Chemistry of Crude Oils

PRODUCTS MADE FROM

BARREL OF CRUDE OIL
 BOILING RANGE-CARBON NUNBER
-MOL. WT. OF HYDROCARBONS
Boiling Range C. No. Mol. wt
LPG - 44 TO -310C C3-C4 44-56
Gasoline IBP-2150C C5-C11 100-110
Kerosene Jet fuel 193-2710C C11-C18 160-190
Diesel 271-3430C C15-C20 160-245
Atmos.Gas oil 343-4270C C20-C25 320
Atmos. Residue 427+ C25+ 320+
VGO 427-5380C C28-C40 320-430
Vac. Residue 5580C+ C50 Onwards 430-800
Pet. Coke 10930C C200+ 2500+
 PETROLEUM - CRUDE OIL
❑ “Petro (Πέτρα)” from Greek : rock + “oleum” from Latin:
oil, the name represents its source of formation (find in oil
reservoirs associated with sedimentary rocks beneath the
earth’s surface)

❑ Crude oil (petroleum) is a naturally occurring brown to

black flammable liquid with viscosity varying from that of
water to almost solid
❑ Consists of a complex mixture of hydrocarbons of various
molecular weights and other liquid organic compounds

❑ Because of its complex nature and the presence of

impurities it is also called “Crude Oil”

IIP Dehradun
 COMPOSITION OF CRUDE OIL
❑ Regardless of their origin, all crude oils mainly
constitute of
❑ Hydrocarbons
❑ variable amounts of sulfur, nitrogen, and oxygen compounds
❑ Trace amounts of metals in the forms of inorganic salts or
organo-metallic compounds

❑ The composition vary appreciably from one reservoir to

another

❑ Crude oil is unsuitable for direct use as fuel/ feedstock

The complex nature of crude oil mixture and the presence of some
impurities that are corrosive or poisonous to processing catalysts
 ELEMENTAL COMPOSITION
OF CRUDE OIL
Elements Wt%
Carbon 83.9-86.8
Hydrogen 11.0-14.0
Sulfur 0.06-8.00
(More than 5% in heavy Missisippi or
Mexican crudes, middle east-5%),
(0.37% in Brent light crude, API 38.06)

Nitrogen 0.02-1.70
(0.1-0.9 % in californian & south American crude)
Oxygen 0.08-1.82
Metals 0.00-0.14
 PHASES OF CRUDE
• Includes gas, liquid and solid hydrocarbon phases
• Gas: methane, ethane, propane and butane
• Liquid and solid: pentane and heavier ones are in the form
of liquids or solids.
• However, 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
• An oil well produces predominantly crude oil, with some
natural gas dissolved in it. Because the pressure is lower at
the surface than underground, some of the gas will come
out of solution and be recovered (or burned) as associated
gas or solution gas
Natural gas flares in the Zubair oil field in southern Iraq /
The World Bank: Global gas flaring has remained largely stable over
the past twelve years, in the range of 150 to 170 billion cubic meters.
Flaring adds about 400 million tons of carbon dioxide into the
atmosphere each year.
 HYDROCARBONS
❑ The compounds of Carbon and hydrogen with
the General formula: CnH2n+z

n = 1,2,3..........
z = 0,2,-2,-4,-6.......... – 30

❑ Paraffins, isoparaffins, naphthenes and

aromatics

❑ C/H ratio increases from P to A

❑ C/H decreases with alkyl substitution on N

and A
CLASSES OF HYDROCARBONS

❑ n-alkanes
(n-paraffins, Z = +2)

❑ i-Alkanes
(iso paraffins, z = +2)

❑ Naphthenes
(cyclo paraffins, Z = 0,-2,-4 etc.)

❑ Aromatics ( z = -6,-8,-10 etc.)

