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Petroleum Products 3

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petroleum products

by
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Prof. Ayman M.Atta


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Types of petroleum products

o LPG (C1-C4) BP 25 oC.


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o Naphthas (C5-C8) BP 60-110 oC.


o Motor spirit, petrol-gasoline (C5-C10) BP 30-65 oC.
o Kerosene (C10-C14) BP 65-170 oC.
o Aviation turbine fuel (jet) (C10-C14) BP 65-170 oC.
o Diesel fuel (gas fuel (C14-C16) BP 175-270 oC.
o Fuel oil (C16-C20) BP 275-370 oC.
o Petroleum hydrocarbon solvent
o Lubricating oil
o Petroleum waxes
o Bitumens
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o Petroleum cocke
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Petroleum refining principles


TURBISCA Crude oil and refining
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HFO
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1-LPG properties
o LPG is mixture of light hydrocarbon gaseous
(saturated and unsaturated ranged from C-3
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to C-4). It is characterized by high purity and


calorific values.
o Compostion; 90 % propane-propylene and
butane-isobutane-butylene.
o It is produced by two ways
a- extraction from natural gaseous by
(compression and cooling, adsorption and
cryogenic process which based on
refrigeration by direct expansion).
b- refining of crude oil (distillation).
o LPG is washed by caustic to remove
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mercaptane below 50 ppm.


o It was washed by amine to remove H2S.
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Petroleum refining principles


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2-Naphthas

o It is light hydrocarbons boiling in the


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gasoline range.
o It is a mixture of paraffin, olefin, naphtha
and aromatics (paraffin 32-40 %,
naphthenes 43-52%, aromatic 16-17 %)
o It is classified to:
A- light BP 60-85 oC.
B-intermediate BP 85-110 oC.
C-heavy BP 110-140 oC.
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Uses of naphtha

o Naphtha has 10-12%aromatic is used in


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fertilizer feddstock to produce synthetic


gas (CO+H2) which used as starting
material.
CH4 + H2O--- CO+H2 CH3OH
H2 + N2  NH3
o Light naphtha IS USED IN GASOLINE.
o Intermediate is used in gasoline, solvent,
ammonia production and olefine –diolefine
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production.
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o Heavy is used as solvent for dry cleaning


and thinner, mineral oil.
3- Gasoline
(motor spirit or petrol)
o Composition from C5-C10.
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o It is a mixtures of n-paraffin, isoparaffin and


cycloparaffin. BP 30-65 oC.
o Oxidation instability of gasoline mechanism
The presence of olefin initiate oxidation of gasoline
H2C=CR2  H2C. – CR3 INITIATION
H2C. – CR3 + O2  .O-O-CH2-CR3 propagation
.
O-O-CH2-CR3 +H2C=CR2  . H2C-CR2-OOCH2CR3
.
CH2-CR3 + .OOCH2CR3  R3CCH2OOCH2CR3 term
.
OOCH2CR3 + INHIBITOR (HA) HOOCH2CR3 + A.

low energy radical

o It is used as fuel.
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Octane number
antiknock quality

Octane number is defined as:


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The volume percentage of iso-octane (2,2,4-


trimethyl pentane) in a blend with n-
heptane which is equal to the test fuel
in knock intensity under standard and
closely controlled conditions of the test
in a single cylinder.
Iso-octane has octane number =100
N-heptane has octane number = 0
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The knocking in an engine may result in loss


of energy and may cause severe damage to
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engine.
Gasoline as fuel

o Spark ignition engine


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1. Gasoline is pumped from tank and delivered


to carburetor which have two function:
- metering (mixing fuel and air)
- atomization (adequate homogeneity of
the air and fuel.
2. The fuel is pumped to engine through valve
by accelerator pedal.
3. Spark start ignition of gasoline which is
based on volatility.
4. Complete ignition is responsible for high
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speed of vehicle.
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Types of gasoline additives
o Antiknock (lead alkyl) to improve octane
number.
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-1cm3 leadoctane 83, - 2cm3 86 , 3cm3 89 and 6cm3 92


