Petroleum Refining

Technology

Unit-2

CHEG 437
4 credit course
Paraffins
 Known as alkanes
 Saturated compounds.
 General formula is Cn H 2n+2 where n is the number of carbon atoms
 Simple alkane is methane. (first three are gases, upto C16
liquids beyond semisolid. >C30 solid blocks.
 N-paraffins or n-alkanes are unbranched straight chain
molecules.
 Isoparaffins are branched type of H/C’s that exhibit
Structural isomerism .

N-butane N-pentane i-butane

 Contd…

Name No. of C atoms Mol formula St. Formula No. of Isomers

Methane 1

Ethane 1

Propane 1

Butane 2

Pentane 3

Hexane 5

Heptane 9
 Contd…
Name No. of C atoms Mol formula St. Formula No. of Isomers

octane 18

nonane 35

decane 75

12 355

15 4347

18 60523

25 35,797,588
Properties of Paraffins:
 Paraffins are stable not attacked by H2SO4.
 Higher paraffins are insoluble in water.
 Paraffins upto 3 carbon atoms have inclination to form hydrates CH4 7
H20. C2H6 7 H2O. These offer clogging and corrosion. Hence drying is
essential before usage.
 Specific gravity of the series increases with m.wt , but still have less
than aromatics.
 Viscosity of paraffins is less but viscosity index is high in contrast to
aromatics.
 The smoke point of the paraffins is very high.
 The pour point (freezing point) of paraffins is usually high.
 Due to this paraffinic rich crudes and products bring difficulties in
transportation and storage.
 Contd….
 Isoparaffins are more reactive than n-paraffins.

 High molecular weight >C20 may be of saturated or unsaturated nature

and decompose if exposed to a tempt of 370oC.

 Vacuum distillation is essential for distilling such boiling stocks to prevent

them from thermal degradation.
Cycloalkanes (Cycloparaffins)
 Cyclic analogues of alkanes

 Naphthenes in petroleum industry

 Saturated ring H/C’s

 Cn H2n

n is the no of carbon atoms and N is the no of naphthenic rings.

Contd….
 Prominency of ring structures starts with five carbon atoms.

 Although C3 and C4 ring structures exist their stability is decreased.

 Naphthenes exhibit both the properties of saturated paraffins and

unsaturated aromatics, the result of which all the properties like
sp.gravity, viscosity, pour point, thermal characteristics lie in
between the two mentioned homologues.
 Contd….
 Multi-ring naphthenes are present in the heavier parts of the crude oil.

 Bicyclic naphthenes are important constituents of the kerosene

fractions.

 Tetra cyclic and pentacyclic compounds appear in the lubricating oil

fractions.
Olefins
 Alkenes are unsaturated H/C containing carbon-carbon double
bonds.

 Compounds containing C-C triple bonds are known or alkynes.

 General formula of alkenes CnH2n

 Acetylens Cn H2n-2

 They are more reactive than paraffins.

 The lightest alkenes are ethylene and propylene which are

important feedstocks for the petrochemical industry.
Contd….
 The first four are gases and upto C15 are liquids and beyond C15 are
solids.

 The boiling points of olefins are generally lower by few degrees.

 Chemically different.

 Easily attacked by sulphuric acid and some of them even polymerize.

 Treatment with sulphuric acid and subsequent hydrolysis yields alcohols

and with permanganate oxidation glycols are formed.

 Do not appear in measurable quantities.

 Mainly formed during cracking operations.

Aromatics
 Aromatics are unsaturated cyclic compounds composed one or
more benzene rings.

 Aromatics have a general formula is Cn H2n-6.

 They are very reactive chemically.

 The first compound in the series is benzene other simple aromatics

to follow are toluene, xylene and cumene etc…
 Contd….
 The benzene ring has three double bonds with unique electron arrangements that
made it quite stable.

 Alkyl derivatives of benzene e.g., Toluene, ethylbenzene and ortho, meta and para
xylenes are present in crude oils.

 The most common mononuclear aromatics found in crude oils are toluene and m-
xylene.
Contd….
 Aromatics have high boiling points, low pour points, high octane
numbers, high viscosity, and low viscosity index.

 Burn with red flame with much soot.

 Aromatics beyond three ring structure (anthracene) are probably

non existent.

 Aromatics usually extend their presence from a temperature of 80oC

onwards and well dominate in lower middle cuts and heavy cuts.

 Lighter aromatics do not exceed even 5% of crudes of general

nature.
 Inorganics

1. Sulfur

2. Oxygen and nitrogen

3. Less Inorganics

4. Asphalts, Resins and Bitumens

 Sulfur
 Found in most of the crudes in variable amounts.

