Che353-3 Petroleum Processing

7/30/2019 Che353-3 Petroleum Processing

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PETROLEUM PROCESSING

AND PETROCHEMICALS


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petroleum, crude oil

a fossil fuel, made naturally from decaying

plants and animals living in ancient seas millionsof years ago

color: from clear to tar-black,

viscosity: from water to almost solid.

mixture of hydrocarbons (over 200 differentcompounds, 1-70 carbon molecules)

i) source of energyii) starting material for synthesis of manyimportant chemical substances


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Elements and compounds found in crude oil

Carbon - 84%Hydrogen - 14%Sulfur - 1 to 3% (hydrogen sulfide, sulfides,

disulfides, elemental sulfur)Nitrogen - less than 1% (basic compounds with

aminegroups)Oxygen - less than 1% (found in organic

compounds such as carbon dioxide,phenols, ketones, carboxylic acids)

Metals - less than 1% (nickel, iron, vanadium,copper, arsenic)

Salts - less than 1% (sodium chloride, magnesiumchloride, calcium chloride)


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Hydrocarbons found in Petroleum

Alkanes, n-paraffin series (CnH2n+2)(poorantiknock properties)

Iso-alkanes, iso-paraffin series (CnH2n+2)

(high antiknock properties) Cycloalkanes, naphtene series (CnH2n)

(good antiknock properties) Aromatic, benzenoid series (CnH2n-6)

(high antiknock properties)


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TYPICAL PARAFFINS

Example ofsimplestHC molecule(CH4):

Examples of straight chain paraffin molecule (Butane) and branchedparaffin molecule (Isobutane) with same chemical formula (C4H10):

METHANE

(CH4)

BUTANE (C4H10) ISOBUTANE (C4H10)


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TYPICAL NAPHTHENES

Example of typical single-ring naphthene:

Examples of naphthene with samechemical formula (C6H12) but differentmolecular structure:

CYCLOHEXANE (C6H12) METHYL CYCLOPENTANE (C6H12)


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TYPICAL AROMATICS.

Example of simple aromaticcompound:

Examples of simple double-ring aromaticcompound:

BENZENE (C6H6) NAPTHALENE (C10H8)


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TYPICAL ALKENES (OLEFINS)

Simplest Alkene(C2H4):

Typical Alkenes with the same chemical formula(C4H8) but different molecular structures:

ETHYLENE (C2H4) 1-BUTENE (C4H8) ISOBUTENE (C4H8)

(not present in crude oil, form during cracking)


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Paraffins Aromatics Naphthenes Sulfur

API

gravity

Octane

no

(% vol) (% vol) (% vol) (% wt) (approx.) (typical)

Nigerian-Light 37 9 54 0.2 36 60

Saudi-Light 63 19 18 2 34 40

Saudi -He avy 60 15 25 2,1 28 35

Venezuela -Light 35 12 53 2,3 30 60

Venezuela-Heavy 52 14 34 1,5 24 50

USA Midcont. - - - 0.4 40 -

USA-W. Texas 46 22 32 1,9 32 55

North Sea-Brent 50 16 34 0.4 37 50

TYPICAL APPROXIMATE CHARACTERISTICS AND

PROPERTIES AND GASOLINE POTENTIAL OF VARIOUS CRUDES

(Representative average numbers)

Crude source


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API gravity : classification of

crude oil

API , low specific gravity, lighter oil

larger yields of gasoline and lightpetroleum products.


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Products of petroleumrefining


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COMMON REFINERY FRACTIONS

Natural gas Intermediate Distillates Residues

Natural gasoline Fuel oils Lubricating oils

Diesel oils Heavy fuel oils

LPG Gas oils Petrolatum

Road oilsLight Distillates Heavy Distillates Asphalts

Motor gasolines Heavy mineral oils Coke

Solvent naphtas Heavy flotation oils

Jet fuel Lubricating oils

Karosene Waxes (candles, sealing,Light heating oils insulating)


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FRACTION MADE OF BOILING RANGE USES

petroleum gas 1-4 C alkanes, alkenes less than 400 C LPG-heating, cooking,

alkenes petrochemicals

precursers ofpetrochemicals

1-10 C alkenes less than 600 C petrochemicals

naphta or ligroin

(liquid)

