Topics/Course Outline Oil Coal Natural Gas Photovoltaics Artificial Photosynthesis Batteries Fuel Cells Hydrogen Economy

Transcription

1 Topics/Course utline il Coal Natural Gas Photovoltaics Artificial Photosynthesis Batteries Fuel Cells Hydrogen Economy

2 Bond Energies 2 H = 2 H kj (1) Think of this in three steps: 2 H = 2 H E -H - 2 E H-H - E - (5) Since (1) = (5): 4 E -H - 2 E H-H - E - = 482 kj We measure E H-H (432 kj) and E - (494 kj) directly, Hence deduce E -H = 460 kj

3 Bond Energies 2 H = 2 H kj (1) Think of this in three steps: 2 H 2 = 4 H - 2 E H-H (2) 2 H = 2 H E -H - 2 E H-H - E - (5) Since (1) = (5): 4 E -H - 2 E H-H - E - = 482 kj We measure E H-H (432 kj) and E - (494 kj) directly, Hence deduce E -H = 460 kj

4 Bond Energies 2 H = 2 H kj (1) Think of this in three steps: 2 H 2 = 4 H - 2 E H-H (2) 2 = 2 - E - (3) 2 H = 2 H E -H - 2 E H-H - E - (5) Since (1) = (5): 4 E -H - 2 E H-H - E - = 482 kj We measure E H-H (432 kj) and E - (494 kj) directly, Hence deduce E -H = 460 kj

5 Bond Energies 2 H = 2 H kj (1) Think of this in three steps: 2 H 2 = 4 H - 2 E H-H (2) 2 = 2 - E - (3) 4 H + 2 = 2 H E -H (4) 2 H = 2 H E -H - 2 E H-H - E - (5) Since (1) = (5): 4 E -H - 2 E H-H - E - = 482 kj We measure E H-H (432 kj) and E - (494 kj) directly, Hence deduce E -H = 460 kj

6 Bond Dissociation Energies H-H 432 C= 1,071 = 494 C-C 347 -H 460 C=C 611 C-H 410 C--C 519 C- 360 N= 623 C= 799 N=N 941 H-H strong, but -H stronger (more ionic) C= very strong; = weaker (π* orbitals) -H stronger than C-H C-H stronger than C-C

7 Combustion H-H 432 C= 1,071 = 494 C-C 347 -H 460 C=C 611 C-H 410 C--C 519 C- 360 N= 623 C= 799 N=N 941 CH = C H 2 C= very strong; = weaker (π* orbitals) -H stronger than C-H Reaction is exothermic (120 kj/gm CH 4 )

8 Fossil Fuels: Petroleum utline: Crude il origin composition Major petroleum products Crude oil refining Gasoline additives References : n reserve Petroleum Geochemistry and Geology; John M. Hunt, 2nd ed. Petroleum Refining; Gary & Handwerk, 2nd ed. n the web

9 rigins of Crude il The origin and formation of oil is still debated; both organic and inorganic sources have been proposed Most common and accepted theory is that oil is the organic matter of ancient oceanic plants buried in oxygen-poor sediments and cooked at low temperature (< 200 C) and high pressure over millions of years

10 Accumulation and Burial of rganic Matter rganic matter (remains of plants and animals) in sediments has two main sources: marine plankton and continental plant material. Plankton, one celled plants and animals, that live in the ocean, may settle to the bottom where they accumulate. Continental organic matter, which is mostly plant material, may be washed into oceans along with sediments. Clay rich sediments are highest in organic matter, these will eventually become lithified to form shale.

11 Plant organic matter: rigins of Crude il R R R R N N R R R N N R R R R R Chlorophylls Cyclic terpanes Carotenoids < 1% of the lipids deposited in sedimentary rocks over geologic time scales provides enough organic material to account for all known petroleum reserves

12 Petroleum Maturation The most oil is produced between the temperatures of 60 and 120 degrees C, at a depth range known as the oil window.

13 Bond Dissociation Energies H-H 432 C= 1,071 = 494 C-C 347 -H 460 C=C 611 C-H 410 C--C 519 C- 360 N= 623 C= 799 N=N 941 H-H strong, but -H stronger (more ionic) C= very strong; = weaker (π* orbitals) -H stronger than C-H C-H stronger than C-C

14 Porosity and Permeability

15 100 µm Examples of Reservoir Porosity

16 Migration and Accumulation of Crude il Petroleum is formed in porous source rocks, then migrates upward through reservoir rocks to geologic structural traps by capillary action Reservoirs are sealed by gas hydrates or nonporous rocks which prevent further vertical migration seal reservoir

17 Migration Phases separate according to density, with the most dense water on the bottom, least dense gas on top and oil between the two.

18 Structural Trap-Fold Structural traps form after the sedimentary rocks are deposited, usually by tectonic forces. An anticline is where rocks are folded or bent upwards. Hydrocarbons migrate up the flanks of the anticline and are trapped in the crest.

