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CHEMISTRY OF CRUDE OILS

BY
DR.Y.K.SHARMA

AN INTRODUCTION
OF
CRUDE EVALUTION LAB
THE CRUDE EVALUATION LAB IS ONE OF THE
HEART LABORATORIES OF THE INSTITUTE.
EVALUATION OF CRUDE OILS
TO

ASSESS
CHEMICAL
ACTIVITY)

THE YIELD AND PHYSICOCHARACTERISTICS


(MAIN

TO

EVALUATE THE CRUDE OILS & ITS


PETROLEUM
PRODUCTS
FOR
THE
INDIGENOUS AS WELL AS THE IMPORTED
CRUDE OILS.THE DATA GENERATED ARE
VERY MUCH USEFUL

TO

ASSESS THE QUALITY AND POTENTIAL


OF THE CRUDE OILS AND ITS PETROLEUM
PRODUCTS.

TO DESIGN THE GRASS ROOT REFINERY


TO STUDY THE CHANGE IN THE QUALITY OF THE
CRUDE OVER A PERIOD OF TIME

TO OPTIMISE THE PRODUCTION PATTERN,


SELECTION AND DESIGNING OF SECONDARY
CONVERSION UNITS.

TO UNDERSTAND THE QUALITY OF THE


PRODUCTS SO THAT THE PRODUCTS CAN BE
MARKETED WELL WITHIN THE SPECIFICATIONS
LIMITS
TO SUGGEST THE REQUIRED SECONDARY
PROCESSES TO MEET THE MARKET DEMAND.

THE LABORATORY IS WELL EQUIPPED WITH ALL


THE MODERN INSTRUMENTS FOR ASSESSING
THE QUALITY OF THE PRODUCTS MORE
PRECISELY.

CHEMISTRY OF CRUDE OILS


PETROLEUM: THE

WORD PETROLEUM IS
DERIVED FROM THE PETRA-ROCK AND
OLEUM-OILS.HENCE IT CAN BE DEFINE AS

NATURAL

OCCURING ORGANIC MATERIAL


COMPOSED OF MAINLY BY HYDROCARBONS ,
IN GASEOUS AND LIQUID STATE.

CRUDE OILS:
CRUDE OIL IS

A COMPLEX MIXTURE OF
(I.E.
PARAFFINS,
HYDROCARBONS,
NAPHTHENES & AROMATICS)
BROWNISH BLACK IN COLOUR AND
COLLOIDAL IN NATURE.

IMPURITIES:
HETEROCOMPOUNDS OF OXYGEN, SULPHUR
AND NITROGEN TRACE METALS LIKE NI, V,
Fe, AND Ce.
PHYSICALLY CRUDE OILS CAN VARY FROM
LIGHT, MOBILE, STRAIN COLOURED LIQUIDS
CONTAINING LARGE PROPORTION OF EASILY
DISTILLABLE MATERIAL TO HIGHLY VISCOUS,
SEMI SOLID BLACK SUBSTANCES WITH VERY
LITTLE MATERIAL THAT CAN BE RECOVERED
BY DISTILLATION.

ELEMENTAL COMPOSITION
OF
CRUDE OILS (%WT)
CARBON
86.8
HYDROGEN

83.911.0-14.0

SULFUR
0.06-8.00
(MORE THAN 5% IN HEAVY MISSISIPPI OR
MEXICAN CRUDES, MIDDLE EAST-5%)
NITROGEN
0.02-1.70
(0.1-0.9 % IN CALIFORNIAN &SOUTH
AMERICAN CRUDE)
OXYGEN

0.08-1.82

METALS

0.00-0.14

Main Constituents of Crude Oil


HYDROCARBONS
(COMPOUNDS COMPOSED OF C &
ACCOUNT FOR 75 % OF THE MATERIAL)
CARBON NO.DISTRIBUTIONS IN DISTILLATES
NATURAL GAS
GASOLINE
KEROSINE

PARAFFINS
C1-C4
PARAFFINS,
C5-C10
AROMATICS & NAPHTHENES
DO
C11-C18

GAS OIL

DO

C18-C28

VGO

DO

C28-C40

RESIDUE

ASPHALTIC

C40

ONWARDS

Base of the Crude Oil


1.

KEY FRACTION METHOD


Sp.Gr At 60/60 oF
Fr.1

Fr2

(250-275 oC)

(275-300oC)
40mm Hg

BASE
P

0.8251 or less

0.8762 or less

0.8251-0.8602

0.934 to 0.8762

0.8602 or heavier

0.934 or heavier

2.