5-9 C alkanes 60-100 0 C solvent, processed into

gasoline

gasoline (liquid) 5-12 C alkanes, aromatics 40-205 0 C motor fuel

kerosene (liquid) 10-18 C alkanes,aromatics

175-325 0 C fuel for jet engines,

tractors, processed further

gas oil or dieseldistillate (liquid)

12 or more C

alkanes

250-350 0 C diesel fuel, heating oil

processed further

lubricating oil

(liquid)

20-50 C alkanes,

cycloalkanes, aromatics

300-370 0 C motor oil, grease, other

lubricants

heavy gas or fueloil (liquid)

20-70 C, alkanes,

cycloalkanes, aromatics

370-600 0 C ndustrial fuel, processedfurther (cracking stock)

residuals (solid) 70 and more alkanes,cycloalkanes, aromatics

larger than 600 0 C Coke, asphalt, tar, waxes

processed further

PRODUCTS OF PETROLEUM REFINING


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Natural gas

a fossil fuel, like oil and coal, a combustible mixture of hydrocarbon gases.

Most important fuel and petrochemical feedstock. considered 'dry' when it is almost pure methane,

having had most of the other commonly associatedhydrocarbons removed. When other hydrocarbons(vapors) are present, referred as 'wet'.

natural gasoline: liquid condensed from wet gas.Contains fewer higher-boiling constituents (morevolatile) as compared to straight-run gasoline

Products:gaseous fuel, LNG, He, Hydrogen,synthesis gas petrochemicals


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Methane CH4 70-90%Ethane C2H6

Propane C3H8

Butane C4H10

Carbon Dioxide CO2 0-8%

Oxygen O2 0-0.2%

Nitrogen N2 0-5%

Hydrogen

sulphide H2S 0-5%

Rare gases

A, He, Ne,

Xe trace

Typical Composition of Natural Gas

0-20%}


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Precursors of Petrochemicals

Acetylene HC CH

Ethylene H2C CH2

Propylene CH3CH CH2

Butene H2C CHCH2CH3


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Benzene

Toluene

o-Xylene

Naphthalene

CH3

CH3

CH3


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coke

Sources and uses of precursors


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GASOLINE - OCTANE NUMBER

A measure of the antiknock property of gasoline.

Determined by comparing the performance of thegasoline being tested with the performance of amixture of 2,2,4, trimethyl pentane (also called iso-octane) and normal heptane.The octane number is the percentage of iso-octanein that mixture whose performance (in regard toknocking) is the same as that of the gasoline undertest.

Example: if the performance of the gasoline under test

is the same as that of a mixture of 80% iso-octaneand 20% normal heptane, the gasoline is 80 octane.


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Major Operations of Refining Process Separation Operations

(distillation, fractionation)

Conversion Operations

i. decompositionii. unification

iii. alteration or rearrangement

Treatment operations


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OVERVIEW OF PETROLEUM REFINING PROCESSES

Process name Action Method Purpose Feedstock(s) Product(s)

FRACTIONATION PROCESSES

Atmospheric

distillation

Separation Thermal Separate

fractions

Desalted crude oil Gas, gas oil,

distillate,residual

Vacuum distillation Separation Thermal Separate w/ocracking

Atmospherictower residual

Gas oil, lubestock, residual


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CONVERSION PROCESSES-DECOMPOSITION

Catalytic

cracking

Alteration Catalytic Upgrade gasoline Gas oil, coke distillate Gasoline, petrochemical

feedstock

Coking Alteration Thermal Convert vacuumresiduals

Gas oil, coke distillate Gasoline, petrochemicalfeedstock, coke

Hydrocracking Hydrogenate Catalytic Convert to lighterHC's

Gas oil, cracked oil,residual

Lighter, higher-quality products

Steam cracking Decompose Thermal Crack largemolecules

Atm tower hvy fuel/distillate

Olefins, cracked naphtha, coke,residual

Visbreaking Decompose Thermal reduce viscosity Atmospheric towerresidual

Distillate (high in waxy residues),tar



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CONVERSION PROCESSES-UNIFICATION

Alkylation Combining Catalytic Unite olefins &isoparaffins

Tower isobutane/cracker olefin

Iso-octane (alkylate)

