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Introduction :Composition of petroleum,laboratory tests,refinery feedstocks and

products

Fig:1.1[15]

Fig.1.2 Distribution of world energy resources.


(From World Energy Outlook 2005, International Energy Agency.)[16,17]
Introduction to petroleum refinery Petroleum refineries have goal to convert as much of the
barrel of crude oil into transportation fuels which is economically practical. Refineries produce
many profitable products however, the high-volume profitable products are the transportation
fuel gasoline, diesel and turbine (jet) fuels, and the light heating oils. These transportation fuels
have boiling points between 25 and 350oC. Although products such as lubricating oils,
refrigeration and transformer oils, and petrochemical feedstocks are profitable.They amount to
less than 5 percent of the total crude oil charged to refineries. The processing equipment
indicated is for processing crude oils of average gravities and sulfur contents. Crude oils with
low API gravities (high specific gravities) and high sulfur contents require additional
hydrotreating equipment. The quality of crude oils processed by worldwide refineries is expected
to worsen slowly in the future with the sulfur contents and densities to increase. Therefore
refineries will require processing the entire barrel of crude rather than just the material boiling
below (550 oC).Sulfur restrictions on fuels, coke and heavy fuel oils affects the bottom-of-the-
barrel processing as well. These factors requires extensive refinery additions modernization the
shift in market requirements among gasolines and reformulated fuels for transportation
challenges.[16]
Refinery Overview[15-20] The crude oil is heated in a furnace and charged to an
atmospheric distillation tower, where it is separated into light gas (C1-C4), light naphtha, heavy
naphtha, kerosine, atmospheric gas oil, and reduced (topped) crude . The reduced crude is sent to
the vacuum distillation tower and separated into vacuum gas oil stream and vacuum reduced
crude bottoms (residua, resid). The reduced crude bottoms from the vacuum distillation tower is
thermally cracked in a delayed coker to produce gas, coker gasoline, coker gas oil, and coke. The
atmospheric and vacuum crude unit gas oils and coker gas oil are used as feedstocks for the
catalytic cracking or hydrocracking units where heavy molecules get converted into lower
molecular weight compounds boiling in the gasoline and distillate fuel ranges. The hydrocracked
products are saturated whereas catalytic cracker products are unsaturated and further need
improvement in quality by either hydrotreating or by reforming. The light naphtha streams from
the crude tower, coker and cracking units are sent to an isomerization unit to convert straight-
chain paraffins into isomers which have higher octane numbers. The heavy naphtha streams from
the crude tower, coker, and cracking units are fed to the catalytic reformer to improve octane
numbers. The products from the catalytic reformer can be blended into regular and premium
gasolines for marketing. The wet gas streams from the crude unit, coker, and cracking units are
separated in the vapor recovery section (gas plant) into fuel gas, liquefied petroleum gas (LPG),
unsaturated hydrocarbons (propylene, butylenes, and pentenes), normal butane, and isobutane.
The fuel gas is burned as a fuel in refinery furnaces and the normal butane is blended into
gasoline or LPG. The unsaturated hydrocarbons and isobutane are sent to the alkylation unit to
react olefins with isobutane to yield isoparaffins. The alkylation is done at high pressure and low
temperature in the presence of sulfuric or hydrofluoric acid as catalyst. The product is called
alkylated gasoline, which is a high-octane product blended into premium motor gasoline and
aviation gasoline. The middle distillates from the crude unit, coker, and cracking units are
blended into diesel and jet fuels and furnace oils. In some refineries, the heavy vacuum gas oil
and reduced crude from paraffinic or naphthenic base crude oils are processed into lubricating
oils. The asphaltenes are removed in a propane deasphalting unit, and the reduced crude from
bottoms are processed with the vacuum gas oils to produce lubeoil base stocks (LOBS). The
vacuum gas oils and deasphalted stocks are solvent-extracted to remove the aromatic compounds
followed by dewaxing to improve the pour point. These LOBS are further treated with acid clays
to improve their color and stability before being blended into lubricating oils. Each refinery has
its own unique processing scheme which is determined by the process equipment available,
crude oil characteristics, operating costs, and product demand.
Refinery Feed Stocks[19-20] The basic raw material for refineries is petroleum or crude oil.
The chemical compositions of crude oils obtained from various sources are almost uniform
although their physical characteristics vary widely. The elementary composition of crude oil
usually falls within the following ranges: C 84-88; H 11-15; S up to 5%, N up to 0.5 %. Crude
oils are classified as paraffin base, naphthene base, asphalt base, or mixed base depending upon
the composition of the residue left after distillation. Crude oils which have up to 80% aromatic
content are known as aromatic-base oils. The U.S. Bureau of Mines has developed a system
which classifies the crude according to two key fractions obtained in distillation: No. 1 from 250
to 275 oC at atmospheric pressure and No. 2 from 275 to 300 oC at 40 mmHg pressure. The API
gravity of these fractions varies depending upon paraffinic and naphthenic grade of the
crude(Paraffin : API 40 for No. 1 and 30 for No. 2, Naphthene : API < 30 for No. 1 oil and <=20
for No. 2 oil). The paraffinic and asphailtic classifications in common use are based on the
properties of the residuum left from nondestructive distillation and are more descriptive to the
refiner because they convey the nature of the products to be expected and the processing
necessary.
Composition Of Petroleum[19-20] Crude oils are composed of many members of
homologous series of hydrocarbons. Petroleum is essentially a mixture of hydrocarbons, and
even the non-hydrocarbon elements are generally present as components of complex molecules
predominantly hydrocarbon in character, but containing small quantities of oxygen, sulfur,
nitrogen, vanadium nickel, and chromium. The composition of the total mixture, in terms of
elementary composition, does not vary a great deal, but small differences in composition can
greatly affect the physical properties and the processing required to production marketable
products. The hydrocarbons present in crude petroleum are classified into three general types:
paraffins, naphthenes, and aromatics. Olefins are generally not present in crude oil, however
these are formed during processing by the dehydrogenation of paraffins and naphthenes. The
paraffin series of hydrocarbons is characterized by the rule that the carbon atoms are connected
by a single bond and the other bonds are saturated with hydrogen atoms.The general formula for
paraffins is CnH2n+2. Crude oil contains molecules with up to 70 carbon atoms, and the number of
possible paraffinic hydrocarbons is very high .Olefins do not naturally occur in crude oils but are
formed during the processing. They are very similar in structure to paraffins but at least two of
the carbon atoms are joined by double bonds. The general formula is CnH2n. Olefins are generally
undesirable in finished products because the double bonds are reactive and the compounds are
more easily oxidized and polymerized to form gums and varnishes. Olefins containing five
carbon atoms have high reaction rates with compounds in the atmosphere that form pollutants
and, even though they have high research octane numbers, are considered generally undesirable.
Some diolefins (containing two double bonds) are also formed during processing, but they react
very rapidly with olefins to form high-molecular-weight polymers consisting of many simple
unsaturated molecules joined together. Diolefins are very undesirable in products because they
are so reactive they polymerize and form filter and equipment plugging compounds.
Cycloparaffin hydrocarbons in which all of the available bonds of the carbon atoms are saturated
with hydrogen are called naphthenes. There are many types of naphthenes present in crude oil,
but except for the lower-molecular-weight such as cyclopentane and cyclohexane, are generally
not handled as individual compounds. They are classified according to boiling range and their
properties determined with the help of correlation factors such as the characterization (Kw) factor
or correlation index ( CI) . The aromatic series of hydrocarbons is chemically and physically
very different from the paraffins and cycloparaffins (naphthenes). The cyclic hydrocarbons, both
naphthenic and aromatic, can add paraffin side chains in place of some of the hydrogen attached
to the ring carbons and form a mixed structure.
Petroleum /crude oil[19]

