PETROLEUM PROCESSING AND PETROCHEMICALS

petroleum, crude oil a fossil fuel, made naturally from decaying plants and animals living in ancient seas millions of years ago color: from clear to tar-black, viscosity: from water to almost solid. mixture of hydrocarbons (over 200 different compounds, 1-70 carbon molecules)

i) source of energy ii) starting material for synthesis of many important chemical substances

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 amine groups) 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, magnesium chloride, calcium chloride)

Hydrocarbons found in Petroleum

Alkanes, n-paraffin series (CnH2n+2) (poor antiknock 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)

TYPICAL PARAFFINS
Example of simplest HC molecule (CH4): Examples of straight chain paraffin molecule (Butane) and branched paraffin molecule (Isobutane) with same chemical formula (C4H10):

METHANE (CH4)

BUTANE (C4H10)

ISOBUTANE (C4H10)

TYPICAL NAPHTHENES
Example of typical singlering naphthene: Examples of naphthene with same chemical formula (C6H12) but different molecular structure:

CYCLOHEXANE (C6H12) METHYL CYCLOPENTANE (C6H12)

TYPICAL AROMATICS.
Example of simple aromatic compound: Examples of simple double-ring aromatic compound:

BENZENE (C6H6)

NAPTHALENE (C10H8)

TYPICAL ALKENES (OLEFINS)

(not present in crude oil, form during cracking)

Simplest Alkene (C2H4):

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

ETHYLENE (C2H4)

1-BUTENE (C4H8)

ISOBUTENE (C4H8)

TYPICAL APPROXIMATE CHARACTERISTICS AND PROPERTIES AND GASOLINE POTENTIAL OF VARIOUS CRUDES
(Representative average numbers) NOctane Paraffins Aromatics Naphthenes Sulfur a no ( (% vol) (% vol) (% vol) (% wt) (approx.) % (typical) API gravity

Crude source

Nigerian-Light Saudi-Light Saudi -Heavy Venezuela -Light Venezuela-Heavy USA Midcont. USA-W. Texas North Sea-Brent

37 63 60 35 52 46 50

9 19 15 12 14 22 16

54 18 25 53 34 32 34

0.2 2 2,1 2,3 1,5 0.4 1,9 0.4

36 34 28 30 24 40 32 37 -

60 40 35 60 50 55 50

API gravity : classification of crude oil

API , low specific gravity, lighter oil larger yields of gasoline and light petroleum products.

Products of petroleum refining

COMMON REFINERY FRACTIONS

Natural gas Natural gasoline LPG Light Distillates Motor gasolines Solvent naphtas Jet fuel Karosene Light heating oils Intermediate Distillates Fuel oils Diesel oils Gas oils Heavy Distillates Heavy mineral oils Heavy flotation oils Lubricating oils Waxes (candles, sealing, insulating) Residues Lubricating oils Heavy fuel oils Petrolatum Road oils Asphalts Coke

PRODUCTS OF PETROLEUM REFINING

FRACTION
petroleum gas

MADE OF
1-4 C alkanes, alkenes

BOILING RANGE
less than 400 C

USES
LPG-heating, cooking, alkenes petrochemicals petrochemicals solvent, processed into gasoline motor fuel fuel for jet engines, tractors, processed further diesel fuel, heating oil processed further motor oil, grease, other lubricants ndustrial fuel, processed further (cracking stock) Coke, asphalt, tar, waxes processed further

precursers of petrochemicals naphta or ligroin (liquid) gasoline (liquid) kerosene (liquid)

1-10 C alkenes 5-9 C alkanes 5-12 C alkanes, aromatics 10-18 C alkanes, aromatics 12 or more C alkanes 20-50 C alkanes, cycloalkanes, aromatics 20-70 C, alkanes, cycloalkanes, aromatics 70 and more alkanes, cycloalkanes, aromatics

less than 600 C 60-100 0 C 40-205 0 C 175-325 0 C

gas oil or diesel distillate (liquid) lubricating oil (liquid) heavy gas or fuel oil (liquid) residuals (solid)

250-350 0 C 300-370 0 C 370-600 0 C

larger than 600 0 C

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 associated hydrocarbons removed. When other hydrocarbons (vapors) are present, referred as 'wet'. natural gasoline: liquid condensed from wet gas. Contains fewer higher-boiling constituents (more volatile) as compared to straight-run gasoline Products: gaseous fuel, LNG, He, Hydrogen, synthesis gas petrochemicals

Typical Composition of Natural Gas Methane Ethane Propane Butane CH4 C2H6 C3H8 C4H10 70-90%