19 Structural Trap-Fault Faults occur where there is movement along a joint or fracture. ffset of the beds could result in an impermeable layer being on top of a permeable layer.

20 Finding il Fields: Satellite Imagery This image of the Appalachian Mountains near Harrisburg PA shows the Valley and Ridge Province, an area of folded and thrust faulted sedimentary rocks

21 Finding il Fields: Aerial Photography Little Dome, WY Doubly plunging anticline

22 Finding il Fields: Geophysical Surveys/Seismic Surveys

23 Seismogram There are two structural traps in this image

24 Seismogram Structural traps occur below the A and B.

25 Seismic Analysis of Petroleum Reservoirs The American il and Gas Reporter, July 2002 Change detection very useful

26 Fields are Highly Inhomogeneous ver 1.5 million holes in Texas!

27 % World il Reserves By Region North America 18 W. Europe 57 7 Eastern Europe 3 8 Middle East Asia & ceania C./S. America 6 Africa il Source: EIA, International Energy utlook, 2002

28 Proven il Reserves Country Proven Reserves (billions of barrels) Saudi Arabia 265 Iraq 110 United Arab Emirates 100 Kuwait 95 Iran 90 Venezuela 75 Former USSR 60 Mexico 40 Libya 30 China 25 United States 23 1 boe = 42 gallons = 6.12x10 9 J 900 billion barrels = 9x10 11 x 6 x 10 9 = 4.5 x J Current burn rate: 3x10 12 W = 1.0x10 20 J/yr (3.15x10 7 s/yr) So 50 years of supply

29 Untapped US Petroleum Reserves 24.2 million acres 10.6 billion barrels 1.9 million acres 10.4 billion barrels US consumption = 7 billion barrel/yr World consumption = 29 billion barrel/yr

30 Petroleum Products: Gasoline Commercially most important petroleum product 119 billion gallons sold/year Composed of numerous compounds to vaporize under a variety of different ambient air temperatures and humidities, engine temperatures, and driving conditions Blending is changed with weather conditions, time of year, and geographical region Gasoline Composition Chevron Motor Gasolines Technical Review, 1996

31 Industry name Crude il Composition Name Chemical formula Examples Three Major Products Paraffins Alkanes C n H 2n+2 (n = 1-20) C 4 H 10 C 10 H 22 Napthenes Cycloalkanes C n H 2n (n = 1-20) C 6 H 12 C n H 2n-2 (n = 1-20) C 9 H 16 Aromatics Aromatics C 6 H 5 - R (R usually a paraffin) (CH 2 ) 10 CH 3 ther Minor Products Alkenes, Dienes Sulfides Alkenes, Dienes Thiols C n H 2n (n = 1-20) C n H 2n-2 (n = 1-20) R-S-R S

32 Crude il Composition (CH 2 ) 10 CH 3 S Crude Nigerian Light Saudi Light Saudi Heavy Venezuela Light Venezuela Heavy West Texas Sour Paraffins (% vol) Naphthenes (% vol) Aromatics (% vol) Sulfur (% wt) ctane number North Sea All Saudi oils are considered sweet, regardless of sulfur content All West Texas oils are considered sour, regardless of sulfur content Crude oil is also contaminated with small amounts of N,, heavy metals (Ni, Fe, V, Cu, As), and chloride salts (NaCl, MgCl 2, CaCl 2 ), all < 1% (wt/wt) Processing required to improve octane number

33 Compression ratio of 8:1 to 12:1

34 ctane Rating and Knocking Since PV = nrt During Compression (pre-ignition) stroke: (P 2 V 2 /P 1 V 1 ) = T 2 /T 1 Hence compression heats up the gas; We don t want preignition: knocking

35 Bond Strengths Combustion is radical chain process: -CH- + 2 = -C- + --H etc etc. Bond Dissociation Energies: Compound Bond Energy (kj/mol) Methane H 3 C-H 427 Ethane H 3 CH 2 C-H 406 Isopropane [H 3 C] 2 HC-H 393 Tertiary Butane [H 3 C] 3 C-H 381 Methanol HH 2 C-H 393 Benzene H 5 C 5 C-H 427 Toluene H 5 C 6 H 2 C-H 326 Branched chains more stable than straight chains (more -CH 3 than -CH 2 -) Aromatic C-H more stable than aliphatic C-H

36 ctane Number and Internal Combustion Engines ctane number: test measurement of how much gasoline can be compressed before it ignites spontaneously (which results in engine knocking) Compound RN Compound RN (defined) 1) 2) ctane number is determined in a laboratory using two different methods that test gasoline at city driving conditions (research octane number, RN) and highway driving conditions (motor octane number, MN). The average of the two is defined as the anti-knock index (AKI), which is the value reported at the pump. 3) 4) Chevron Motor Gasolines Technical Review, 1996