CHARACTERIZATION FACTOR

3TB
Kuop = ----------------------Sp.Gr. 60/60 oF
TB = Mean Av. Boiling Point in Degree Rankin
(a) Suppose we have Crude assay distillation data
IBP
300oF
50%
440 oF
FBP
580 oF
If 50% data is available then we should consider it
as Volume Average Boiling Point (VABP)
VABP
= 440 oF
FBP-IBP
Slope of the Curve=---------------- =
100
= 2.8 oF %

580 - 300
------------100

TB(Mean Average Boiling Point) can be


determined from the curve which shows
difference to be added to VABP in Y axis vs
Slope of the assay in X axis.
From the curve this difference comes -6oF
therefore TB(Mean Average Boiling Point)
= 440+ (- 6) = 434oF
TB in Degree Rankin = 434+460=894
(b) If T20,T50,T80 data are available
VABP = (T20,+T50+,T80) / 3
Slope = (T70-T10) / 60
With this slope we calculate the difference to be
added with VABP.
(c) If T10,T50,T90 are available than
VABP = (T10+2 T50+ T90) / 4
Slope = (T70 -T10) / 60
Rest of the procedure is same as above .
BASE
P
K
12.1
I
K
11.5-12.1
N
K
11.5
KUOP was Proposed in 1937 by UOP

3. BMCI
(a) PHILIPS CARBON METHOD
BMCI
= 48640/oK+473.7 g - 456.8
g
= Sp.Gr. 60/60 oF
K
= Av. B.Pt in Degree Kelvin
(b) STONE & WEBSTER METHOD
BMCI
= 439.9 x Sp.Gr.[@ 15oC] - 333.8
(c) MURABLANK METHOD FOR BMCI
Measure Vis. in cSt.
Calculate Vis in cSt;
cSt = time in seconds. * Vis. Constant.
Convert KV in cSt between 1.81 and 500 cSt at
100oF and between 1.77 and 139.8 cSt at 210 oF, to
equivalent SUS directly from table (ASTM D-2161)
If greater than upper limit of the table at 100 oF and
210 oF than calculate as follows.
SUS = cSt * Constant (B)
Constant B= 4.632 at 100 oF and 4.664 at 210 oF
or
SUS
= (cSt + cSt2 + 176.28) / 0.452
Measure oAPI Gravity.
Derive BMCI using SUS & oAPI by Chart
BASE
BMCI
P
15
I
15-50
N
50

4. VISCOSITY GRAVITY CONSTANT

VGC

10 g - 1.0752 log (V-38)


--------------------------------10 - log (V-38)

Where as
g

Sp.Gr. 60/60 o F

S U S Viscosity

BASE
P

0.80-0.83

0.83-0.88

0.88-0.95

HYDROCARBONS:
THE

COMPOUNDS
HYDROGEN

OF

CARBON

AND

GENERAL FORMULA: CnH 2n+z


n =
z =

1,2,3..........
0,2,-2,-4,-6.......... - 30

NORMAL ALKANES OR N-PARAFFINS:


SATURATED

ALIPHATIC NORMAL CHAIN


COMPOUNDS CONSTITUTING HOMOLOGUS
SERIES OF GENERAL FORMULA CnH 2n+2.

FORMULA & BOILING POINT RANGE


OF
DIFFERENT COMPOUNDS
COMPOUNDS
ETHANE
PROPANE
N-BUTANE
N-PENTANE
N-HEXANE
N-HEPTANE
N-OCTANE
N-NONANE
N -DECANE
N-UNDECANE
N-DODECANE
N-TRIDECANE

FORMULA
(C2H6)
(C3H8)
(C4H10)
(C5H12)
(C6H14)
(C7H16)
(C8H18)
(C9H20)
(C10H22)
(C11H24)
(C12H26)
(C13H28)
etc.

BOILING
POINT OC
-88.6
-42.1
-0.5
36.1
68.8
98.4
125.7
150.9
174.0
195.8
216.3
234.0

Compounds above (C16):


THE

COMPOUNDS ABOVE

CETANE

(C16H34) i.e.

N-

ARE SOLID AT ROOM TEMPERATURE

AND SIMILAR IN NATURE TO PARAFFIN WAX.