0-20%
0-8% 0-0.2% 0-5% 0-5% trace

Carbon Dioxide CO2 Oxygen O2 Nitrogen Hydrogen sulphide Rare gases N2 H2S A, He, Ne, Xe

Precursors of Petrochemicals
Acetylene
Ethylene Propylene Butene

HC CH
H2C CH2 CH3CH CH2 H2C CHCH2CH3

Benzene

Toluene

CH3

o-Xylene

CH3 CH3

Naphthalene

Sources and uses of precursors

coke

GASOLINE - OCTANE NUMBER

A measure of the antiknock property of gasoline.
Determined by comparing the performance of the gasoline being tested with the performance of a mixture of 2,2,4, trimethyl pentane (also called isooctane) and normal heptane. The octane number is the percentage of iso-octane in that mixture whose performance (in regard to knocking) is the same as that of the gasoline under test. Example: if the performance of the gasoline under test is the same as that of a mixture of 80% iso-octane and 20% normal heptane, the gasoline is 80 octane.

Major Operations of Refining Process

Separation Operations (distillation, fractionation) Conversion Operations i. decomposition ii. unification iii. alteration or rearrangement Treatment operations

OVERVIEW OF PETROLEUM REFINING PROCESSES

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

FRACTIONATION PROCESSES Atmospheric distillation Vacuum distillation Separation Thermal Separate fractions Separate w/o cracking Desalted crude oil Gas, gas oil, distillate, residual Atmospheric tower residual Gas oil, lube stock, residual

Separation

Thermal

Process name

Action Method Purpose

Feedstock(s)

Product(s)

CONVERSION PROCESSES-DECOMPOSITION
Catalytic cracking Alteration Catalytic Upgrade gasoline Gas oil, coke distillate Gasoline, petrochemical feedstock

Coking

Alteration

Thermal Convert vacuum residuals

Gas oil, coke distillate

Gasoline, petrochemical feedstock, coke

Hydrocracking

Hydrogenate Catalytic Convert to lighter HC's Decompose Thermal Crack large molecules

Gas oil, cracked oil, residual Atm tower hvy fuel/ distillate

Lighter, higher-quality products

Steam cracking

Olefins, cracked naphtha, coke, residual

Visbreaking

Decompose Thermal reduce viscosity

Atmospheric tower residual

Distillate (high in waxy residues), tar

Process name Action

Method

Purpose

Feedstock(s)

Product(s)

CONVERSION PROCESSES-UNIFICATION Alkylation Grease compounding Polymerizing Combining Catalytic Unite olefins & isoparaffins Tower isobutane/ cracker olefin Iso-octane (alkylate) Lubricating grease High-octane naphha, petrochemical feedstocks

Combining Thermal Combine soaps & oils Lube oil, fatty acid, alky metal Polymerize Catalytic Unite 2 or more olefins Cracker olefins

CONVERSION PROCESSES-ALTERATION OR REARRANGEMENT Catalytic reforming Isomerization Alteration/ Catalytic Upgrade low-octane dehydration naphtha Rearrange Catalytic Convert straight chain to branch Coker/ hydrocracker naphtha Butane, pentane, hexane High oct. Reformate/ aromatic Isobutane/ pentane/ hexane

Process name

Action

Method

Purpose

Feedstock(s) Product(s)

TREATMENT PROCESSES Am ine treating Treatm ent Absorption Rem ove acidic contam inants Sour gas, HCs w /CO2 & H2S Crude oil Acid free gases & liquid HCs

Desalting Drying & sw eetening Furfural extraction

Dehydration Treatm ent Solvent extr.

Absorption

Hydrodesulfurizat Treatm ent ion

Rem ove contam inants Abspt/ therm Rem ove H2O & sulfur cm pds Absorption Upgrade m id distillate & lubes Catalytic Rem ove sulfur, contam inants

Desalted crude oil Liq HCs, LPG, Sw eet & dry alkyl feedstk. hydrocarbons Cycle oils & lube High quality feed-stocks diesel & lube oil High-sulfur Desulfurized residual/ gas oil olefins

Process name Action

Method

Purpose

Feedstock(s) Product(s)

TREATMENT PROCESSES (continue)

Phenol extraction Solvent deasphalting Solvent dew axing Solvent extraction Sw eetening Solvent extr. Abspt/ therm Im prove visc. Lube oil base index, color stocks Rem ove asphalt High quality lube oils

Treatm ent Absorption

Treatm ent Cool/ filter

Solvent extr.

Abspt/ precip.