Petroleum (also called crude oil) is a mixture of gaseous, liquid , and solid hydrocarbon
compounds.
Petroleum occurs in sedimentary rock deposits throughout the world and also contains
small quantities of nitrogen oxygen and sulfur-containing compounds as well as trace
amounts of metallic constituents.

Petroleum[19]

The fuels derived from Petroleum contribute approximately one-third to one-half of the
total world energy supply and are used for transportation fuels (gasoline,diesel fuel,and
aviation fuel,among others) and heating buildings.
Petroleum products have a wide variety of uses that vary from gaseous and liquid fuels to
near-solid machinery lubricants. Residue of many refinery processes asphaltis now a
premium value product for highway surfaces, roofing materials, and miscellaneous
waterproofing uses.
Crude petroleum is a mixture of compounds boiling at different temperatures that can be
separated into a variety of different generic fractions by distillation and the terminology
of these fractions has been bound by utility and often bears little relationship to
composition.

Major Processes:[19-20]

Desalting
Sweetening
Hydrogen Generation Unit
DHDS/DHDT
Reformer
Isomerisation
Amine Treating
Sulphur Recovery Unit
Bitumen Blowing Unit
Lube and wax
Solvent Extraction
Solvent dewaxing
Solvent Deoiling
Solvent deasphalting
Lube isomerisation
Hydrodesulfurisation
Fig:1.3[15]A typical REFINERY PROCESS CHART
Typical Refinery Products

LPG 2.1%
NAPHTHA 5.0%
MS 11.2%
OTHERS 18.3%
LIGHT DISTILLATE 36.6%
ATF 9.0

Chemistry in Fuel refining Key properties of Fuels

MS: Octane number, Sulphur, distillation, Oxidation stability, Bz/ Aromatics/ Olefin
content.
HSD: Cetane number,Sulphur,distillation,lubricity.
Kerosene: Smoke Point.
ATF: Freezing point.
Furnace oil: Stability.
Bitumen: Penetration, viscosity, Softening point.
LOBS: Viscosity, Viscosity Index.