UPTO (C40H82) i.e. TETRACONTANE


BEYOND UPTO (C100).(IN FEW CASES)
PARAFFINS ARE LOW IN HEAVY GRADED OILS
UPTO 35 % IN LIGHT CRUDES (PARAFFINIC IN
NATURE)

RELATIVELY NON REACTIVE & NON POLAR

SIGNIFICANCE :
OXIDATION OF (C8-C30) N-PARAFFINS RESULTING FATTY
ACIDS FOR SOAP INDUSTRIES

OXIDATION

OF
(C12-C14)
SECONDARY ALCOHOLS

N-PARAFFINS

RESULTING

MONO-CHLOROPARAFFINS (C10-C30) AS CUTTING OIL


ADDITIVES,
PLASTICIZERS AND FIRE
RETARDANT
CHEMICALS.
SULPHONATED

N-PARAFFINS
BIODEGRADABLE DETERGENTS

(C16-C17)

PARAFFIN WAX
FREEZING POINT IN ATF
COLD FLOW PROPERTIES OF DIESEL AND LUBES
IGNITION QUALITY OF GASOLINE AND DIESESL FUELS.

FOR

ISO PARAFFINS:
BRANCHED PARAFFINIC HYDROCARBONS
GENERAL FORMULA OF N-PARAFFINS IS
(Cn-H2n+2).
E.g.
ISO BUTANE
ISO PENTANE etc.
(C4-C33)

HAVE
PETROLEUMS

BEEN

ISOLATED

PREDOMINANT

MEMBERS
CARRY
SIMPLEST TYPE OF SIDE CHAIN i.e. CH3

HIGHEST

CONCENTRATION OF
ALKANES IN (C6-C8) RANGE.

DI

IN
THE

2-METHYLE

AND TRI SUBSTITUTED ARE LESS


ABUNDANT AND ARE MAINLY PRESENT IN
HIGHER BOILING FRACTIONS.

SIGNIFICANCE:
ISO PARAFFINS
MOST DESIRABLE COMPONENTS FOR THE
GASOLINE (DUE TO HIGH OCTANE NO.)
ATF
LUBRICATING OIL
HIGHLY

BRANCHED
ISOMERS
UNDESIRABLE IN DIESEL FUEL.

ARE

NAPHTHENES
SATURATED COMPOUNDS
APPEARS AS A RING STRUCTURES

AND ALSO
OR CYCLIC

KNOWN AS CLOSE CHAIN


SATURATED COMPOUNDS.
GENERAL FORMULA
(Cn-H2n+2)-2RN

RN = NUMBER OF NAPHTHENIC RINGS.

IN

CRUDE OIL NAPHTHENES ARE PRESENT ABOUT

50 %

BY WEIGHT AND ITS QUANTITY IS HIGHER IN HEAVIER


FRACTIONS.

THEY OCCUR

NAPHTHA
PREDOMINATED IN MOST OF THE GAS OILS
LUBRICATING OILS
CHEMICALLY HIGHLY STABLE HYDROCARBONS.
NAPHTHENES PRESENT IN THE CRUDE OILS AS
CYCLOPENTANE
CYCLOHEXANE & THEIR ALKYLATED DERIVATIVES,
CYCLOHEPTANE (B.P 118

C)

HAS

IDENTIFIED IN PETROEUM PRODUCTS.

ALSO

BEEN

AROMATIC HYDROCARBONS:
UNSATURATED CYCLIC HYDROCARBONS
GENERAL FORMULA (Cn-H2n-6) & (C2n-H2n-12).
AROMATICS

ARE FOUND ABOUT


WEIGHT IN CRUDE OILS

15 %

BY

PRESENT

AS DERIVATIVES OF BENZENE AND


POLYNUCLEAR
AROMATIC
HYDROCARBONS
(BOTH CONDENSED AND NON CONDENSED
TYPES) AND THEIR HOMOLOGUES.

THESE

HYDROCARBONS ARE CHEMICALLY


REACTIVE AND CAN FORM BOTH SUBSTITUTION
OR ADDITION PRODUCTS,

THUS

BEHAVE AS SATURATED AS WELL AS


UNSATURATED TYPE OF HYDROCARBONS.

HIGH

AMOUNTS OF POLYCYCLIC AROMATICS


ARE PRESENT IN HEAVY GAS OIL, LUBRICATING
OIL AND IN RESIDUES.

