Refinery Feedstocks

Dr. Shashikant Yadav

Formation of Oils & Gas
 Formation of Oils & Gas
Burial
• The remains of plants and animals, such as diatoms, built up in thick layers on the ocean floor and
earth's surface. These layers were sometimes mixed with sand, silt, and calcium carbonate. Ancient
rivers also carried mud and sand that buried the organic material.

Decomposition
• Over time, the layers were buried under sand, silt, and rock, and microorganisms and high
subterranean heat decomposed the prehistoric organisms.

Transformation
• The absence of air, high pressure, and high temperature transformed the carbon and hydrogen-rich
material into coal, oil, and natural gas. The oil and gas then collected in underground formations,
where they accumulated to form oil and gas fields.
• At about 60C, oil begins to form.
• Oil formation ceases at about 150 C.
• Oil formed at lower temperatures (i.e. closer to the surface) is called immature and is heavy.
 Exploration and Extraction

Exploration Techniques
• Seismic surveys, geological mapping, and drilling.

Extraction Methods
• Primary: Natural pressure drives oil and gas to the surface.
• Secondary: Water flooding or gas injection to maintain reservoir pressure.
• Tertiary: Enhanced Oil Recovery (EOR) techniques like CO2 injection.
 Advanced Concepts in Petroleum
Formation
Unconventional Resources
• Shale gas, tight oil, and tar sands.
• Require advanced extraction methods like hydraulic fracturing and horizontal
drilling.

Geochemical Analysis
• Using biomarkers and isotopic studies to trace the origin and evolution of
petroleum.
 Refinery Feedstocks
• Crude oil comes from different parts of the
world and has different physical and chemical
characteristics.
• On the other hand, the products that are
produced have to meet market requirements
and as such, should comply with certain
specifications.
 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 sulphur,
oxygen, nitrogen and metals such as vanadium, nickel, iron and copper are
also present.
• Despite their low concentrations, impurities such as sulphur, nitrogen,
oxygen and metals are undesirable because they cause concerns in the
processability of crude feedstock and because they affect the quality of the
produced products. Catalyst poisoning and corrosion are the most
noticeable effects during refining.
• Hydrogen to carbon ratios affect the physical properties of crude oil. As
the hydrogen to carbon ratio decreases, the gravity and boiling point of the
hydrocarbon compounds increases. Moreover, the higher the hydrogen to
carbon ratio of the feedstock, the higher its value is to a refinery because
less hydrogen is required.
Elemental composition of crude oils
 Classes of hydrocarbons
• There are three main classes of hydrocarbons:
• 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). 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.
 Paraffins
• Paraffins, also known as alkanes, are saturated compounds
that have the general formula CnH2n+2, where n is the
number of carbon atoms.
• The simplest alkane is methane (CH4), which is also
represented as C1.
• Normal paraffins (n-paraffins or n-alkanes) are unbranched
straightchain molecules.
• Each member of these paraffins differs from the next higher
and the next lower member by a –CH2– group called a
methylene group.
• They have similar chemical and physical properties, which
change gradually as carbon atoms are added to the chain.
 Cont…
Names and formulas of parrafins (alkanes)
 Cont…
• Isoparaffins (or isoalkanes) are branched-type hydrocarbons that exhibit structural
isomerization.
• Structural isomerization occurs when two molecules have the same atoms but
different bonds.
• In other words, the molecules have the same formulas but different arrangements of
atoms, known as isomers.
• For example, butane and pentane have the following structural isomers:

Because of their different structures, these isomers have different properties.

For instance, the presence of isoparaffins in gasoline is essential for
increasing the octane number of gasoline fuels.
 Naphthenes (cycloalkanes)
• Naphthenes, also known as cycloalkanes, are saturated
hydrocarbons that have at least one ring of carbon atoms.
They have the general formula CnH2n. A common
example is cyclohexane (C6H12).