 S compounds are present in more quantities in higher molecular weight

stocks.

 Occurs from less than 0.05 to more than 10 wt % but does not exceed 5%.

 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.

 Occurs in different forms like free S, hydrogen sulphide, mercaptans, and

thiophenes etc.

 Heavier fractions contain sulphides, polysulfides, sulphonates and sulphates.

Contd….
Mercaptans (thiols) CH3SH Methyl Mercaptan
CH3CH2CH2CH2SH n-butyl mercaptan
Sulphides R–S–R’ Dimethyl sulphide

Di sulphides R–S–S–R’ Dimethyl disulphide

Thiophenes Thiophene
Benzothiophene
Dibenzothiophene
Contd…
 Occupies prominent position in refining due to corrosion .

 Pollution problems and following Cost of waste treatment is punitive

for all refiners with high sulphur content.

 S containing residuum when cracked leaves cross linked structures.

 Presence complicates the refining and treatment methods.

Oxygen and Nitrogen
 They do not occur in free state either in crudes or in fractions.

 Nitrogen presence in free form is well known in natural gas

only.

 Oxygen occurs as oxygenated compounds like : Phenols,

cresols, naphthenic acids, sulphonates, sulphates and
sulfoxides.

 Nitrogen occurs as: Indoles, pyridines, quinolines and amines,

usually well below 2%.
Contd…
 Nitrogen compounds creates problems in processing and
stability of products.

 Catalyst deactivation, gum formation are some of the

offshoots of nitrogen.

 Most of the nitrogen pigments impart color to crude and

fractions.

 Most interesting compounds of nitrogen are porphyrins.

Asphalts, Resins and Bitumens
 Asphalts are high molecular weight complex molecules
black in color, soluble preferably in aromatic solvents and
carbon disulphide.

 Resins are mostly compounds of highly condensed ring

structures , containing oxygen , sulphur and nirtrogen

 Though bitumen is manufactured product , it is essentially

made up of three components asphalts , resins and mineral
oil.
Less Inorganics

 The other elements present are nickel, vanadium, iron , silica,

sodium , magnesium and halogens.

 Analysis not desirable as these metals exceed 0.01% yet may be

analysed for sensitive purposes.

 Ash formation is mainly due to these metals and inorganics.

 Corrosion, pollution, ash etc are mainly contributed by inorganics

and the quality of crude and fractions are always debased by these
small amounts.
Product composition
Contd…
Low boiling products

 The classification low-boiling products encompasses the

compounds which are in the gas phase at ambient
temperatures and pressures: methane, ethane, propane,
butane, and the corresponding olefins.

 Methane (C1) is usually used as a refinery fuel, but can be

used as a feedstock for hydrogen production by pyrolytic
cracking and reaction with steam.
Contd…

 Ethane (C2) can be used as refinery fuel or as a feedstock to

produce hydrogen or ethylene, which are used in
petrochemical processes.

 Ethylene and hydrogen are sometimes recovered in the

refinery and sold to petrochemical plants
Contd…

 Propane (C3) is frequently used as a refinery fuel but is also

sold as a liquefied petroleum gas (LPG).
Liquefied Petroleum Gas

 The butanes present in crude oils and produced by refinery processes

are used as components of gasoline and in refinery processing as well
as in LPG.

 Liquified petroleum gas is a group of hydrocarbon-based gases derived

from crude oil refining or natural gas fractionation.

 They include ethane, ethylene, propane, propylene, normal butane,

butylene, isobutane and isobutylene.

 For convenience of transportation, these gases are liquefied through

pressurization.

 Used as an additive for gasoline.

Gasoline
 Gasolines are complex mixtures of hydrocarbons having
typical boiling ranges from 100 to 400°F (38 to 205°C) as
determined by the ASTM method.

 Hydrocarbon range:C5-C10(mainly n-paraffins, iso paraffins,

naphthenes and aromatic hydrocarbons)

 Components are blended to promote high antiknock quality,

ease of starting, quick warm-up, low tendency to vapor lock,
and low engine deposits.
Technological Option For MS Quality
Improvement
 Hydroprocessing:

 For Sulphur production

 For benzene saturation

 For olefin production

 Isomerisation:

 For Octane Improvement

 Reforming:

 For Ocatane Improvement

 Use Of Oxygenates For Octane Improvement

 Gasoline
 Gasoline is classified by octane ratings
(Conventional, oxygenated and reformulated)
into three grades: Regular, midgrade and
Premium.

 Regular gasoline: Gasoline having an antiknock

index, i.e. octane rating, greater than or equal to
85 and less than 88.