 FORMULA & BOILING POINT
RANGE OF PARAFFIN COMPOUNDS
Compounds Formula Boiling Point 0C
Ethane (C2H6) -88.6
Propane (C3H8) -42.1
n-Butane (C4H10) -0.5
n-Pentane (C5H12) 36.1
n-Hexane (C6H14) 68.8
n-Heptane (C7H16) 98.4
n-Octane (C8H18) 125.7
n-Nonane (C9H20) 150.9
n -Decane (C10H22) 174.0
n-Undecane (C11H24) 195.8
n-Dodecane (C12H26) 216.3
n-Tridecane (C13H28) 234.0
 SIGNIFICANCE OF PARAFFINS
❑ Oxidation of (C8-C30) n-paraffins resulting in fatty
acids for soap industries
❑ Oxidation of (C12-C14) n-paraffins resulting in
secondary alcohols
❑ Mono-chloro paraffins (C10-C30) as cutting oil additives,
plasticizers and fire retardant chemicals
❑ Sulphonated LAB from n-paraffins ( C9-C13) for
biodegradable detergents
❑ Paraffin Wax
❑ Freezing point in ATF
❑ Cold flow properties of diesel and lubes
❑ Ignition quality of gasoline and diesel fuels
 ISO-PARAFFINS
❑ Branched paraffinic hydrocarbons
General formula of n-paraffins is (Cn-H2n+2) e.g.
➢ Iso butane
➢ Iso pentane etc.
❑ Predominant members carry the simplest type of
side chain i.e. CH3
❑ Highest concentration of 2-methyl alkanes in (C6-
C8) range
❑ Di and Tri substituted are less abundant and are
mainly present in higher boiling fractions
SIGNIFICANCE OF ISOPARAFFINS

These are most desirable components for the

❑ Gasoline (due to high Octane No.)

❑ ATF (melt significantly below

corresponding alkanes)
❑ Lubricating oil
❑ Highly branched isomers are undesirable
in diesel fuel
 NAPHTHENES
❑ Cyclic saturated compounds
General formula (Cn-H2n+2)-2Rn
Rn = number of naphthenic rings

❑ In crude oil Naphthenes present about 50% by

weight and its quantity is higher in heavier
fractions

❑ Present in naphtha and predominated in most of

the gas oils and in lubricating oils

❑ Chemically highly stable hydrocarbons.

 CLASSIFICATION OF
NAPHTHENES
• Isolated Rings Type
When rings are separated by paraffinic chain e.g. Dicyclo- hexyl
alkane

• Conjugated rings Type

When rings are linked each other by carbon ring to carbon ring
bond e.g Alkyl dicyclo hexyl

• Condensed Rings Type

When two rings have at least two vicinal carbon atom in common
e.g condensed bycyclic or Alkyl decalin
 AROMATIC HYDROCARBONS
❑ Unsaturated cyclic hydrocarbons

❑ General formula (Cn-H2n-6) & (Cn-H2n-12)

❑ Aromatics are found about 15 % by weight in crude

oils

❑ present as derivatives of benzene and poly nuclear

aromatic hydrocarbons (both condensed and non
condensed types) and their homologues

❑ Chemically reactive and can form both substitution

or addition products
 HEAVY AROMATIC HYDROCARBONS
❑ Derivatives of benzene and polynuclear condensed
aromatics (Homologues of following series)
➢ ALKYL AROMATICS
(Z = -6)
➢ ALKYL NAPHTHALENES
(Z = -12)
➢ TRINUCLEAR
(Z = -18)
➢ TETRA NUCLEAR
(Z = -22)
➢ PENTA NUCLEAR
6 OR 7 RINGS STRUCTURES
 NAPHTHENO AROMATICS

❑ These are also a kind of aromatic hydrocarbons in which

aromatic ring is fused with an alicyclic ring with aliphatic
chains. Generally such type of compounds is present in
middle distillates

❑ These types of the compounds start to appear from

kerosene range and are classified according to total
number of rings and the number of aromatic rings they
contain

❑ In polycyclic Naphtheno-aromatic hydrocarbons the rings

are mainly condensed
 Contd..
❑ They have higher polarity and are extracted
selectively by polar solvents

❑ For the same carbon number volatility of aromatics

is lower than its corresponding paraffins

❑ They undergo readily for electrophillic substitution

therefore they are used as good chemical feed stock

❑ They are known carcinogen.