Definations and Terminology[19,20] Petroleum is a mixture of gaseous, liquid, and


solid hydrocarbon compounds that occur in sedimentary rock deposits throughout the world and
also contains small quantities of nitrogen, oxygen, and sulfur-containing compounds as well as
trace amounts of metallic constituents.Petroleum is a naturally occurring mixture of
hydrocarbons, generally in a liquid state, which may also include compounds of sulfur, nitrogen,
oxygen, metals, other elements .Any naturally occurring hydrocarbon, whether in a liquid,
gaseous, or solid state may found explorations. Complexity of a refinery[19,20] The
combination of refining processes and operations employed (complexity) varies from one
refinery to another.Modern refinery is highly complex, energy and capital intensive. Role of
catalytic processes, secondary processing and hydroprocessing is increasing .Factors deciding the
complexity of a refinery.

Nature/source of crude oils- flexibility to process variety of crudes.


Demand pattern in the markets.
Product quality - current/ future.
Production of feedstocks for downstream units.
Inter-fuel substitution.

Separation : Heavy on the bottom, light on the top

The separation of crude oil by atmospheric and vacuum distillation into groups of
hydrocarbon compounds of different boiling point ranges called fractions or cuts.
The first step in crude oil processing, where the first separation takes place is called
Crude Distillation Unit (CDU) Atmospheric & Vacuum Unit (AVU).
This step is performed in all refineries :These units are called Mother Units
Typical products from CDU are : Gas, LPG, naphtha, SKO/ATF, HSD and RCO.
Vacuum Distillation of RCO produces VGO (or LOBS cuts) and VR
All products need further treatment/processing.

Classification of crude

The hydrocarbons found in petroleum are classified into


the following types:[19,20]
Paraffins(CnH2n+2)saturated hydrocarbons with straight
or branched chains, but without any ring structure.
Cycloparaffins (CnH2n)(naphthenes),saturated
hydrocarbons containing one or more rings, each of
which may have one or more paraffin side-chains(also
known as alicyclic hydrocarbons).
Aromatics(CnH2n-6)i.e,hydrocarbons containing one or
more aromatic nuclei such as benzene, naphthalene,
and phenanthrene ring systems that may be linked up
with (substituted) naphthalene rings or paraffin side-
chains.

Paraffins:
Carbon atoms connected by single bond
Other bonds saturated with hydrogen

Naphthenes:
Ringed Paraffins (Cycloparaffins)
All bonds saturated with hydrogen

Aromatics:
Six Carbon Rings (Multiple Bonding)
All bonds unsaturated

Olefins:
Usually not in crude oil
Formed During Processing
At least two carbon atoms connected by double bond
Fig:1.4 A typical example of n-butane, Cyclopentane,
Decaline, Benzene, Napthalene, and 1-butene.

Paraffin /naphthene/Asphaslt base crude (based on


residue after distillation)[21]
Paraffin base:The presence of paraffin wax in residue
is reflected in the paraffin nature of the constituent.
Asphaltic base:high asphaltic content corresponds with
the naphthene properties of the fractions.Asphalt-
base(black amorphous soild MW 600-30K)crude oils our
mainly of highly Aromatic (or naphthene) hydrocarbons.

Crude oil[19]

Color: Light brown to dark brown


Sp.gr: 0.810.985
Boiling range : 25 400oC
Hydrocarbons C1- C70 (4000 compounds)
Metals: V, Fe, Ni
S-( H2S,Thiols (mercaptans), sulfides, di sulfides, poly
sulfides and thiophenes).
Cause corrosion of equipments, bad odour in
products,catalyst poisoning, Air pollution.
N Indols, pyridines and quinolenes (Difficult to remove).
Oxygen compounds: present as naphthenic acids and
phenols
Are corrosive in nature and cause odour.
Metal: act as catalyst poisons

Crude composition
C: 84-87%,H: 11-14%,S: 0-5%,N: 0-1%,O: 0-2%.

Reservoirs/ sedimentary basin[19-22]


Petroleum occurs underground, at various pressures
depending on the depth.
Because of the pressure, it contains considerable natural
gas in solution. Petroleum underground is much more
amount of fluid with than the surface and is generally
mobile under reservoir conditions because of the
elevated temperature phase(the geothermal gradient) in
subterranean formations decrease the viscosity.
Petroleum is derived from aquatic plants and animals
that lived and died hundreds of millions of years
ago.Their remains mixed with mud and sand in layered
deposits that, over the millennia, were geologically
transformed into sedimentary rock.