Treatm ent Catalytic

Vac. tow er Heavy lube residual, oil, asphalt propane Rem ove w ax Vac. tow er lube Dew axed from lube oils lube stocks basestock Separate Gas oil, High-octane unsat. oils reform ate, gasoline distillate Rem ove H2S, Untreated High-quality convert distillate/ distillate/ m ercaptan gasoline gasoline

Chemical Treatments
1.
2. 3. 4. 5.

Improvement of color and odor Removal of sulfur Removal of gums, resins and asphaltic materials Improvement of light and air stability Improved susceptability to additives

Major conversion operations

1. 2. 3. 4. 5. 6. 7.

Cracking Polymerization Alkylation Hydrogenation Hydrocracking Isomerization Reforming or Aromatization

Cracking:
Splitting large hydrocarbons into smaller molecules by the action of catalysts and heat.

Polymerization:
The linking of similar molecules, joining together light olefins.

Alkylation:

The union of an olefin with an aromatic or paraffinic hydrocarbon.

Hydrogenation:
The addition of hydrogen to an olefin

Hydrocracking:
Splitting large hydrocarbons into smaller molecules by the action of catalysts and heat in the presence of hydrogen.

Isomerization:
Alteration of the arrangement of the atoms in a molecule without changing the number of atoms.

Reforming or aromatization:

The conversion of naphtas into cyclic and aromatic compounds.

Processing Units in Refineries

Stills (major units) Coverters and Treatment Units Other units

PARTS OF PIPE OR TUBE STILLS

1.

2.
3. 4. 5. 6. 7.

Heat Exchangers Furnace Fractionating Tower Steam Strippers Condensers Coolers Auxilliary Equipment

Units Other Than Stills

1.
2. 3. 4. 5.

6.

Crude oil treatment units (desalting, demineralizing, removing other impurities) Tanks (receiving, storing, treatments, blending and mixing) Vapor Recovery Systems Spill and Fire Control Systems Auxilliary Services (Boiler House, Electric Generating System, Pressurized Air, Water Station, Cooling Towers, Waste Treatment) Control Room (Flow rates, temperatures and pressures monitored, regulated continuously)

Unit Operations Used in Refining

1.

2.
3. 4. 5. 6. 7. 8.

Fluid Flow Heat Transfer Distillation (extractive, azeotropic) Absorption, steam stripping (desorption) Adsorption Crystallization Filtration Extraction

PETROLEUM FACTS

Dnya Doal Gaz retimi (106 Ton Petrol Edeeri) World natural Gas Production (106 Tons Oil Equivalent) 2008 2008 2007'ye gre % 2000 2001 2002 2003 2004 2005 2006 2007 2008 Deiim
495,5 164,0 692,0 33,7 12,6 89,3 44,8 490,5 862,6 54,2 21,3 186,1 76,0 16,5 114,1 24,5 59,1 246,7 508,2 167,8 707,4 33,4 13,7 93,6 48,5 488,2 869,8 59,4 24,3 202,3 70,4 19,3 114,2 27,3 58,1 256,3 489,9 169,1 690,8 32,5 15,6 95,3 59,0 499,9 889,1 67,5 26,6 220,2 72,3 20,4 117,3 29,4 63,6 270,0 496,2 166,2 695,0 36,9 22,3 105,2 65,8 520,8 921,3 73,4 28,3 233,9 74,5 22,5 125,9 31,5 65,5 285,1 481,1 165,3 680,4 40,4 24,6 118,5 70,6 531,9 949,7 82,6 35,3 261,7 73,8 24,2 131,2 37,3 65,5 299,2 468,1 168,7 671,7 41,1 27,3 124,7 76,5 538,2 954,5 90,8 41,2 285,8 79,4 31,2 149,0 44,4 61,8 320,2 479,3 169,6 695,3 41,5 32,8 136,0 78,9 534,4 945,7 97,7 45,6 305,2 76,0 49,2 173,4 52,7 63,2 340,7 494,5 165,7 708,8 40,3 35,1 139,5 80,7 532,8 947,9 100,7 56,9 321,9 76,3 50,1 184,0 62,3 60,9 356,7 533,0 157,7 740,0 39,7 35,4 143,0 89,3 541,5 978,6 104,7 69,0 343,0 77,9 53,0 193,3 68,5 62,7 370,1 7,5% -5,1% 4,1% -1,9% 0,5% 2,2% 10,4% 1,4% 2,9% 3,6% 20,9% 6,3% 1,7% 5,4% 4,8% 9,6% 2,7% 3,5% 4% 19,3% 5,7% 26,7% 1,4% 1,3% 5,2% 3,2% 19,6% 35,4% 3,8% 2,5% 12,4% 2,8% 1,9% 7,0% 2,5% 2,3% 13,4% 100%

retim*
ABD Kanada Toplam Kuzey Amerika Arjantin Trinidad & Tobago Toplam Orta v e Gney Amerika Norv e Rusy a Toplam Av rupa-Asy a ran Katar Toplam Ortadou Cezay ir Msr Toplam Af rika in Endonezy a Toplam Asy a Pasif ik TOPLAM DNY A

