10-03-2017

Chapter-
Characterization of crude
and various petroleum
products

Introduction to crude oil

Petroleum/crude oil means rock oil.

Natural organic material, composed principally of hydrocarbons

in geological traps

Composed from hydrocarbon and/ or sulphur, nitrogen and /or

oxygen hydrocarbon derivatives with traces of metallic
elements

Accompanied by extraneous substances (e.g. water, inorganic

matter and gas, etc.)

1
 10-03-2017

Introduction to crude oil

C/H ratio = 6-8

Composition according to its source

Wide range of physical and chemical properties

Light crude oil: brown colour, pleasant aromatic like smell

Heavy crude oil: black brownish colour, unpleasant odour due

to sulphur compounds

Specific gravity = 0.73-1.02

Composition of crude oil

Elemental composition of crude oil (table)

Element Amount, wt%

C 83.9-86.8
H 11-14
S 0.06-8.0
N 0.02-1.7
O 0.08-1.82
Metals 0.0-0.14

Napthenic acids accounts for O, mercaptans for O, resinous

and asphaltic substances for O and S both, dissolved H2S for
inorganic S.
Traces of metals in water impurities and some as complexes in
hydrocarbon

2
 10-03-2017

Composition of crude oil

Small amount of chlorophyll porphyrins are of plant sources and

isoprenoid are linked from biological sources

Water associated with crude, markedly saline, deficient in Mg

and SO42+ as compared to sea water

Hydrocarbons present in crude oil

Alkanes (paraffins)
Straight chain (e.g. butane) & branched chain (e.g. isobutene)

Cycloalkanes (cycloparaffins)
saturated cyclic alkanes, also called napthenes,
General formula = CnH2n+2-2N, n-no. of C atoms, N-no. of rings
mainly found in crude oils: cyclopentane, cyclohaxane and
alkyl derivative of <C10 (e.g. 1, 1, 3 trimethylcyclohaxane)
Heavier fractions of crude have poly cyclic nepthenes
(e.g. Kerosene - decalin, bicyclic, C10H18)

Aromatics (Arenes)
Unsaturated cyclic compounds, very reactive
Single cycle (e.g. benzene, toluene) and multicycle (e.g. Biphenyl)

3
 10-03-2017

Hydrocarbons present in crude oil

Unsaturated cyclic compounds, very reactive
Single cycle (e.g. benzene, toluene) and multicycle (e.g. Biphenyl)
Many polycyclic aromatics in petroleum are carcinogens.

Alkenes
Double bond unsaturated open chain hydrocarbons (e.g. Butene, Pentene)

Alkynes
Triple bond unsaturated open chain hydrocarbons (e.g. Ethylacetylene)

Cycloalkanoarenes (Nepthenoaromatics)
Having fusion of aromatic with alicyclic rings and may carry aliphatic side
chains also.

Hydrocarbons present in crude oil

Indane
Tetralin

4
 10-03-2017

Non-Hydrocarbons present in crude oil

S, N and O derivatives of hydrocarbons and organometallic

Sulphur compounds
Most abundant constituents of crude oil
(S is natural content of tissues of plant and animal. Biogenic
reduction of sulphate is other origin.)

Divided into thiols, mono- and disulphides and thiophenes

Thiols
Mercaptans, sulphur analogues of alcohol, low boiling point
sulphur compounds

Non-Hydrocarbons present in crude oil

Ethanethiol
Cyclohaxanethiol

Causes corrosion problems, catalyst deactivation & bad odours

Stronger acid than alcohols, removed with use of caustic soda
from light gasoline

Monosulphides
Derived by replacement of both H of HSH by hydrocarbons,
highly maladourous

Methyl propyl sulphide

5
 10-03-2017

Non-Hydrocarbons present in crude oil

Disulphides

Methyl disulphide

Low molecular weight disulphides in crude

Occurrence due to secondary reaction of thiols with oxidants as

air or sulphur

Non-Hydrocarbons present in crude oil

Thiophenes

Thiophene

Benzo (b)thiophene

Thiophene and its derivatives are relatively scare constituents of

crude.

Benzothiophene, dibenzothiophene, etc. are important

constituents in all high sulphur crudes.