Reservoiur and Oil field


Gradually the organic matter decomposed and
eventually formed petroleum (or a related precursor),
which migrated from the original source beds to more
porous and permeable rocks, such as sandstone and silt
stone, where it finally became entrapped. Such
entrapped accumulations of petroleum are called
reservoirs.
A series of reservoirs within a common rock structure or
a series of reservoirs in separate but neighboring
formations is commonly referred to as an oil field.
A group of fields is often found in a single geologic
environment known as a sedimentary basin or province.

Estimations of Reserves[22]

Estimation of HC Content :Done by material balance


Estimation of fresh finding:by physical condition of the
reservoir.
Porous sedimentary rocks:porosity(e)
Maximum amount of HC that can present in rock=e * (vol. of
reservoir)
WATER present in oil=SW connate water
Total volume of HC deposited=vol.of reservoir.*e*(1-SW)(
volume Deposited under reservoir condition)
Generally deposits are several meter deep where pressure
>100atm.Lig/ gas volume expan-sion factor Bg at surface
conditions For liquid expansion factor is small but for gas it is
high.
Thus Total vol.of deposit at surface condition=vol. of
reservoir*e*(1-Sw)* Bg.
Refinery Operation

Crude oil is transported to refineries by pipelines, (more than 500,000


barrels per day), or by ocean-going tankers.
The basic refinery process is distillation, which separates the crude oil
into fractions of differing volatility.
After the distillation,other physical methods are employed to separate
the mixtures including absorption adsorption solvent extraction and
crystallization.
After physical separation into such constituents as light and heavy
naphtha, kerosene, light and heavy gas oils selected petroleum fractions
may be subjected to conversion processes such as thermal cracking
(i.e., coking;) and catalytic cracking.
Cracking breaks the large molecules of heavier gas oils into the smaller
molecules that form the lighter, more valuable naphtha fractions.
Reforming changes the structure of straight-chain paraffin molecules
into branched-chain iso-paraffins and ring-shaped aromatics. The
process is widely used to raise the octane number of gasoline obtained
by distillation of paraffinic crude oils.
Fig:1.5[15]A typical REFINERY PROCESS CHART with both Atmospheric
(ADU) and Vaccum distillation process (VDU).
Classification of Crude as a hydrocarbon resource:[19,20]

Fossil energy resources divide into two classes:


Naturally occurring hydrocarbons (petroleum, natural gas, and natural
waxes)
Hydrocarbon sources (oil shale and coal) which may be made to
generate hydrocarbons by the application of conversion processes.Oil
Shale are argillaceous, laminated sediments of generally high organic
content that can be thermally decomposed to yield appreciable amounts
of oil.
The classification of petroleum and natural gas as naturally occurring
mixtures of hydrocarbons occurs by virtue of the fact that they can be
separated into their original hydrocarbon constituents.
The hydrocarbon constituents, separated from petroleum and natural
gas, are the hydrocarbon constituents that existed from the reservoir.
Naturally occurring hydrocarbons are major contributors to the
composition of petroleum and natural gas.
Coal and kerogen do not enjoy this by means of separation and methods
of thermal decomposition and it must be applied before hydrocarbons
are produced.
Kerogen is the complex carbonaceous (organic) material that occurs in
sedimentary rocks and shales.

Subdivision of the earths organic sediments[20]

Fig:1.6

Classification of the earths organic sediments according to hydrocarbon


occurrence and production.[20]
Fig:1.7

Fig:1.5[15]A typical REFINERY PROCESS CHART with both


Atmospheric (ADU) and Vaccum distillation process (VDU).

Classification of Crude as a hydrocarbon resource:[19,20]

Fossil energy resources divide into two classes:


Naturally occurring hydrocarbons (petroleum, natural gas, and
natural waxes)
Hydrocarbon sources (oil shale and coal) which may be made
to generate hydrocarbons by the application of conversion
processes.Oil Shale are argillaceous, laminated sediments of
generally high organic content that can be thermally
decomposed to yield appreciable amounts of oil.
The classification of petroleum and natural gas as naturally
occurring mixtures of hydrocarbons occurs by virtue of the fact
that they can be separated into their original hydrocarbon
constituents.
The hydrocarbon constituents, separated from petroleum and
natural gas, are the hydrocarbon constituents that existed
from the reservoir.
Naturally occurring hydrocarbons are major contributors to the
composition of petroleum and natural gas.
Coal and kerogen do not enjoy this by means of separation and
methods of thermal decomposition and it must be applied
before hydrocarbons are produced.
Kerogen is the complex carbonaceous (organic) material that
occurs in sedimentary rocks and shales.

Subdivision of the earths organic sediments[20]

Fig:1.6

Classification of the earths organic sediments according to


hydrocarbon occurrence and production.[20]
Fig:1.7