Grease

compounding

Combining Thermal Combine soaps & oils Lube oil, fatty acid,

alky metal

Lubricating grease

Polymerizing Polymerize Catalytic Unite 2 or moreolefins

Cracker olefins High-octane naphha,petrochemical feedstocks

CONVERSION PROCESSES-ALTERATION OR REARRANGEMENT

Catalyticreforming

Alteration/dehydration

Catalytic Upgrade low-octanenaphtha

Coker/ hydro-cracker naphtha

High oct. Reformate/ aromatic

Isomerization Rearrange Catalytic Convert straight

chain to branch

Butane, pentane,

hexane

Isobutane/ pentane/ hexane


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Amine treating Treatment Absorption Remove acidic

contaminants

Sour gas, HCs

w/CO2 & H2S

Acid free gases

& liquid HCs

Desalting Dehydration Absorption Remove

contaminants

Crude oil Desalted crude

oil

Drying &

sweetening

Treatm ent Abspt/ therm Rem ove H2O &

sulfur cmpds

Liq HCs, LPG,

alkyl feedstk.

Sweet & dry

hydrocarbons

Furfural

extraction

Solvent extr. Absorption Upgrade mid

distillate &

lubes

Cycle oils & lube

feed-stocks

High quality

diese l & lube

oil

Hydrodesulfurizat

ion

Treatment Catalytic Remove sulfur,

contaminants

High-sulfur

residual/ gas oil

Desulfurized

olefins

TREATMENT PROCESSES



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Phenol

extraction

Solvent

extr.

Abspt/

therm

Improve visc.

index, color

Lube oil base

stocks

High quality

lube oils

Solvent

deasphalting

Treatment Absorption Remove

asphalt

Vac. tower

residual,

propane

Heavy lube

oil, asphalt

Solvent

dewaxing

Treatment Cool/ filter Remove wax

from lube

stocks

Vac. tower lube

oils

Dewaxed

lube

basestock

Solvent

extraction

Solvent

extr.

Abspt/

precip.

Separate

unsat. oils

Gas oil,

reformate,

distillate

High-octane

gasoline

Sw eetening Treatment Catalytic Remove H2S,

convert

mercaptan

Untreated

distillate/

gasoline

High-quality

distillate/

gasoline

Feedstock(s) Product(s)

TREATMENT PROCESSES (continue)

Process name Action Method Purpose


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Chemical Treatments

1. Improvement of color and odor

2.

Removal of sulfur3. Removal of gums, resins and asphaltic materials

4. Improvement of light and air stability

5. Improved susceptability to additives


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Major conversion operations

1. Cracking

2. Polymerization

3. Alkylation

4. Hydrogenation

5. Hydrocracking

6. Isomerization

7. Reforming or Aromatization


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Cracking:

Splitting large hydrocarbons into smallermolecules by the action of catalysts and heat.


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Polymerization:

The linking of similar molecules, joiningtogether light olefins.


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Alkylation:The union of anolefin with anaromatic

or paraffinichydrocarbon.


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Hydrogenation:

The addition of hydrogen to an olefin


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Hydrocracking:

Splitting large hydrocarbons into smaller moleculesby the action of catalysts and heat in the presenceof hydrogen.


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Isomerization:

Alteration of the arrangement of the atoms in amolecule without changing the number of atoms.


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Reforming or aromatization:The conversion of naphtas into cyclic andaromatic compounds.


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Processing Units in Refineries

Stills (major units)

Coverters and Treatment Units Other units


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PARTS OF PIPE OR TUBE STILLS

1. Heat Exchangers

2. Furnace

3. Fractionating Tower

4. Steam Strippers5. Condensers

6. Coolers

7. Auxilliary Equipment


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Units Other Than Stills

1. Crude oil treatment units (desalting, demineralizing,removing other impurities)

2. Tanks (receiving, storing, treatments, blendingand mixing)

3. Vapor Recovery Systems4. Spill and Fire Control Systems5. Auxilliary Services (Boiler House, Electric

Generating System, Pressurized Air, WaterStation, Cooling Towers, Waste Treatment)

6. Control Room (Flow rates, temperatures andpressures monitored, regulated continuously)


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Unit Operations Used in Refining

1. Fluid Flow2. Heat Transfer3. Distillation (extractive, azeotropic)4. Absorption, steam stripping (desorption)5. Adsorption6. Crystallization7. Filtration8. Extraction


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PETROLEUM FACTS

Dnya Doal Gaz retimi (106 Ton Petrol Edeeri)