37 Diesel Fuel and the Compression-Ignition Engine Diesel fuel is ignited by spontaneous combustion of the fuel-air mixture at high pressure Diesel engines draw in air and fuel in separate strokes This allows diesel engines to control the fuel-air ratio in the ignition step, not simply the amount of fuel-air mixture as in ICE This in turn allows diesel engines to run at up to 50% efficiency, (ICE can only achieve 33% efficiency) Fuel injected after air Chevron Diesel Fuels Technical Review, 1998

38 Compression ratio 14:1 to 25:1

39 Petroleum Products: Diesel Fuel Economically important fuel because it is linked to the manufacturing and transportation industries (25 billion gallons sold/year) Fuel for compression engines Composed of paraffins, naphthenes, and aromatics with ~10-20 carbons Want facile ignition: mostly straight chain paraffins Cetane, C 16 C 34 (n-hexadecane) has a cetane number of 100, heptamethylnonane (very branched) has a cetane number of 15 Tends to form particulates because molecules near center of plume heat up before full access to 2, and carbonize (spark engine avoids this by premixing fuel and air) Chevron Diesel Fuels Technical Review, 1998

40 Beginning with 100 Barrels of Crude il

41 Fractional Distillation Gasses 20 C Representatives of all products are in all fractions, simply have different bp from fraction to fraction 40 C 100 C 200 C 400 C 500 C 600 C short hydrocarbons gasoline kerosene diesel, oil distillate heavy fuel oils asphalt, tar Crude

42 Fractional Distillation In non-polar molecules (e.g. hydrocarbons) boiling point determined by van der Waals interactions BP ( C) BP ( C) Atmospheric Distillation C 18 H Desalting Crude oil 264 Use boiling points to separate a mixture of chemically similar compounds: Distillation!

43 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees Celsius Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees Celsius Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

44 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees Celsius Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees Celsius Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

45 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / C Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees Celsius Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

46 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / C Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / C Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

47 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / C Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / C Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / C Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

48 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / C Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / C Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / C Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / C Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

49 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / C Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / C Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / C Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / C Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / C Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / > 600 C

50 Beginning with 100 Barrels of Crude il Product: 6 Barrels 3 Barrels 45 Barrels 8 Barrels 22 Barrels 16 Barrels = 100 Barrels Petroleum gas - used for heating, cooking, making plastics, often liquified under pressure to make liquified petroleum gas small alkanes (1 to 4 C), commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 C Naphtha - intermediate that will be further processed to make gasoline longer alkanes (mix of 5 to 9 carbon atoms) boiling range = 140 to 212 degrees Fahrenheit / C Gasoline - mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / C Kerosene - fuel for jet engines and tractors; starting material for making other products mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / C Gas oil or Diesel distillate - used for diesel fuel and heating oil alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / C Lubricating oil - used for motor oil, grease, other lubricants long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / C Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / C Solid residuals - coke, asphalt, tar, waxes; starting material for making other products multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / > 600 C

51 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gases Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

52 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

53

54 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

55 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

56 Vacuum Distillation Vacuum Distillation Vacuum distallates Tower residue Increase vapor pressure of heavy, non-volatile hydrocarbons by heating under vacuum Feed is residue from atmospheric distillation tower -- Hydrocarbons with 70 or more carbons, usually many-ringed compounds -- Boiling points greater than 600 C

57 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

58 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gases Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gases Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

59 Alkylation Gas Plant Separated Gasses Alkylation Alkylate Combine low FW molecules to form longer, heavier molecules that can be blended to form gasoline Basic Formula: R + R R-R Examples: + Δ catalyst Propane (C 3 H 8 ) and butane (C 4 H 10 ) are important fuel gases, but comprise a much smaller portion of the petroleum market than gasoline. They can be combined in the process of alkylation to make heptane (C 7 H 16 ), which is mixed with other longer-chain hydrocarbons to make gasoline.

60 Alkylation Gas Plant Separated Gasses Basic Formula: R + R Alkylation Alkylate R-R Combine low FW molecules to form longer, heavier molecules that can be blended to form gasoline Examples: + Δ catalyst Propane (C 3 H 8 ) and butane (C 4 H 10 ) are important fuel gases, but comprise a much smaller portion of the petroleum market than gasoline. They can be combined in the process of alkylation to make heptane (C 7 H 16 ), which is mixed with other longerchain hydrocarbons to make gasoline. + Δ catalyst = a big mess, sent back to the refinery for further processing

61 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

62 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

63 Isomerization Light crude distallate Isomerization Isomerate Convert molecules into structural isomers of the same or nearly the same FW Δ catalyst Starting materials are distallates or products from alkylation or cracking Relatively uninteresting short-chain hydrocarbons can be isomerized, or reformed, to produce important gasoline additives with higher octane numbers or better volatility