 EFFECT OF HYDROCARBON
TYPES ON OCTANE NUMBER
❑ Normal paraffins have the least desirable knocking
characteristics, and these become progressively
worse as the molecular wt. increases
❑ Iso-paraffins and naphthenes have higher octane
than corresponding n-paraffins
❑ Octane number of isoparaffins increase as the
degree of branching of the chain is increased
❑ Olefins have markedly higher octane numbers
than the corresponding paraffins
❑ Aromatics have the highest octane number for the
same number of carbon atoms
 OCTANE NUMBERS OF ALL C7
HYDROCARBONS
Hydrocarbons Octane numbers
n-Heptane Zero
2-3,Di-methyle pentane 42
2-4,Di-methyle pentane 83
2 Methyle Hexane 91
1-Heptene 54
2-Heptene 84
1,1Dimethyl cyclopentane 92
4,4Di-methyl 2 Pentene 106
Methyle cyclo hexane 75
Toluene 120
 MAIN IMPURITIES
❑ Water content
❑ BS & W
❑ Salt content
❑ Sulphur content
❑ Nitrogen content
❑ Inorganic and total acid value
❑ Trace metals
❑ Inorganic electrolytes,
❑ Inorganic gases like (co2, and h2s)
❑ Siliceous debris
HETERO ATOMIC COMPOUNDS

❑ The hydrocarbon compounds containing

nitrogen, oxygen & sulphur as a constituent
with carbon and hydrogen are known as
hetero hydrocarbons
 Contd.
❑ Sulphur compounds
➢ Sulphur is present in crude oils as hydrocarbon type as
well as non-hydrocarbon type
➢ In crude oils it varies from 0.1-3.0 percent by weight but
values upto 7.0% sulphur content of crude are also
known
➢ Indian crudes are sweet in nature, contain about (0.05-
0.4 % by Wt.) of sulphur

❑ Non hydrocarbon type sulphur

➢ Sulphur is also found in crude as hydrogen sulphide
 HYDROCARBON TYPE SULPHUR
❑ Sulphur is present with carbon & hydrogen. It is found
in the form of :
• Mercaptans RSH
• Thiophenes Cyclic sulphur compounds
• Sulphides (thio ether) RSR
• Disulfides RSSR
• Sulphoxides
• Sulphones

❑ In low and medium molecular weight range (upto C25) it is

associated with carbon and oxygen where as in heavier
fractions it is associated with polycyclic molecules which
may also contain nitrogen and oxygen
 Contd.
❑ H2S (BP–61.8) toxic, distinct odor present in light
petroleum fractions and in natural gas, acts like a week
mineral acid but corrosive
❑ Thiol or mercaptans are more acidic, highly volatile and
have disagreeable odour
❑ Sulphides, thioethers and disulphides are relatively
unstable and easily converted back to mercaptan by
heating them
❑ Thiophene and its derivative have reasonably good thermal
stability
❑ Refining techniques are applied to reduce sulphide
products due to their disagreeable odor, corrosiveness,
because their combustion produces sulfurous and sulfuric
anhydride (SO2 and SO3)
 SULPHUR COMPOUNDS IN
CRUDE FRACTION (IBP-1000C)
COMPOUNDS BOILING POINT (0C )
Methane thiol 5.96
Ethane thiol 34.00
2-Thiopropane 37.31
2-Propanethiol 52.56
2-Methyl 2-propanethiol 64.22
2-Thiobutane 66.65
1-Propanethiol 67.50
3-Methyl-2-thiobutane 84.81
2-Butanethiol 85.51
2-Methyl 1-propanethiol 88.72
3-Thiopentane 95.52
1-Butanethiol 98.40
3,3 Dimethyl-2-thiobutane 99.00
2-Methyl-2-Butanethiol 99.00
 EFFECTS OF SULPHUR
COMPOUND IN CRUDE OIL
❑ Sulphur compounds are most undesirable constituents
of crude oil
❑ Corrosive in nature
❑ Acts as gum precursors during storage
❑ Pollution (Toxic)
❑ Increases deposits in engine
❑ Reduce lubricating oil life
❑ Causes wear in engines
❑ Acts as catalyst poison during reforming
 OXYGEN COMPOUNDS
❑ Oxygen present in the crude oil is relatively low
varying from traces to maximum 2% by weight.
❑ Its concentration also increases with increasing
the boiling point of the crude fraction