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2008 2008

2007'ye gre %

retim* 2000 2001 2002 2003 2004 2005 2006 2007 2008 Deiim

ABD 495,5 508,2 489,9 496,2 481,1 468,1 479,3 494,5 533,0 7,5% 19,3%Kanada 164,0 167,8 169,1 166,2 165,3 168,7 169,6 165,7 157,7 -5,1% 5,7%

Toplam Kuzey Amerika 692,0 707,4 690,8 695,0 680,4 671,7 695,3 708,8 740,0 4,1% 26,7%

Arjantin 33,7 33,4 32,5 36,9 40,4 41,1 41,5 40,3 39,7 -1,9% 1,4%

Trinidad & Tobago 12,6 13,7 15,6 22,3 24,6 27,3 32,8 35,1 35,4 0,5% 1,3%

Toplam Orta ve Gney Amerika 89,3 93,6 95,3 105,2 118,5 124,7 136,0 139,5 143,0 2,2% 5,2%

Norve 44,8 48,5 59,0 65,8 70,6 76,5 78,9 80,7 89,3 10,4% 3,2%

Rusy a 490,5 488,2 499,9 520,8 531,9 538,2 534,4 532,8 541,5 1,4% 19,6%

Toplam Av rupa-Asy a 862,6 869,8 889,1 921,3 949,7 954,5 945,7 947,9 978,6 2,9% 35,4%

ran 54,2 59,4 67,5 73,4 82,6 90,8 97,7 100,7 104,7 3,6% 3,8%

Katar 21,3 24,3 26,6 28,3 35,3 41,2 45,6 56,9 69,0 20,9% 2,5%

Toplam Ortadou 186,1 202,3 220,2 233,9 261,7 285,8 305,2 321,9 343,0 6,3% 12,4%

Cezay ir 76,0 70,4 72,3 74,5 73,8 79,4 76,0 76,3 77,9 1,7% 2,8%

Msr 16,5 19,3 20,4 22,5 24,2 31,2 49,2 50,1 53,0 5,4% 1,9%

Toplam Af rika 114,1 114,2 117,3 125,9 131,2 149,0 173,4 184,0 193,3 4,8% 7,0%

in 24,5 27,3 29,4 31,5 37,3 44,4 52,7 62,3 68,5 9,6% 2,5%

Endonezy a 59,1 58,1 63,6 65,5 65,5 61,8 63,2 60,9 62,7 2,7% 2,3%

Toplam Asy a Pasif ik 246,7 256,3 270,0 285,1 299,2 320,2 340,7 356,7 370,1 3,5% 13,4%

TOPLAM DNYA 2190,9 2243,6 2282,6 2366,4 2440,7 2506,0 2596,3 2658,8 2768,0 4% 100%

Kaynak: BP Statistical Review of World Energy JUNE 2009

Dnya Doal Gaz retimi (10 Ton Petrol Edeeri)

World natural Gas Production (106 Tons Oil Equivalent)

6


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2008 2008

%

retim* 2000 2001 2002 2003 2004 2005 2006 2007 2008

ABD 352,6 349,2 346,8 338,4 329,2 313,3 310,2 309,8 305,1 -1,8% 7,8%

Kanada 126,9 126,1 135,0 142,6 147,6 144,9 153,4 159,5 156,7 -2,0% 4,0%

Toplam Kuzey Amerika 650,8 651,8 660,2 669,8 667,4 645,3 646,7 642,0 619,2 -3,8% 15,8%

Brezily a 63,2 66,3 74,4 77,0 76,5 84,6 89,2 90,4 93,9 3,6% 2,4%

Venezuela 167,3 161,6 148,8 131,4 150,0 151,0 144,2 133,9 131,6 -1,9% 3,4%

Toplam Orta ve Gney Amerika 345,3 339,9 334,2 318,3 337,9 347,1 345,0 332,7 335,6 0,6% 8,5%