SIGNIFICANCE:
THE

OCTANE

NUMBER

OF

AROMATIC

HYDROCARBONS ARE MUCH HIGHER THAN


PARAFFINS,

ISOPARAFFINS

CYCLOPARAFFINS

OF

NUMBER

THE

THEREFORE

SAME

AS

AND
CARBON

RESULT

OF

REFORMING THE NAPHTHA BY INCREASING


THE CONCENTRATION OF AROMATICS OCTANE
NUMBER CAN BE BOOSTED.

NAPHTHENO AROMATICS
THESE

ARE
A
KIND
OF
AROMATIC
HYDROCARBONS IN WHICH AROMATIC RING IS
FUSED WITH AN ALICYCLIC RING WITH
ALIPHATIC CHAINS.Generally such type of

compounds
distillates.

are

present

in

middle

EFFECT OF COMPOSITION ON OCTANE NO.


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 cooresponding n-paraffins,
Octane number of isoparaffins incresse 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

HETERO COMPOUNDS
THE

HYDROCARBON

NITROGEN, OXYGEN

&

COMPOUNDS

CONTAINING

SULPHUR AS A CONSTITUENT

WITH CARBON AND HYDROGEN ARE KNOWN AS


HETERO HYDROCARBONS.

SULPHUR COMPOUNDS
SULPHUR

IS PRESENT IN
HYDROCARBON
TYPE
AS
HYDROCARBON TYPE.

CRUDE OILS AS
WELL
AS
NON -

IN CRUDE OILS IT VARIES FROM 0.1-3.0


BY WEIGHT BUT VALUES UPTO 7.0 %
CONTENT OF CRUDE ARE ALSO KNOWN.

PERCENT
SULPHUR

INDIAN

CRUDES ARE SWEET IN NATURE , CONTAIN


ABOUT (0.05-0.4 % BY WT.) OF SULPHUR.

NON HYDROCARBON TYPE SULPHUR


SULPHUR
ELEMENTAL
SULPHIDES.

IS

ALSO FOUND
SULPHUR
AND

IN
AS

CRUDE AS
HYDROGEN

HYDROCARBON TYPE SULPHUR


SULPHUR IS PRESENT WITH CARBON & HYDROGEN.
IT IS FOUND IN THE FORM OF
MERCAPTANS

RSH

THIOPHENES

CYCLIC
SULPHUR COMPOUNDS

SULPHIDES
DISULFIDES

RSR
RSSR

IN LOW AND MEDIUM MOLECUALR 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.

H2S (BP 61.8)

TOXIC, DISTINCT ODOUR


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

OR 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 REDUCE SULPHIDE
PRODUCTS DUE TO THEIR DISAGREEABLE
ODOUR, CORROSIVENESS, BECAUSE THEIR
COMBUSTION PRODUCES SULFUROUS AND
SULFURIC ANHYDRIDE (SO2 AND SO3)

SULPHUR COMPOUNDS IDENTIFIED IN


CRUDE FRACTION (IBP-100 oC):
COMPOUNDS

BOILING POINT OC

METHANE THIOL
ETHANE THIOL
2-THIOPROPANE
2-PROPANETHIOL
2-METHYL 2-PROPANETHIOL
2-THIOBUTANE
1-PROPANETHIOL
3-METHYL-2-THIOBUTANE
2-BUTANETHIOL
2-METHYL 1-PROPANETHIOL
3-THIOPENTANE
1-BUTANETHIOL
3,3 DIMETHYL-2-THIOBUTANE
2-METHYL-2-BUTANETHIOL

5.96
34.00
37.31
52.56
64.22
66.65
67.50
84.81
85.51
88.72
95.52
98.40
99.00
99.00

EFFECTS OF SULPHUR COMPOUNDS


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

REFORMING

POISON

CATALYST

DURING

APPLICATION OF SULPHUR COMPOUNDS:


SULPHUR

COMPOUNDS ARE NOT ALWAYS


HARMFUL TO THE PETROLEUM PRODUCTS. SOME
TIME
SULPHUR
COMPOUNDS
NATURALLY
PRESENT OR DELIBERATELY ADDED TO THE
PETROLEUM FRACTIONS.
SULPHUR COMPOUNDS ACTS AS

ANTI-OXIDANTS
ADDITIVE FOR HIGH PRESSURE LUBRICANTS
DIESEL FUEL IGNITION QUALITY IMPROVER
CETANE NO.IMPROVER
CUTTING OIL IMPROVER
DETERGENTS
ASPHALT IMROVER

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 NONBASIC IN NATURE.