 Mid-grade gasoline: Gasoline having octane

rating, greater than or equal to 88 and less than
or equal to 90.

 Premium gasoline: Gasoline having octane

rating greater than 90.
Distillate Fuels
 Middle Distillate fuels can be divided into three types:

 Jet or turbine fuels

 Diesel fuels

 Heating oils

 These products are blended from a variety of refinery

streams to meet the desired specifications.
Jet and Turbine Fuels
 Jet fuel is blended for use by both commercial aviation and
military aircraft.

 It is also known as turbine fuel and there are several

commercial and military jet fuel specifications.

 For most refineries the primary source of jet fuel blending

stocks is the straight-run kerosine fraction from the
atmospheric crude unit
Kerosene
 Kerosene (kerosine):also called paraffin or paraffin oil, is a
flammable pale-yellow or colorless oily liquid with a
characteristic odor.

 It is obtained from petroleum and used for burning in lamps

and domestic heaters or furnaces, as a fuel or fuel
component for jet engines, and as a solvent for greases and
insecticides.

 It is a medium oil distilling between 150 oC and 300 oC (HC:

C10-C14).
Contd….

 Kerosene has a flash point of about 25 oC (77 oF) and is suitable for use as
an illuminant when burned in a wide lamp.

 Fuel oil : any liquid or liquid petroleum product that produces heat when
burned in a suitable container or that produces power when burned in an
engine.
Kerosene Composition
 Chemically, kerosene is a mixture of hydrocarbons; the
chemical composition depends on its source, but it usually
consists of about 10 different hydrocarbons, each containing
from 10 to 16 carbon atoms per molecule;

 Kerosene is less volatile than gasoline; it boils between about

140 oC (285 oF) and 320oC (610 oF).
Contd…
 Kerosene, because of its use as a burning oil, must be free of
aromatic and unsaturated hydrocarbons, as well as free of
the more obnoxious sulfur compounds.

 The desirable constituents of kerosene are saturated

hydrocarbons, and it is for this reason that kerosene is
manufactured as a straight-run fraction, not by a cracking
process.
Aviation Turbine Fuels
 Aviation fuels consist primarily of straight and branched alkanes
and cycloalkanes.

 Aromatic hydrocarbons are limited to 20% to 25% of the total

mixture because they produce smoke when burned.

 Jet fuel comprises both gasoline and kerosene type jet fuels
meeting specifications for use in aviation turbine power units and is
often referred to as gasoline-type jet fuel and kerosene type jet fuel.

 The major jet fuels used by the military are

JP-4, JP-5, JP-6, JP-7, and JP-8.

Contd….

 JP-4 is a wide-cut fuel developed for broad availability.

 JP-6 has a higher cut than JP-4 and is characterized by fewer

impurities.

 JP-5 is specially blended kerosene, and

 JP-7 is high flash point special kerosene used in advanced

supersonic aircraft.

 JP-8 is kerosene modeled on Jet A-l fuel (used in civilian

aircraft).
Contd…
 Usually jet fuels sell at higher prices than diesel fuels and No. 1
and No. 2 heating oils, and it is more profitable for the refiner
to blend the kerosine fractions from the atmospheric crude
unit and the hydrocracker into jet fuel rather than other
products.

 Commercial jet fuel is a material in the kerosine boiling range

and must be clean burning.
AUTOMOTIVE DIESEL FUELS
 Volatility, ignition quality (expressed as cetane number or
cetane index), viscosity, sulfur content, percent aromatics,
and cloud point are the important properties of automotive
diesel fuels.

 No.1 diesel fuel ( super-diesel) is generally made from virgin

or hydrocracked stocks having cetane numbers above 45.

 It is has a boiling range from 360 to 600 °F (182 to 320 °C) and
is used in high-speed engines in automobiles, trucks, and
buses.
Contd…
 High speed engines above 1500 rpm, need high C.N 45-50.

 No.2 diesel fuel is very similar to No. 2 fuel oil, and has a wider boiling range

than No.1.

 It usually contains cracked stocks and may be blended from naphtha,

kerosine, and light cracked oils from the coker and the fluid catalytic

cracking unit.

 Limiting specifications are flash point [125 °F (52 °C)], sulfur content (0.05%

max.), distillation range, cetane number or cetane index (40 min.),percent

aromatics, and cloud point.