6
 10-03-2017

Non-Hydrocarbons present in crude oil

Nitrogen compounds
Occurs less than half of S in crude

Generally found in heavier grades of oil

Relatively stable towards heat (compared to S compounds), do

not compose in refining processes

Distribute in lighter to heavier fraction but largest amount (65-

75%) in residue only

Presence of even trace amount in distillates, lead to loss in

catalyst activity, colour instability in products, gum formation

Types (i) basic N compounds (ii) non-basic N compounds

Non-Hydrocarbons present in crude oil

Basic N compunds
Titratable with perchloric acid, found in lower boiling point crude

Pyridine Quinoline
Non-basic N compunds
Most abundant in crude, found in higher boiling point fraction

Pyrrole Pyrrole
Additional N compounds as anilines, phenazines and nitriles are
found in petroleum fraction after catalytic cracking.

7
 10-03-2017

Non-Hydrocarbons present in crude oil

Oxygen compounds
Occurs in large amount only in heavier fraction (residue) ( 8%)

As carboxylic acid and/or phenol In lighter and medium ends

Aliphatic monocarboxylic acids (e.g. formatic to palmitic acid)

Dicarboxylic acids

Gasoline (motor spirit)

One of most widely used petroleum product

Light distillate (B.P = 30-180C)
Prepared by mixing various components (C5-C10) produced
from refining process (e.g. atom. distillation, polymerization,
alkylation, etc.)
Constituents: normal and branched paraffins, cycloparaffins,
aromatics, olefins.
Use of additives to inhibit knocking, pre-ignition, gum formation
and icing of carburetor
Primary quality factors in spark-ignition engines: combustion,
volatility and cleanliness (w.r.t. engine & emission)
Isoparffins, cycloparaffins, aromatics: good octane numbers
Olefins: unstable for storage and gum forming tendency

8
10-03-2017

9
 10-03-2017

Volatility characteristics:
sufficient volatile fuel, easy starting, rapid warm-up and adequate
vaporization for proper distribution between cylinders
Not highly volatile to prevent excessive vapour loss from fuel tank
and vapour lock in fuel line
Can be met by using more volatile gasoline in winter than summer

Oxidation stability of gasoline:

Slow oxidation (with atmospheric air or auto oxidation) in
prolonged storage, forming gummy residue
Chain reactions in auto oxidation, producing hydroperoxides
(mainly), alcohols, aldehydes, acids, etc.
Olefins are prone to gum formation.
Darkening in colour, gum formation and insufficient performance
are symbols of storage instability of gasoline.

10
 10-03-2017

Additives used in gasoline

Anti-knocking compounds:
required to enhance the octane number
Examples: TEL, MEL, Iron carbonyl, etc.

Anti-oxidants:
Examples: alkyl phenols, phenylene diamine
Reacts peroxides to inhibit chain reactions

Metal deactivators:
To have pronounced damage on the storage quality (Certain
metals such as copper can catalyse the oxidation reactions.)
Example: ethylene diamine and propylene diamine derivatives
of disalicydene, etc.

Additives used in gasoline

Anti-icing compounds:
At high humidity and low ambient temperature, moisture in air
freeze in carburettor
Icing upset air/fuel ratio, increases fuel consumption
Cryoscopic additives lower freezing point (e.g. dipropylene
glycol, ethylene glycol mono methyl ether)
Surface active additives form protective layer at carburettor
(e.g. amides, fatty amines, etc.)

11
 10-03-2017

Diesel Oil

High speed diesel (HSD): consumed in automotive purposes

Light diesel oil (LDO): used in ships end electricity generation
India has six times demand of diesel as compared to gasoline.
Suitable B.P. range:150-400 C
Hydrocarbons present: paraffins, naphthenes, olefins and
aromatics
Carbon numbers: 12-18
Primary quality factor of concerned: combustion, volatility,
cleanliness
Cetane number: measure of ignition quality, must be > 45, high
cetane number for molecular weight normal alkane
Must be suitable for handling by injection equipment (function
of volatility, fluidity and contamination during refinement)