o Antioxidant (phynelene diamine, alkyl
phenols) to minimize gum formation.
o Metal deactivator to prevent oxidation,
dislicylidene-propane diamine.
o Anti-icing (isopropanol, glycols).
o Detergent-dispersant.
o Combustion improver (MTBE).
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(CH3)2C=CH2 + CH3OH CH3OC(CH3)3


methyl teriary butyl ether (MTBE)
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4- kerosene
o It is fraction of BP 150-250 oC.
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o The carbon numbers are C10-C14 (naphthene,


paraffins and aromatics). Aromatics should
removed
o Liq. SO2 is used to remove aromatics from
kerosene (Edeleanu process). Aromatic and
olifine are completely miscible with liquid SO2
but naphthenes and paraffins are immiscible.
o Kerosene dose not ignite in liquid form but
ignited in vapor and converted to vapor at
heating and mixed with air
o the mechanism of combustion is based on
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heating with air to form vapour followed by


ignition.
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5. Turbine fuel (Jet)
gas turbine engine

o It is fraction having BP 150-270 oC.


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o Paraffin and naphthenes are the


major, maximuim aromatic contnt
20% and olefin 5%.
o The density should below 0.775-0.83.
o Freezing point should below -50 oC.
o Turbine fuel used in the air craft requires high
thermal stability, high heat content, low vapour
pressure, good combustion characteristics, good
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viscosity-temperature relationship, high denisty,


high specific heat.
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Performance number
octane number >100

o It is measure knock rating above 10


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octane.
o The reference fuel is blend of is-
octane and tetraethyl lead
Octane number=100+ [(performance number-100)/3]
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Jet fuel additives

o Anti oxidant (to retard peroxide formation and


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prevent gum formation).


o Metal deactivator (to remove Cu by chelate to
prevent oxidation).
o Anti-icing (to avoid freezing of dissolved water
in fuel)
o Static dissipater
o Corrosion inhibitors (amine salt of high MWt,
alkyl amino phosphate)
o Antismoke (reduce amount of smoke)
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o biocide (inhibit microbial growth in aircraft


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fuel system).
6. Diesel fuel
o It is fraction BP 150-400 oC.
o Composition C12-C18 (n- and branched
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paraffin, naphthenes low quantity of


olefine and aromatics. Water
content causes corrosion.
o Viscosity, flash point, heat of
combustion, cloud point, carbon
residue, sulphur content and heat of
combustion should be measured.
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Cetane number
ignition delay in adiesel engine
It is measure how rapidly combustion begins after injection of the
fuel into the combustion chamber.
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Hexadecane (cetane) has cetane number=100 (low ignition time).


2,2.4.4.6.8.8 heptamethyl nonane has cetane number 15 (high
ignition time)
Cetane number= %cetane + 0.15(%heptamethyl nonane)

o Centane number
1. High MWt n-alkane have high cetane number while branched
and olifin has lower cetane number.
2. High cetane number show short ignition delay period
3. Low cetane number show long ignition delay period.
4. Control start up and smoke.
5. Distillation range affect the performance (presence of high
boiling point fraction affect degree of combustion solid).
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Diesel index

Diesel index is an indication of the ignition


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quality of a diesel fuel.


Higher diesel index is better ignition quality.
Diesel index= [(aniline point oF x API)/100]

CETANE NUMBER= 0.72X DIESEL INDEX +10.