Diesel Cetane Number

 One key to diesel quality Measures the ability for auto-ignition

 Essentially the opposite of octane number May be measured

but frequently approximated

 ASTM D 976 —Standard Test Methods for Calculated Cetane

Index of Distillate Fuels
WORLDWIDE-DIESEL QUALITY
 Diesel Specification
NO.1 NO.2 NO.4
Minimum Cetane 40 40 30
Sulphur Current,wt% 0.5 0.5 2.0
Low Sulphur Diesel 500 ppm
Ultra Low Sulphur Diesel 15 ppm
Temp For 90% Recovery

MinimumoF 540
MaximumoF 550 640

Mostly From Virgin

Stock."SuperDiesel" Used
NO.1
For Auto & High Speed
Engines

Wider Boiling & Contain

Cracked Stock.Very
NO.2
Similar To Home Heating
Fuel(w/o additives)

Traditionally Largest
Volume Produced.Used For
NO.4 Marine,Railroads,& Other
Low To Medium Speed
Power Plant
Ignition delay
 The time interval between injection and the onset of the pressure
rise. Distillate fuels having high cetane number will show a short
ignition delay period while those fuels with poor cetane number will
give long ignition delay period.

 Rapid pressure rise results from the accumulation of fuel in the

combustion chamber during ignition delay period. And large
number of ignition points occurring throughout the fuel/air mixture

 With long ignition delay time, rapid rapid pressure rise causes
uncontrollable inefficient engine smoking.

 Rapid pressure rise results undesirable knocks, high stresses and

severe engine vibration (Diesel knocking).
Cetane Number
 The ignition properties of diesel fuels are expressed in terms of cetane
number or cetane index.

 These are very similar to the octane number (except the opposite) and
the cetane number expresses the volume percent of
cetane(C16H34,high-ignition quality =>100 CN) in a mixture with alpha-
methyl-naphthalene (C11H10, (Aromatic)low ignition quality CN= 0).

 The fuel is used to operate a standard diesel test engine according to

ASTM test method D-613. Since many refineries do not have cetane test
engines,a mathematical expression developed to estimate the cetane
number is used.
 High Cetane No: shorter ignition delay period, low pressure
rise rates and hence tend to cause less combustion noise.

 Extremely high cetane number cause incomplete combustion

because of insufficient fuel or air mixing due to very short
ignition delay period

 The higher the H/C ratio, the better the burning characteristics
(i.e., the higher the smoke point and the higher the cetane
index) To improve air quality, more severe restrictions are
placed on the sulfur and aromatic contents of diesel fuels. As
the cetane index is an indicator of the H/C ratio, it is also an
indirect indicator of the aromatic content of the diesel fuel.
 Therefore, frequently a minimum cetane index specification is
used an alternative to maximum aromatics content.Lowering
sulfur and aromatics contents specifications also lowers the
particulate emissions from diesel engines.

 Aniline point: Defined as temperature at which a liquid just

becomes completely miscible with equal volume of aniline.

 Aromatics are easily miscible=>. Low A.P

 Paraffins have high A.P.

Heating Oils
 The principal distillate fuel oils: No. 1 and No. 2 fuel oils.

 No. 1 fuel oil :very similar to kerosine, but generally has a

higher pour point and end point. Limiting specifications are
distillation, pour point, flash point, and sulfur content.

 No. 2 fuel oil:very similar to No. 2 diesel fuel, contains cracked

stock, and is blended from naphtha, kerosine, diesel, and
cracked gas oils.Limiting specifications are sulfur content,
pour point, distillation, and flash point.
Lube Oils
 Principle source: fraction left after gasoline kerosine and
diesel oil.

 ASTM Boiling point>35 oC

 Mainly composed of paraffins,Naphthenes and aromatics.

 Use: machine engine oils, turbine oils, Transformer oils

 Viscosity Index: Change in viscosity with temperature

Atmospheric Gas Oil

 ASTM end point 42oC

 Not a market product

 VGO: Product obtained from vacuum distillation unit. ASTM

boiling range 420-600 C.
Bitumen

 Residue obtained from CDU.

 Solid at room temperature. High viscosity.

 Asphalt: mixture of bitumen in oil containing mineral matter.

 Use: high way construction, water proofing coating

Residual Fuel Oils
 Residual fuel oil :composed of the heaviest parts of the crude
and is generally the fractionating tower bottoms from vacuum
distillation.

 Critical specifications:viscosity and sulfur content. Sulfur

content specifications are generally set by the locality in
which it is burned.Only low sulfur fuel oils can be burned in
some areas and this trend will continue to expand.

 Heavy fuel oils: with very low sulfur contents are much in
demand and sell at prices near those of the crude oils from
which they are derived.
Asphalt
 Mixture of Bitumen in oil containing much mineral matter

 Bitumen obtained from distillation column is poor in quality.

 Air blowing is done to obtain suitable grade.

 Use: High way construction, water proofing coating etc.