12
10-03-2017

13
 10-03-2017

Volatility: determinant of tendency to produce explosive

vapours, important to start and warm up
Proper viscosity to flow in pipelines, injector nozzles, etc.
Diesel should not cause deposits in fuel injector system.
Minimum pollution, corrosion and wear & tear by less S amount

Table 5.18: Fuel properties needed for

acceptable performance

14
 10-03-2017

Additives for diesel oil

Cetane improvers:
Compounds which readily decompose to give free radicals and
promotes fast oxidation of fuel
e.g. Alkyl nitrates (iso-octyl nitrate), used as about 1 lbs/10
barrels

Detergents:
Used as cleaners to remove carbonaceous and gummy
material from fuel injector and its further formation
Composed mainly of ashless amines and amides
Minimum dose = 40-50 lbs/10 barrels

Stabilizers:
Retard natural degradation of diesel in long term storage

15
 10-03-2017

Includes free-carbonaceous particulate fall out and

sedimentation sludge build up in fuel delivery system and fuel
storage tank
Different type of stabilizers, e.g.: de-emulsifier, sludge retardant,
dispersant (polyamides), rust corrosion inhibitor, metal
deactivator, anti-oxidants

Cold weather additives:

Paraffins tends to crystallize in cold and plug filters and lines.
Use of depressants, flow improvers and cloud point reducers,
reduce crystal formation rate effectively

Lubricity additives:
Low S diesel fuels has less lubricity
additive required in range of 3-8 lbs/10 barrels

Lubricating oil

Also termed as lube oil or lubricants

Basic functions: reduce friction and wear, remove heat, prevent
corrosion
Requirements: proper viscosity and fluidity, good thermal and
oxidation stability
PM, moisture, acidic combustion products enter in use of it.
Fraction which has average volatility less than gas oil
Only 2-4% of total crude processed
Blend of lubricating oil base stock and desired additives
Ranging in heavy duty to light duty, as per applications
All crudes do not provide lube oil base. Most of naphthenic
crudes are better for lube oil extraction.
Bottom residue from atmospheric distillation as feedstock for it

16
 10-03-2017

Types as per formulation method: Mineral oil based lubricants,

synthetic lubricants
Types of lube oil base stocks (Low viscosity index, medium
viscosity index and high viscosity index), See table

17
 10-03-2017

Petroleum waxes

Consists of normal and iso-paraffins and alkylated naphthenes

in range of C18-C70
Broadly classified as paraffin wax, microcrystalline wax and
petroleum
Paraffin wax: produced from waxy distillate of paraffin-base or
mixed-base crudes of high pour point
Microcrystalline wax: manufactured from distillation residue of
above crudes, waxy sludge deposited in their storage tanks
Petroleum: popularly known as vaseline, can be produced from
certain heavy distillate or residue
Recovery of these waxes from a crude depends on presence of
wax in crude, nature, quantity and the distribution of wax
content in crude.
Indian crudes are mostly suitable for paraffin and
microcrystalline waxes.

18
 10-03-2017

Paraffin waxes

Consist mainly of normal and slightly branched paraffins,

pronounced crystalline structure
Important specifications: melting point, blocking point, colour,
odour, oil content, penetration, viscosity, FDA purity etc.
Paraffin wax type 1: extra refined paraffin wax, very low oil,
used in foodstuff packaging industry and cosmetic preparation
Paraffin wax type 2: refined paraffin wax, used for candle
manufacturing, coating of paper for general packaging other
than foodstuff, polishes, water proofing formulations, processing
rubber goods, etc.
Paraffin wax type 3: semi-refined wax, comparatively soft wax,
used in impregnation of match sticks, textile, pencil industries
See table for characteristics of three types for paraffin wax

19
 10-03-2017

Microcrystalline wax

Consist considerable quantity of branched-chained

hydrocarbons
Grade I microcrystalline wax: refined type, flexible, mostly used
in lamination, sealing compounds, petroleum jellies, rust
preventives, cosmetics
Grade II microcrystalline wax: extra refined wax
Grade III microcrystalline wax: hard and higher melting point,
used in applications where low oil content is major
consideration, main application are polishes, carbon paper,
printing ink, paper coating and electrical insulation
Refer table to see properties

20
10-03-2017

21