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® petroleum products

byProf. Ayman M.Atta

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Types of petroleum products

o LPG (C1-C4) BP 25 oC.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 oilo Petroleum waxeso Bitumenso Petroleum cocke

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Petroleum refining principles

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HFO

Crude oil and refining

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1-LPG propertieso LPG is mixture of light hydrocarbon

gaseous (saturated and unsaturated ranged from C-3 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 waysa- 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

mercaptane below 50 ppm.o It was washed by amine to remove H2S.

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Petroleum refining principles

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LPG fuel

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2-Naphthas

o It is light hydrocarbons boiling in the 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 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 production.

o Heavy is used as solvent for dry cleaning and thinner, mineral oil.

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3- Gasoline(motor spirit or petrol)

o Composition from C5-C10.

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 numberantiknock quality

Octane number is defined as: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 =100N-heptane has octane number = 0The knocking in an engine may result in loss

of energy and may cause severe damage to engine.

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Gasoline as fuel

o Spark ignition engine1. 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

speed of vehicle.

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Types of gasoline additiveso Antiknock (lead alkyl) to improve octane

number. -1cm3 leadoctane 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).(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.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 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.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 viscosity-temperature relationship, high denisty, high specific heat.

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Performance numberoctane number >100

o It is measure knock rating above 10 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 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 dissipatero Corrosion inhibitors (amine salt of high

MWt, alkyl amino phosphate)o Antismoke (reduce amount of smoke)o biocide (inhibit microbial growth in aircraft

fuel system).

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6. Diesel fuel

o It is fraction BP 150-400 oC.

o Composition C12-C18 (n- and branched 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 numberignition delay in adiesel engine

It is measure how rapidly combustion begins after injection of the fuel into the combustion chamber.

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 number1. 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 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 shipso Combustion performance is function of:1. Compression ratio2. Fuel injection time3. Rapid homogeneous mixing of fuel and

air4. Ignition delay time

o Diesel engine1. 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

additiveso Additives are1.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)

5.Lubricity additives.

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7. Fuel oil (mazzout)

o It is residue remaining from atmospheric and vacuum distillation.

o It has viscosity 125 cSto Pour point 18 oCo Sulphur content 4 %o Flash point 66 oCo Sediment 0.25 %o Water content 1 %.

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8. Petroleum solvents

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

oC (aliphatic solvent such as hexane, heptane).

2. Isoparaffin solvent3. 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.o Chemical conversion:1. Dehydrogenation (aromatic solvent)

methyl cyclohexane toluene +H22. 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)o Solvent treatment (finishing to remove

sulfur and sludge)

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ALKYLATION

Conversion of isobutylene and isobutane to isooctane (gasoline).

(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+

Termination (CH3)3C+ (CH3)2C=CH2 + H+

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® Properties of petroleum

solvent

o It must be inert to the material which 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.

o Solubility (able to dissolve solute to flow).

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9. Lubricating oil

o It is produced from naphthene crude oilo Manufacture:1. Vacuum distillation to isolate raw lube oil

fraction2. Deasphalting3. Solvent extraction to improve viscosity4. Dewaxing5. Finishing to improve colour and oxidation

stability.6. Viscosity is important factorHigh viscous lube oil increases the engine

cooling and increase fuel consumption.Low viscous lube oil increase lube oil

consumption and increases engine noise.

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10. Petroleum wax

o It is mixtures of n-, iso-paraffin and alkylated naphtenes (C18-C70).

o TYPES:1. Paraffin wax2. Microcrystalline (branched)3. Petrolatum (microcrystalline+oil)

vaseline.o Manufacture:1. Ketone dewaxing/deoiling used MEK.2. Urea adduct

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11. bitumen

o It is viscous liquid or solid products. It solubilized in CS2

o Asphalt classified according to penetration point

o Oxidized asphalt (rubbery)o Hard asphalto Cutback bitumen (bitumen+kerosine)o Composition-combined carbon 82-85 %-hydrogen 12-15 %2-3 % sulphuro It contains asphaltene (solid), maltene (oil)

and resin

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Thanks for attention