and
other liquid organic compounds
– The name petroleum covers both naturally occurring
unprocessed crude oils and petroleum products that are made
up of refined crude oil

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Origin
– Fossils remains settled to sea or lake bottoms, mixing
with sediments and being buried under anoxic
conditions.

– As further layers settled to the sea or lake bed, intense

heat and pressure built up in the lower regions.

Liquid &
Organic
Kerogen Gaseous
Matter
Hydrocarbons

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COMPOSITION
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• Petroleum includes all liquid, gaseous, and solid

hydrocarbons.
– Under surface pressure and temperature conditions,
lighter hydrocarbons methane, ethane, propane and
butane occur as gases
– Pentane and heavier ones are in the form of liquids
or solids
– In an underground oil reservoir the proportions of
gas, liquid, and solid depend on subsurface
conditions and on the phase diagram of the
petroleum mixture
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PETROLEUM – WORLD DATA

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Oil Reserves

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Oil Producing Countries

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Oil Consumption

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Oil Imports

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Oil Exports

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USES OF PETROLEUM

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• Fuels • Aromatic
• Lubricants petrochemicals
• Wax • Pesticides
• Tar • Fertilizers
• Asphalt • Sulfuric acid

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PETROLEUM REFINING

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• Petroleum refining refers to the process of

converting crude oil into useful products such as
liquefied petroleum gas (LPG), gasoline or petrol,
kerosene, jet fuel, diesel oil and fuel oils

• The refining process is divided into three basic

steps:
– Separation
– Conversion
– Treatment
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• Petroleum refineries are very large industrial

complexes that involve many different
processing units and auxiliary facilities such
as utility units and storage tanks.

• Each refinery has its own unique

arrangement and combination of refining
processes largely determined by the refinery
location, desired products and economic
considerations.
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Separation
• Crude oil is heated in a furnace so that hydrocarbons
can be separated via their boiling point.

• Inside large towers, heated petroleum vapors are

separated into fractions according to weight and
boiling point.

• The lightest fractions, which include gasoline, rise to

the top of the tower before they condense back to
liquids.

• The heaviest fractions will settle at the bottom

because they condense early.
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Conversion
• Conversion is the process of changing one kind
of hydrocarbon into another.
– Normally, the desired product is gasoline.

– Cracking is the process of taking heavier, less

valuable fractions of crude and converting them into
lighter products.
• Cracking uses heat and pressure to break heavier elements
into lighter ones.

– Alkylation is the opposite of cracking.

• In alkylation, small gaseous byproducts are combined to
form larger hydrocarbons.

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Treatment
• Treatment is the final process of refining, and
includes combining processed products to create
various octane levels, vapor pressure properties,
and special properties for products used in extreme
environments.

– One common example of treatment is the removal of

sulfur from diesel fuel, which is necessary for it to meet
clean air guidelines.
– Treatment is highly technical and is the most time
consuming step of refining.
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PROCESSING UNITS USED IN REFINERIES

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• 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.

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• Isomerization unit
– Converts linear molecules such as normal pentane into
higher-octane branched molecules for blending into
gasoline.
– Also used to convert linear normal butane into isobutane
for use in the alkylation unit.

• Catalytic reforming unit

– Converts the desulfurized naphtha molecules into higher-
octane molecules to produce reformate

• Alkylation unit
– Converts isobutane and butylenes into alkylate, which is a
very high-octane component of the gasoline or petrol.

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• 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.

• Distillate hydrotreater unit

– Uses hydrogen to desulfurize some of the other distilled
fractions from the crude oil distillation unit (such as diesel
oil).

• Merox (mercaptan oxidizer) or similar units

– Desulfurize LPG, kerosene or jet fuel by oxidizing
undesired mercaptans to organic disulfides.

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• 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
– It 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.

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THERMAL PROPERTIES – E
MPIRICAL RELATIONS
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Heat of Combustion
• At a constant volume:

𝑄𝑣 = 12400 − 2100𝑑 2

Where:
𝑄𝑣 is measured in cal/gram
𝑑 is the specific gravity at 60 °F (16 °C)

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Thermal Conductivity

0.823 0.547
𝐾= 1 − 0.0203 𝑇 − 32
𝑑

Where:
𝐾 is measured in BTU · hr−1ft−2
𝑇 is measured in °F
𝑑 is the specific gravity at 60 °F (16 °C)

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Specific Heat
1
𝑐= 0.388 + 0.00046𝑇 eq. 1
𝑑
For eq.1:
𝑐 is measured in BTU/lbm°F
𝑇 is measured in °F
𝑑 is the specific gravity at 60 °F (16 °C)

1
𝑐= 0.4042 + 0.00081𝑇 eq.2
𝑑
For eq.2:
𝑐 is measured in kcal/kg.°C
𝑇 is measured in °C
𝑑 is the specific gravity 15 °C

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PETROLEUM REFINING PROCESSES

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• Physical Separation Processes
– Crude Distillation
– Solvent Deasphalting
– Solvent Extraction
– Solvent Dewaxing

• Chemical Catalytic Conversion Processes

– Catalytic Reforming
– Hydrotreating
– Catalytic Hydrocracking
– Catalytic Cracking
– Alkylation
– Isomerization

• Thermal Chemical Conversion Processes (Upgrading Processes)

– Delayed Coking
– Flexicoking
– Visbreaking
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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 operating at about 50
mmHg, where heavier products are obtained.

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Typical products from both columns and their boiling point ranges

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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. This oil is
also called ‘‘Bright Stock’’ and is used as feedstock for lube
oil plant.

• The DAO can also be sent to cracking units to increase light

oil production.
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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.

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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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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.

• The produced naphtha reformate has a much higher

octane number than the feed. This reformate is
used in gasoline formulation and as a feedstock for
aromatic production (benzene–toluene–xylene,
BTX).
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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.

• The catalyst is selected to suit the degree of

hydrotreating and type of impurity. Catalysts, such
as cobalt and molybdenum oxides on alumina
matrix, are commonly used.
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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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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

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Alkylation
• Alkylation is the process in which isobutane reacts
with olefins such as butylene 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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Isomerization
• Isomerization of light naphtha is the process in
which low octane number hydrocarbons (C4, C5,
C6) are transformed to a branched product with the
same carbon number. This process produces high
octane number products.

• One main advantage of this process is to separate

hexane (C6) before it enters the reformer, thus
preventing the formation of benzene which
produces carcinogenic products on combustion with
gasoline. The main catalyst in this case is a Pt-zeolite
base.
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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
– 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.
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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.

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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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Petroleum Products

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Homework
Physical Property
Characterization Data Chemical Analysis Data
• Fractionation
• True Boiling Point Distillation
• Elemental Analysis
• ASTM Distillation • Carbon Residue
• API Gravity
• Pout Point • Detailed Hydrocarbon
• Viscosity Analysis
• Refractive Index
• Freezing Point • Hydrocarbon family analysis
• Aniline Point
• Flash Point • Aromatic Carbon Content
• Octane Number • SARA Analysis
• Cetane Number
• Smoke Point
• Reid Vapor Pressure
• Water, Salt and Sediment
• Molecular Weight
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References
• Fundamentals of Petroleum Refining. Elsevier
B.V. 2010. ISBN: 978-0-444-52785-1
– Chapter no. 1, 2

• H. N. Giles & C. O. Mills, Crude Oils – Their

Sampling, Analysis and Evaluation. ASTM
International. 2010.
– Chapter no. 1, 3

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THANK YOU

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