Chemical forms of oxygen containing HC

➢ Phenols
➢ Furanes
➢ Fatty acids
➢ Naphthenic acids
➢ Esters
➢
 EFFECT OF OXYGEN
COMPOUNDS IN CRUDE OIL
❑ Contribute to acidity (Naphthenic
acids)

❑ Corrosive in nature and corrode the

distillation unit

❑ peroxide formation
 ORGANO-NITROGEN
COMPOUNDS
❑ Nitrogen compounds present in crude oil generally
less than sulphur compounds in weight percent

❑ Most of the crudes contain < 0.2 % wt of total

nitrogen

❑ Nitrogen compounds present as basic as well as

non-basic in nature

❑ Generally their concentrations are less upto 3000C

 CONTD..
❑ Basic nitrogen compounds
➢ Amines, Amides, Pyridine
➢ Quinoline
➢ Iso-quinoline

❑ Non basic nitrogen compounds

➢ Pyrrole
➢ Indole
➢ Carbazole
➢ Porphyrines (Pyrrole nucleus)
 HIGH MOLECULAR WEIGHT
NITROGEN AND SULPHUR
❑ These compounds present in the crude oil as a complex
structure known as porphyrines
❑ Generally they are present in the asphaltenes, resins
❑ Asphaltene molecules probably consist of sheet
❑ Comprising of some 10-20 % condensed aromatic rings
linked with the naphthenic and paraffinic groups
❑ Asphaltene molecules form aggregates
➢ Micelles : Molecular weight 30,000
➢ Particle : Molecular weight 3000-10000
❑ Resins possess lower molecular weight (500-1200)
 BOILING RANGE-CARBON NUNBER
-MOL. WT. OF HYDROCARBONS
Boiling Range C. No. Mol. wt
LPG - 44 TO -310C C3-C4 44-56
Gasoline IBP-2150C C5-C11 100-110
Kerosene Jet fuel 193-2710C C11-C18 160-190
Diesel 271-3430C C15-C20 160-245
Atmos.Gas oil 343-4270C C20-C25 320
Atmos. Residue 427+ C25+ 320+
VGO 427-5380C C28-C40 320-430
Vac. Residue 5580C+ C50 Onwards 430-800
Pet. Coke 10930C C200+ 2500+
APPLICATIONS OF MAJOR CRUDE
FRACTIONS FOR VALUE ADDITION
Naphtha • Feed stock for petrochemicals through
olefins
• Feed stocks for petrochemicals through
aromatics
• Feed stocks for FGH
• Potential of pure chemicals
• Potential of SBP solvents.
Kerosene • Potential of n-paraffins (nC10-nC14) for
linear alkyl benzene – Detergents
• Naphthalene precursors
 CONTD..
Gas Oils • n-paraffins for synthetic fatty acids and
higher alcohols
VGOs • Potential for lubes, waxes and
microcrystalline waxes and feed stock
for secondary conversion
Deep • Distillates for additional quantities of
Distillation feed stock for secondary conversion
Cuts • Potential for Microcrystalline waxes

IIP Dehradun
 DEFINITIONS…..
• Watson K RCR
• UOP K CCR
• API gravity VI
• Kinematic viscosity Flash Point
• RVP Bromine Number
• Octane no Aniline Point
• Cetane no
• Smoke point
• Cloud Point
• Pour point

IIP Dehradun