Norve 160,2 162,0 157,3 153,0 149,9 138,2 128,7 118,8 114,2 -4,1% 2,9%

Rusya 323,3 348,1 379,6 421,4 458,8 470,0 480,5 491,3 488,5 -0,8% 12,4%

Toplam Avrupa ve AvrupaAsya 724,7 746,6 786,0 818,9 850,1 844,8 848,1 860,0 851,0 -1,3% 21,7%

ran 189,4 186,5 172,7 203,7 209,7 210,1 211,3 209,7 209,8 -0,2% 5,3%

Sudi Arabistan 456,3 440,6 425,3 485,1 506,0 526,8 514,3 494,2 515,3 4,0% 13,1%

Toplam Ortadou 1141,2 1110,8 1039,4 1123,0 1193,1 1215,0 1223,5 1202,2 1253,7 4,0% 31,9%

Angola 36,9 36,6 44,6 42,5 48,2 61,2 69,7 84,3 92,2 9,1% 2,3%

Nijery a 105,4 110,8 102,3 110,3 121,9 125,4 120,0 114,2 105,3 -8,0% 2,7%

Toplam Af rika 370,9 374,1 378,1 397,8 440,9 467,1 473,4 488,5 488,1 -0,4% 12,4%

in 162,6 164,8 166,9 169,6 174,1 180,8 183,7 186,7 189,7 1,4% 4,8%

Endonezy a 71,5 68,0 63,0 57,7 55,2 53,0 49,9 47,4 49,1 3,2% 1,2%

Toplam Asy a Pasif ik 381,2 377,1 377,5 373,3 377,2 377,7 377,6 377,0 381,2 0,9% 9,7%

TOPLAM DNYA 3614,1 3600,3 3575,3 3701,1 3866,7 3897,0 3914,3 3902,3 3928,8 0,4% 100,0%

Kaynak: BP Statistical Review of World Energy JUNE 2009

2007'ye

Gre Deiim

Dnya Ham Petrol retimi (106 Ton)World Oil Production (106 Tons)


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Rezervuardaki Gaz

Original Gas In Place(*)

retilebilir GazRecoverable Gas

Kmlatif retimCumulative Production

Kalan retilebilir GazRemaining Recoverable Gas

23 839 226 253 18 255 174 736 12 029 895 091 6 225 279 645

2010 Yl Sonu tibariyle Trkiye Doal Gaz Rezervleri (M3)

Natural Gas Reserves Of Trkiye By The End Of 2010 (M3)

2010 YILI REZERVLER


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M.Ton

M.Tons

M.Ton

M.Tons

M.Ton

M.Tons

1 007 741 018 178 706 979 43 138 994

2010 Yl Sonu tibariyle Trkiye Ham Petrol Rezervleri

: Crude Oil Reserves Of Trkiye By The End Of 2010

2010 YILI REZERVLER

HAM PETROL

Kalan retilebilir PetrolRmn. Recoverable Oil

Rezervuardaki Petrol (*)

Original Oil In Place

retilebilir PetrolRecoverable Oil

Yllar itibariyle Trkiye Ham Petrol


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1999 2 939 896 731.098.727

2000 2 749 105 639.222.969

2001 2 551 467 311.562.545

2002 2 441 534 378.402.738

2003 2 375 044 560.633.511

2004 2 275 530 707.008.763

2005 2 281 131 896.424.950

2006 2 175 668 906.587.974

2007 2 134 175 893.055.000

2008 2 160 067 1.014.530.570

2009 2 401 799 729.414.369

2010 2 496 113 725.993.340

Yllar itibariyle Trkiye Ham Petrolretimi (M.Ton)Crude Oil Production Based On Years

(M Tons)

Yllar itibariyle Trkiye Doal Gaz retimi (M3)Natural Gas Production Of Trkiye Based On

Years (Cubic Meter)

YllarYears


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Natural Gas and Petroleum Consumption of Turkey

Years Natural Gas Consumption

(billion m3)

Petroleum Consumption

(million m.tons)

2000 14,6 24,2

2004 22,4 23,9

2009 35,7 28,2

2010 39,2 (1) 28,7 (2)

(1) 1.2% of total World Consumption

(2) 0.7% of total World Consumption


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2005 estimate 22.600


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CRUDE OIL PROCESSED IN REFINERIES ( 000 TONS)

1998 1999 2000 2001 2002

BATMAN 863 688 776 717 1,001

IZMIT 8,537 7,218 6,442 9,467 9,830

IZMIR 11,000 10,645 10,668 9,138 9,075

ATAS 3,486 3,724 2,949 3,101 2,818

OAR (KIRIKKALE) 3,248 3,900 3,392 3,463 3,416

TOTAL 27,134 26,175 24,227 25,886 26,140


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PRODUCTS OBTAINED IN TURKISH REFINERIES (TONS)