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Diesel as fuel
o It is used as fuel for train bus and ships
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o Combustion performance is function of:


1. Compression ratio
2. Fuel injection time
3. Rapid homogeneous mixing of fuel and air
4. Ignition delay time
o Diesel engine
1. Air is compressed to certain value in the clynder and raises
the temperature to 500 oC.
2. Fuel compressed in the second stage and start ignition>
3. Engine start ignition.
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SOLAR gas fuel oil
additives
o Additives are
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1.Cetane improver (isooctyl nitrite


produces radicals which initiate ignition)
2.Detergent dispersants (amines and
amides remove gum formation).
3.Pour point depressants.
4.Stabilizers (demulsifier, rust corrosion
inhibitors, sludge retardant and
antioxidant)
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5.Lubricity additives.
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7. Fuel oil (mazzout)

o It is residue remaining from


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atmospheric and vacuum distillation.


o It has viscosity 125 cSt
o Pour point 18 oC
o Sulphur content 4 %
o Flash point 66 oC
o Sediment 0.25 %
o Water content 1 %.
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8. Petroleum solvents

o Classification:
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1. Special boiling point spirits SBPS 45-160 oC


(aliphatic solvent such as hexane,
heptane).
2. Isoparaffin solvent
3. Aromatic solvent (BTX)
4. White spirit 150 -220 oC(mineral oil not
contain aromatic)
5. Dearomatic solvent 150 -250 oC.
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Manufacture of solvent
o Distillation.
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o Chemical conversion:
1. Dehydrogenation (aromatic solvent)
methyl cyclohexane  toluene +H2
2. Dehydrocyclization (aromatic, naphthenes)
n-paraffin (n-C17H36 ethylcyclopentane)
n-C17H36  Toluene +H2
3. Hydrocracking reaction with H2 (heavy ->low fraction).
n-C7H16 +H2  C4H10 +C3H8
methylcyclohexane + H2  C4H10 + C3H8
4. Isomerization (n-paraffin isoparaffin
H3CCH2CH2CH2CH2CH3  CH3CH2CH(CH3)CH2CH2CH3

CH3CH2C(CH3)2CH2CH3
ethylcyclopentane  methylcyclohexane
5. Dealkylation (toluene +H2  benzene +CH4)
6. Alkylation (reaction between isobutylene and isobutane)
o Separation (Solvent extraction)
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o Solvent treatment (finishing to remove sulfur


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and sludge)
ALKYLATION
Conversion of isobutylene and isobutane
to isooctane (gasoline).
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(CH3)2C=CH2 + H+  (CH3)3C+
(CH3)3C+ + (CH3)2C=CH2 
(CH3)3CCH2(CH3)2C+

(CH3)3CCH2(CH3)2C+ + (CH3)2CHCH3
regeneration  (CH3)3CCH2(CH3)2CH +
(CH3)3C+
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Termination (CH3)3C+  (CH3)2C=CH2 + H+


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Properties of petroleum
solvent
o It must be inert to the material which
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used to dissolve.
o Drying time should be short. High
volatile
o High solvation power
aromatic > naphthene >n-paraffin >
iso-paraffin (anilne usede to
determine the solvation power.
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o Solubility (able to dissolve solute to


flow).
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9. Lubricating oil

o It is produced from naphthene crude oil


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o Manufacture:
1. Vacuum distillation to isolate raw lube oil
fraction
2. Deasphalting
3. Solvent extraction to improve viscosity
4. Dewaxing
5. Finishing to improve colour and oxidation
stability.
6. Viscosity is important factor
High viscous lube oil increases the engine
cooling and increase fuel consumption.
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Low viscous lube oil increase lube oil


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consumption and increases engine noise.


10. Petroleum wax

o It is mixtures of n-, iso-paraffin and


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alkylated naphtenes (C18-C70).


o TYPES:
1. Paraffin wax
2. Microcrystalline (branched)
3. Petrolatum (microcrystalline+oil)
vaseline.
o Manufacture:
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1. Ketone dewaxing/deoiling used MEK.


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2. Urea adduct
11. bitumen

o It is viscous liquid or solid products. It


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solubilized in CS2
o Asphalt classified according to penetration
point
o Oxidized asphalt (rubbery)
o Hard asphalt
o Cutback bitumen (bitumen+kerosine)
o Composition
-combined carbon 82-85 %
-hydrogen 12-15 %
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2-3 % sulphur
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o It contains asphaltene (solid), maltene (oil)


and resin
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Thanks for attention


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