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. Examples of naphthenes are shown below.
 Olefins
• Olefins, also known as alkenes, are unsaturated hydrocarbons containing
carbon–carbon double bonds.
• Compounds containing carbon–carbon triple bonds are known as
acetylenes, and are also known as biolefins or alkynes.
• The general formulas of olefins and acetylenes are CnH2n(R–CH=CH–R’)
and CnH2n-2(R–CH≡C–R’), respectively.
• Unsaturated compounds may have more than one double or triple bond. If
two double bonds are present, the compounds are called alkadienes or,
more commonly, dienes (R–CH=CH–CH=R’). There are also trienes,
tetraenes and even polyenes.
• 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 feedstocks for the
petrochemical industry. The lightest alkyne is acetylene.
 Aromatics
• Aromatics are unsaturated cyclic compounds
composed of one or more benzene rings.
• The benzene ring has three double bonds with
unique electron arrangements that make it
quite stable.
 Cont…
• 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.
 Cont…
• More complex aromatic compounds consist of a number of ‘‘fused’’
benzene rings. These are known as polynuclear aromatic compounds.
• They are found in the heavy petroleum cuts, and their presence is
undesirable because they cause catalyst deactivation and coke deposition
during processing, besides causing environmental problems when they are
present in diesel and fuel oils.
• Examples of polynuclear aromatic compounds are shown below.
 Sulphur Compounds
• The Sulphur 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 % sulphur is referred to as low sulphur or
sweet, and that with more than 1 wt% sulphur is referred to as high sulphur
or sour.
• Sulphur containing constituents of crude oils vary from simple mercaptans,
also known as thiols, to sulphides and polycyclic sulphides. Mercaptans are
made of an alkyl chain with –SH group at the end (R–SH). Examples of
mercaptans and sulphides are as follows:
 Cont…
• In sulphides and disulphides, the sulphur atom replaces one or
two carbon atoms in the chain (R–S–R’ or R–S–S–R’). These
compounds are often present in light fractions. Sulphides and
disulphides may also be cyclic or aromatic.
 Cont…
• Thiophenes are polynuclear aromatic compounds in which the sulphur
atom replaces one or more carbon atoms in the aromatic ring. They are
normally present in heavier fractions. Thiophenes present in crude oils may
have the following formulas:
 Oxygen Compounds
• The oxygen content of crude oil is usually less than 2 wt%.
• A 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.
• Examples of alcohols, phenols and ethers are:
 Cont…
• Carboxylic acids have a carboxyl group as their functional
group (–COOH), and their general formula can be written as:

• Examples of aliphatic and aromatic carboxylic acids are:

 Cont…
• Carboxylic acid anhydrides are formed by removing water from two
carboxyl groups and connecting the fragments. The most important
aliphatic anhydride is acetic anhydride.

• Carboxylic acid esters are formed by replacing the –COOH by –COOR

group. Examples are:
 Cont…
• Ketones are compounds with two carbon atoms bounded to the
carbon of a carbonyl group ˃C = O.
• Furans are hetroaromatic compounds with five member
oxygenated rings. Benzofuran is a furan condensed with an
aromatic ring. Examples are:
 Nitrogen Compounds
• Crude oils contain very low amounts of nitrogen
compounds.
• In general, the more asphaltic the oil, the higher its
nitrogen content.
• 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.
 Cont…
• The nitrogen compounds in crude oils may be classified as basic or non-
basic. Basic nitrogen compounds consist of pyridines. The greater part of
the nitrogen in crude oils is the non-basic nitrogen compounds, which are
generally of pyrrole types.
• Pyridines are six-membered heteroaromatic compounds containing one
nitrogen atom. When fused with benzene rings, pyridines are converted to
the polycyclic heteroaromatic compounds quinolines and isoquinolines.
 Cont…
• In non-basic nitrogen compounds, pyrroles are five-membered
heteroaromatic compounds containing one nitrogen atom.
• When fused with benzene ring, pyrrole is converted to the
polycyclic heteroaromatic compounds indole and carbazole.
 Metallic 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.
• For high-temperature power generators, the presence of vanadium in the fuel may lead to ash
deposits on turbine blades and cause severe corrosion, and the deterioration of refractory
furnace linings.
• Part of the metallic constituents of crude oils exist as inorganic water-soluble salts, mainly as
chlorides and sulphates of sodium, potassium, magnesium and calcium.
• These are removed in desalting operations.
• More important are metals which are present in form of oil-soluble organometallic
compounds.
• Zinc, titanium, calcium and magnesium appear in the form of organometallic soaps.
• However, vanadium, nickel, copper and iron are present as oil-soluble compounds, capable of
complexing with pyrrole compounds.
 Asphaltenes and Resins
• The physical properties of crude oils, such as the
specific gravity (or API), are considerably
influenced by high-boiling constituents, in which
the heteroatoms (sulphur, nitrogen and metals)
concentrate.
• It is therefore important to characterize the
heaviest fractions of crude oils in order to
determine their properties and ease of processing.
• This calls for determining the percentage of two
generally defined classes of compounds, namely
asphaltenes and resins.
 Cont…
• Asphaltenes are dark brown friable solids that have no definite melting
point and usually leave carbonaceous residue on heating.
• Their molecular weights span a wide range, from a few hundred to several
million.
• 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.
• In refinery operations, asphaltenes have markedly adverse effects on the
processability of crude oils. They lead to coke formation and metal
deposition on the catalyst surface causing catalyst deactivation.
• They are made up of condensed polynuclear aromatic layers linked by
saturated links. These layers are folded, creating a solid structure known as
a micelle.
 Cont…
• Resins are polar molecules in the molecular
weight range of 500–1000, 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.
• The resin molecules surround the asphaltene
clusters (micelles) and suspend them in liquid oil.
• Because each asphaltene is surrounded by a
number of resin molecules, the content of resins
in crude oils is higher than that of the asphaltenes.
Thanks