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

Kaynak: BP Statistical Review of World Energy JUNE 2009

Dnya Ham Petrol retimi (106 Ton) World Oil Production (106 Tons) 2008 2008 % 2007'ye 2007 2008 Gre Deiim
309,8 159,5 642,0 90,4 133,9 332,7 118,8 491,3 860,0 209,7 494,2 84,3 114,2 488,5 186,7 47,4 377,0 305,1 156,7 619,2 93,9 131,6 335,6 114,2 488,5 851,0 209,8 515,3 92,2 105,3 488,1 189,7 49,1 381,2 -1,8% -2,0% -3,8% 3,6% -1,9% 0,6% -4,1% -0,8% -1,3% -0,2% 4,0% 4,0% 9,1% -8,0% -0,4% 1,4% 3,2% 0,9% 0,4% 7,8% 4,0% 15,8% 2,4% 3,4% 8,5% 2,9% 12,4% 21,7% 5,3% 13,1% 31,9% 2,3% 2,7% 12,4% 4,8% 1,2% 9,7% 100,0%

retim*
ABD Kanada Toplam Kuzey Amerika Brezily a Venezuela Toplam Orta v e Gney Amerika Norv e Rusy a Toplam Av rupa v e Av rupaAsy a ran Sudi Arabistan Toplam Ortadou Angola Nijery a Toplam Af rika in Endonezy a Toplam Asy a Pasif ik TOPLAM DNY A

2000 2001 2002 2003 2004 2005 2006

352,6 126,9 650,8 63,2 167,3 345,3 160,2 323,3 724,7 189,4 456,3 36,9 105,4 370,9 162,6 71,5 381,2 349,2 126,1 651,8 66,3 161,6 339,9 162,0 348,1 746,6 186,5 440,6 36,6 110,8 374,1 164,8 68,0 377,1 346,8 135,0 660,2 74,4 148,8 334,2 157,3 379,6 786,0 172,7 425,3 44,6 102,3 378,1 166,9 63,0 377,5 338,4 142,6 669,8 77,0 131,4 318,3 153,0 421,4 818,9 203,7 485,1 42,5 110,3 397,8 169,6 57,7 373,3 329,2 147,6 667,4 76,5 150,0 337,9 149,9 458,8 850,1 209,7 506,0 48,2 121,9 440,9 174,1 55,2 377,2 313,3 144,9 645,3 84,6 151,0 347,1 138,2 470,0 844,8 210,1 526,8 61,2 125,4 467,1 180,8 53,0 377,7 310,2 153,4 646,7 89,2 144,2 345,0 128,7 480,5 848,1 211,3 514,3 69,7 120,0 473,4 183,7 49,9 377,6

1141,2 1110,8 1039,4 1123,0 1193,1 1215,0 1223,5 1202,2 1253,7

3614,1 3600,3 3575,3 3701,1 3866,7 3897,0 3914,3 3902,3 3928,8

Kaynak: BP Statistical Review of World Energy JUNE 2009

2010 Yl Sonu tibariyle Trkiye Doal Gaz Rezervleri (M3) Natural Gas Reserves Of Trkiye By The End Of 2010 (M 3)

Rezervuardaki Gaz Original Gas In Place(*)

retilebilir Gaz Recoverable Gas

Kmlatif retim Cumulative Production

Kalan retilebilir Gaz Remaining Recoverable Gas

23 839 226 253

18 255 174 736

12 029 895 091

6 225 279 645

2010 YILI REZERVLER HAM PETROL

2010 Yl Sonu tibariyle Trkiye Ham Petrol Rezervleri : Crude Oil Reserves Of Trkiye By The End Of 2010
Rezervuardaki Petrol (*) Original Oil In Place retilebilir Petrol Recoverable Oil Kalan retilebilir Petrol Rmn. Recoverable Oil