64 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

65 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

66 Reforming Reforming Reformate Polymerize and cyclize low FW alkenes + Δ catalyst + Although many reactions occur simultaneously in reforming, certain products can directed based on the reaction conditions (ie temperature and catalyst used)

67 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

68 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

69 Cracking Light cracked hydrocarbons Heavy cracked hydrocarbons Cracking 1) Cleave (or crack ) complex, high FW molecules into smaller hydrocarbons that can be blended to form gasoline 2) Ring-open napthenes 1) 2) CH 3 (CH 2 ) 18 CH 3 Δ catalyst Δ catalyst 2 Many possible products - can direct cracked products by tuning reaction conditions Products are separated by fractional distillation and sent either to be blended or to be reformed cracking is the most important process in crude oil refining

70 A Word About Catalysts Catalysts allow petroleum refining to take place at lower temperatures and direct the production of specific products The primary catalysts used in refining are platinum and rhodium metals and silica-alumina (zeolite) catalysts. These are solids over the large temperature ranges used in petroleum refining (up to 1000 F) and so can be removed from the reactors easily. Catalysts are poisoned as heavy hydrocarbons (coke), sulfides, and trace metal impurities deposit on the surface of the solid. Catalysts have to be regenerated to remove these deposits and expose a fresh catalyst surface. --remove catalyst from reactor to burn off coke at very high T --steam-striping reduces inorganic impurities so they can be rinsed off the catalyst

71 Zeolite Catalysts for Cracking Si 2 /Al 2 3 networks: an acidic solid matrix Si - Al H + H + H + Si - Al Si - Al Si -H 2 + Si Al + Si Al + Si Al + Si Brønsted Acid Lewis Acid Matrix assembles into a 3D structure: Cavity sizes vary: ~7 Å

72 Zeolite Catalysts for Cracking Zeolites catalyze formation of products based on size selectivity zeolite + hydride transfer Al H + Si H -H 2 H H

73 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

74 Desalting Crude oil Atmospheric Distillation Gasses Gas Plant Light naphtha Heavy naphtha Kerosene Middle and heavy distallates Tower residue Separated Gasses Light crude distallate Isomerization Reforming Cracked gasses Cracking Alkylation Isomerate Reformate Alkylate Light cracked hydrocarbons Heavy cracked hydrocarbons Fuel Gasses Gasoline Distallate Aviation gasoline Automotive gasoline Light Solvents and Petrochemical Feedstocks Kerosene Jet Fuels Diesel Fuel Heavy Solvents and Petrochemical Feedstocks Vacuum Distillation Vacuum distallates Tower residue Coking Asphalt Deasphalted oils Deasphalting Dewaxed oils Dewaxing Waxes Residual Residual fuel oils Lubricants Greases

75 Solvent Purification Deasphalted oils Deasphalting Dewaxing Dewaxed oils Separate asphalts and waxes from coke residues through recrystallization Just as boiling point increases with molecular weight, freezing point decreases with molecular weight -- van der Waals interactions Find examples of molecules in Aldrich - arrange similarly to distillation slide Waxes and asphalts are less branched than lubricating oils, and crystallize at higher T

76 Solvent Purification Strategy: dissolve tower residue in solvent, lower temperature of solution, collect waxes and asphalts as they crystallize out (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 Cool (CH 2 ) 40 CH 3 Filter (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 (CH 2 ) 40 CH 3 Solvents: Propane Methyl ethyl ketone (MEK) Methyl isobutyl ketone (MIBK)

77 A real refinery is actually much more complicated Chevron Motor Gasolines Technical Review, 1996

78 Emission Considerations: Reformuated Gasoline Initially Et 4 Pb or Me 4 Pb shown to reduce knocking by quenching radical formation from paraffins Pb not so good for humans to breathe Replaced by blending to generate higher octane BTX primarily through introduction of benzene Benzene is carcinogenic Xylene reacts with H radicals to help form smog better than benzene So now use oxygenates

79 Emission Considerations: xygenated Gasoline Fuel additives: oxygenates that improve combustion to increase C 2 :C ratio Helps on cold starts, also better for anti-knock BUT: lower fuel efficiency because compounds with high content have lower combustion enthalpies Two most common additives are ethanol and methyl t-butyl ether (MTBE) CH 3 CH 2 H Regulated: must be 2% by weight (15% MTBE by vol, 7.6% EtH) Ethanol common in the midwest (distilled from corn) MTBE was used in California until recently - has contaminated groundwater in much of the state But ethanol is not appropriate to use in California because it is too volatile California requested, and has been denied, oxygenate exception With MTBE, remove butanes to get volatility target, ethanol requires removal of pentanes; more expensive Next additive could be ethyl t-butyl ether (ETBE)