BASIC NITROGEN COMPOUNDS


PYRIDINE
QUINOLINE
ISO-QUINOLINE
NON BASIC NITROGEN COMPOUNDS
PYRROLE
INDOLE
CARBAZOLE
PORPHYRINES (PYRROLE NUCLEUS)

EFFECT OF NITROGEN COMPOUNDS


IN
CRUDE OIL
NITROGEN COMPOUNDS ACTS
POISON TO THE CATALYST DUE TO BASIC
NITROGENOUS COMPOUND ADSORPTION ON
THE ACTIVE CENTRES OF THE CATALYST.

IT IS A TEMPORARY PHENOMENON.
THE COMPOUNDS ALSO IMPART ON THE
DETERIORATION

OF

THE

COLOUR

OF

PETROLEUM FRACTIONS.

QUININE & QUINALIDINE DO NOT DECOMPOSE.

OXYGEN COMPOUNDS:
OXYGEN PRESENT IN THE CRUDE OIL IS RELATIVELY
LOW VARYING FROM TRACES TO MAXIMUM 2 % BY
WEIGHT. ITS CONCENTRATION INCREASES WITH
INCREASING THE BOILING POINT THEREFORE
OXYGEN CONTENT IS FOUND ABOUT 8 % BY
WEIGHT.IN RESIDUAL OILS.

OXYGEN PRESENTS AS
FATTY ACIDS
NAPHTHENIC ACIDS (MAINLY OF CYCLOPENATNE
& CYCLOHEXANE))
PHENOLS
IN ASPHALTENES AS BRIDGE ATOM BETWEEN
POLYCYCLIC RINGD

EFFECT OF OXYGEN COMPOUNDS


IN
CRUDE OIL:
NAPHTHENIC ACIDS
CORROSIVE IN NATURE
DISTILLATION UNIT.

AND

CORRODE

THE

HIGH MOLECULAR WEIGHT NITROGEN &


SULPHUR COMPOUNDS
THESE COMPOUNDS PRESENT IN THE CRUDE OIL AS
A COMPLEX STRUCTURE KNOWN AS PORPHYRINES.
GENERALLY

THEY
ARE
ASPHALTENES, RESINS.

PRESENT

IN

THE

ASPHALTENE

MOLECULES PROBABLY CONSIST OF


SHEET COMPRISING OF SOME 10-20 PERI
CONDENSED AROMATIC RINGS LINKED WITH THE
NAPHTHENIC AND PARAFFINIC GROUPS.
ASPHALTENE MOLECULES FORM AGGRGATES

MICELLES: MOLECULAR WEIGHT


30,000
PARTICLE: MOLECULAR WEIGHT 3000-10000.
RESINS POSSESS LOWER MOLECULAR WEIGHT
(500-1200).

METALLIC DERIVATIVES
METALS FOUND IN THE ASH OF PEROLEUM
RESIDUE.AND PEROLEUMFRACTIONS AS SUCH.

ASSOCIATED IN THE BRINES WHICH IS EMULSIFIED


WITH OR AS SUCH IN CONTACT WITH THE CRUDE
OIL,

SALTS OF ORGANIC ACIDS PRESENT IN THE CRUDE


OIL, PARTICULARLY IN CASE OF NI, CU & V MAY BE
PRESENT AS ORGANIC PORPHYRINS ALSO.

METALLIC CONCENTRATION IN THE CRUDES IS


VERY OFTEN LESS THAN 0.1 % WT.

PHYSICO-CHEMICAL CHARACTERISTICS
OF CRUDE OIL:
BASIC PROPERTIES
DENSITY & API
REID VAPOUR PRESSURE
LIGHT END ANALYSIS
POUR POINT
VISCOSITY
WAX CONTENT
ASPHALTENES
CARBON RESIDUE
ASH CONTENT
DISTILLATION CHARACTERTISTICS
BASE OF CRUDE OIL

IMPURITIES:
WATER CONTENT
SALT CONTENT
BS & W
SULPHUR CONTENT
NITROGEN CONTENT
INORGANIC AND TOTAL ACID VALUE
TRACE METALS

DENSITY & o API GRAVITY:


MASS (M)
DENSITY = -----------VOLUME (V)
DENSITY OF THE
SAMPLE
SPECIFIC GRAVITY= --------------------------DENSITY OF THE
WATER
(AT SAME TEMPERATURE)
o