M.Ton M.Tons

M.Ton M.Tons

M.Ton M.Tons

1 007 741 018

178 706 979

43 138 994

Yllar Years
1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Yllar itibariyle Trkiye Ham Petrol retimi (M.Ton) Crude Oil Production Based On Years (M Tons)
2 939 896 2 749 105 2 551 467 2 441 534 2 375 044 2 275 530 2 281 131 2 175 668 2 134 175 2 160 067 2 401 799 2 496 113

Yllar itibariyle Trkiye Doal Gaz retimi (M3) Natural Gas Production Of Trkiye Based On Years (Cubic Meter)
731.098.727 639.222.969 311.562.545 378.402.738 560.633.511 707.008.763 896.424.950 906.587.974 893.055.000 1.014.530.570 729.414.369 725.993.340

Natural Gas and Petroleum Consumption of Turkey

Years
2000 2004 2009 2010

Natural Gas Consumption (billion m3)

14,6 22,4 35,7 39,2 (1)

Petroleum Consumption (million m.tons)

24,2 23,9 28,2 28,7 (2)

(1) (2)

1.2% of total World Consumption 0.7% of total World Consumption

2005 estimate 22.600

CRUDE OIL PROCESSED IN REFINERIES ( 000 TONS)

BATMAN IZMIT IZMIR ATAS OAR (KIRIKKALE) TOTAL 1998 863 8,537 11,000 3,486 3,248 27,134 1999 688 7,218 10,645 3,724 3,900 26,175 2000 776 6,442 10,668 2,949 3,392 24,227 2001 717 9,467 9,138 3,101 3,463 25,886 2002 1,001 9,830 9,075 2,818 3,416 26,140

PRODUCTS OBTAINED IN TURKISH REFINERIES (TONS) Products

Refinery fuel gas LPG Naphtha Normal gasoline S uper gasoline Unleaded gasoline S olvent Jet fuel Kerosene Diesel oil Heating oil Fuel oil-6 Asphalt Lube oil H.V.G.O Others

1998
662.613 791.071 1.875.546 1.581.277 1.296.268 678.602 2.503 1.294.255 65.464 7.771.198 1.449.718 6.722.569 1.800.799 324.277 218.141 120.515

1999
578.615 735.929 1.881.619 1.443.546 1.151.495 703.034 1.484 1.100.167 27.741 7.707.192 1.558.515 6.596.064 1.259.936 327.988 218.330 121.455

2000
556.982 669.642 1.851.164 959.072 917.650 801.164 2.833 1.023.526 26.241 6.646.908 1.458.968 6.563.104 1.282.265 317.232 456.007 113.952

2001
620.084 691.316 2.026.243 796.283 781.132 1.352.626 1.896 1.197.496 27.073 7.338.585 1.207.046 7.249.943 1.099.114 248.050 557.043 120.476

2002
629.803 739.636 1.453.384 286.279 993.348 2.428.974 2.772 1.181.393 40.363 7.461.455 1.160.477 6.809.005 1.245.574 298.594 485.025 129.253

Total

25.992.203 24.834.495 23.089.728 24.694.322 24.715.532

CONSUMPTION OF PETROLEUM PRODUCTS IN TURKEY (TONS) Products

Refinery fuel gas LPG Naphtha Normal gasoline S uper gasoline Unleaded gasoline S olvent Jet fuel Kerosene Diesel oil Heating oil Fuel Oil-6 Asphalt Lube oil Others

1998
662.614 3.174.090 1.647.190 2.142.998 1.469.257 862.271 216.224 1.038.409 56.029 6.596.661 1.516.797 6.233.546 1.768.636 368.800 120.761

1999
578.615 3.338.535 1.583.732 1.745.813 1.464.362 1.096.091 288.675 899.443 42.917 7.834.198 1.511.516 5.452.114 1.273.762 387.484 121.115

2000
556.982 4.546.884 1.562.018 1.200.003 1.068.236 1.387.639 267.179 970.995 36.577 8.774.281 1.464.170 6.202.133 1.247.415 489.841 115.626

2001
620.084 3.851.176 1.522.901 890.670 739.650 1.540.978 179.889 1.055.047 29.350 8.763.828 1.280.098 6.528.936 1.149.339 335.350 142.808

2002
629.803 3.500.383 1.678.374 470.832 933.200 1.699.819 208.530 1.199.223 30.540 9.063.456 1.318.510 6.824.004 1.238.357 412.162 127.033

Total

27.211.669 27.039.757 29.332.997 28.010.020 29.334.226

ENERGY DEMAND AND

SOURCES

Renewable Energy Sources

Sunlight Wind Tides Geothermal heat Biomass: wood, wastes, manures Hydroelectricity Biofuel (fermentation products)