Products 1998 1999 2000 2001 2002

Refinery fuel gas 662.613 578.615 556.982 620.084 629.803

LPG 791.071 735.929 669.642 691.316 739.636

Naphtha 1 .8 75 .5 46 1 .8 81 .6 19 1 .8 51 .1 64 2 .0 26 .2 43 1 .4 53 .3 84

Normal gasoline 1.581.277 1.443.546 959.072 796.283 286.279

Super gasoline 1.296.268 1.151.495 917.650 781.132 993.348

Unleaded gasoline 678.602 703.034 801.164 1.352.626 2.428.974

Solvent 2.503 1.484 2.833 1.896 2.772

Jet fuel 1 .2 94 .2 55 1 .1 00 .1 67 1 .0 23 .5 26 1 .1 97 .4 96 1 .1 81 .3 93

Kerosene 65.464 27.741 26.241 27.073 40.363

Diesel oil 7 .7 71 .1 98 7 .7 07 .1 92 6 .6 46 .9 08 7 .3 38 .5 85 7 .4 61 .4 55

Heating oil 1 .4 49 .7 18 1 .5 58 .5 15 1 .4 58 .9 68 1 .2 07 .0 46 1 .1 60 .4 77

Fuel oil-6 6 .7 22 .5 69 6 .5 96 .0 64 6 .5 63 .1 04 7 .2 49 .9 43 6 .8 09 .0 05

Asphalt 1 .8 00 .7 99 1 .2 59 .9 36 1 .2 82 .2 65 1 .0 99 .1 14 1 .2 45 .5 74

Lube oil 324.277 327.988 317.232 248.050 298.594

H.V.G.O 218.141 218.330 456.007 557.043 485.025

Others 120.515 121.455 113.952 120.476 129.253

Total 25.992.203 24.834.495 23.089.728 24.694.322 24.715.532

CONSUMPTION OF PETROLEUM PRODUCTS IN TURKEY (TONS)


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CONSUMPTION OF PETROLEUM PRODUCTS IN TURKEY (TONS)

Products 1998 1999 2000 2001 2002

Refinery fuel gas 662.614 578.615 556.982 620.084 629.803

LPG 3 .1 74 .0 90 3 .3 38 .5 35 4 .5 46 .8 84 3 .8 51 .1 76 3 .5 00 .3 83

Naphtha 1 .6 47 .1 90 1 .5 83 .7 32 1 .5 62 .0 18 1 .5 22 .9 01 1 .6 78 .3 74

Normal gasoline 2.142.998 1.745.813 1.200.003 890.670 470.832

Super gasoline 1.469.257 1.464.362 1.068.236 739.650 933.200

Unleaded gasoline 8 62 .2 71 1 .0 96 .0 91 1 .38 7.63 9 1 .5 40 .9 78 1 .6 99 .8 19

Solvent 216.224 288.675 267.179 179.889 208.530Jet fuel 1.038.409 899.443 970.995 1.055.047 1.199.223

Kerosene 56.029 42.917 36.577 29.350 30.540

Diesel oil 6 .5 96 .6 61 7 .8 34 .1 98 8 .7 74 .2 81 8 .7 63 .8 28 9 .0 63 .4 56

Heating oil 1 .5 16 .7 97 1 .5 11 .5 16 1 .4 64 .1 70 1 .2 80 .0 98 1 .3 18 .5 10

Fuel Oil-6 6 .2 33 .5 46 5 .4 52 .1 14 6 .2 02 .1 33 6 .5 28 .9 36 6 .8 24 .0 04

Asphalt 1 .7 68 .6 36 1 .2 73 .7 62 1 .2 47 .4 15 1 .1 49 .3 39 1 .2 38 .3 57

Lube oil 368.800 387.484 489.841 335.350 412.162

Others 120.761 121.115 115.626 142.808 127.033

Total 27.211.669 27.039.757 29.332.997 28.010.020 29.334.226


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ENERGY DEMAND AND

SOURCES


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Renewable Energy Sources

Sunlight

Wind

Tides

Geothermal heat Biomass: wood, wastes, manures

Hydroelectricity

Biofuel (fermentation products)


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Che353-3 Petroleum Processing