141.5
API GRAVITY = --------------- - 131.5
SP.GR AT 60/60oF

DENSITY

BY

DIGITAL

DENSITO-METER

(ASTM-D 4052/ IP365) FOR PETROLEUM &


ITS FRACTION
DENSITY

BY

CAPILLARY

STOPPRED

PYKNOMETER METHOD
(ASTM D-287/ IP-190)

SIGNIFICANCE
WEIGHT TO VOLUME OR VICE VERSA
CALCULATION.
CHACKNG THE CONSISTANCY OF CRUDE
SUPPLY
CONTROL OF REFINERY OPERATION
USED IN VARIOS CORRELATION
(BASE OF CRUDE OIL, BMCI,D.INDEX,NDM
METHODS ETC.
ALSO GIVES A IDEA ABOUT THE COST
ASSESSMENT OF THE CRUDE OIL

REID VAPOUR PRESSURE (ASTM D-323/ IP-69)


DEFINED AS RELATIVE PERCENTAGE
OFGASEOUS & LIGHT HYDROCARBONS
IN CRUDE OIL.
MEASURE OF HOW QUICKLY FUEL
EVAPORATES:
ITS REDUCTION PROVIDES THE
MAJORITY OF VOLATILE EMISSION
REDUCTIONS.
COMPONENT
RVP Kg/Cm2
PROPANE
BUTANE
CRUDE OIL

14.1
6.6
0.01-0.05

FOR LPG POTENTIAL


LIGHT END ANALYSIS CARRIED OUT BY
GLC FOR PERCENTAGE DISTRIBUTION
OF HYDROCARBONS UPTO C5.

SIGNIFICANCE:
VOLATILITY

AFFECTS

EVAPORATIVE

EMISSIONS AND DRIVEABILITY.


CHANGES WITH LOCATION AND SEASON.
MID SUMMER FUEL CAN NOT BE USED IN
MID WINTER.
IN

CORRECT

FUEL

MAY

RESULT

IN

DIFFICULT STARTING IN COLD WEATHER,


CARBURETOR ICING, VAPOR LOCK IN HOT
WEATHER AND CRANKCASE OIL DILUTION.

CONTROLLED

BY

DISTILLATION

SPECIFICATION.
HIGHER BOILING FRACTIONS OF GASOLINE
HAVE SIGNIFICANT EFFECT ON EMISSIONS
OF UNDESIRABLE HYDROCARBONS AND
ALDEHYDES.
4DEG REDUCTION IN FBP MAY REDUCE
LEVELS

OF

BENZENE,

BUTADIENE,

FORMALDEHYDE, ACETALDEHYDE BY 25%


AND HC BY 20 %

FOUR CLASSES OF HYDROCARBONS


USUALLY PRESENT IN PETROLEUM:
n-ALKANES
(n-PARAFFINS,Z = +2)
i-ALKANES (ISO PARAFFINS, Z = +2)
ALKYL NAPHTHENES
(CYCLO PARAFFINS, Z = 0,-2,-4 etc.)
AROMATICS ( Z = -6,-8,-10 etc.)

ALKANES:
Alkanes are the saturated aliphatic
normal or branched chain compounds
constituting homologous series of general
formula CnH 2n+2.
Alkanes are present in all crude oils
and natural gas.
Their ranges are from C1 to about C100.
They are relatively non-reactive and
non-polar.
Uniquely described by the molecular
formula upto C3 and from C4 onwards are
as isomers.

POSSIBLE NUMBER OF ISOMERS OF


NORMAL ALKANES:
CARBON
NUMBERS
5
8
10
12
15
20
25
30
35
40
45
60
80
100

nALKANES
B.Pt
(Atm.Eq.)
36
125.6
174.0
216.0
270.6
343.9
401.7
449.0
488.9
522
550
615.0
672.9
707.8

NUMBER OF
ISOMERS
3
18
75
355
4347
36.6 X 104
36.7 X 106
41.1 X 108
49.3 X 1010
62.4 X 1012
82.2 X 1014
221.5 X 1020
1056.4 X 1028
5920 X 1036

Reference: M.M.Boduszynsky, Energy &


Fuels 2,(5) 597-613,1988

POSSIBLE STRUCTURES OF NAPHTHENES


ONE RING
TWO RINGS
THREE RINGS
FOUR RINGS

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

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