383
T.K. Ghosh and M.A. Prelas, Energy Resources and Systems:
Volume 1: Fundamentals and Non-Renewable Resources, 383•451.
© Springer Science + Business Media B.V. 2009
8 PETROLEUM
Abstract
Petroleum dominates the world economy. No other commodity affects everyday
life the way petroleum does. Although more than 70% of petroleum is used for
transportation, it is an essential raw material for making a variety of products that
we use in our everyday life. Petroleum is a complex chemical mixture and its trade
and also processing depend on its physical and chemical properties. Crude petroleum
pumped out from the underground reservoirs goes through a number of
processing steps before the final products are obtained and sold to the public. The
main objective of the processing is to maximize the yield of transportation fuels.
Exploration, extraction from underground reservoirs, benchmarking and processing
of crude petroleum are discussed in this chapter.
8.1 Introduction
The word •petroleum• comes from the Latin words petra, (or rock), and oleum,
(oil). Oil is found in reservoirs in sedimentary rocks. Tiny pores in the rock
allowed the petroleum to seep in. These •reservoir rocks• hold the oil like a
sponge, confined by other non-porous layers that form a •trap.•
According to the most widely accepted theory, oil is composed mainly of
hydrocarbons, and was formed millions of years ago in a process that began when
aquatic plant and animal remains were covered by layers of sediment • particles of
rock and mineral. Over millions of years of extreme pressure and high temperatures,
these particles became the mix of liquid hydrocarbons that we know as oil.
Different mixes of plant and animal remains, as well as pressure, heat, and time,
have caused hydrocarbons to appear today in a variety of forms: crude oil, a liquid;
natural gas, a gas; and coal, a solid. Although the major consumption of oil is in
transportation sector, as can be seen from Table 8.1, petroleum or oil is the key
raw material for a variety of other consumer products.
384 8 Petroleum
Table 8.1. Products that use petroleum as the starting raw material for their manufacturing.
Commercial products
Ink Dishwashing liquids Paint brushes Cameras
Telephones Toys Unbreakable dishes Combs
Insecticides Antiseptics Dolls Dice
Car sound insulation Fishing lures Mops
Deodorant Tires Motorcycle helmets Purses
Linoleum Sweaters Tents Dresses
Refrigerator linings Paint rollers Pajamas
Floor wax Shoes Electrician$s tape Pillows
Plastic wood Model cars Glue Candles
Roller-skate wheels Trash bags Ice buckets
Hand Lotion Clothesline Dyes Crayons
Soft contact lenses Shampoo Panty hose Caulking
Food preservatives
Transparent tape
Disposable diapers
Sports car bodies
Electric blankets
Car battery cases
Synthetic rubber
Vitamin capsules
Rubbing alcohol
Ice cube trays
Insect repellent
Roofing shingles
Balloons
Umbrellas
Beach umbrellas
Putty
Hair coloring
Drinking cups
Yarn
Golf bags
Roofing
LP records
Skis
Fishing rods
Anesthetics
TV cabinets
Salad bowls
Awnings
Safety glass
VCR tapes
Movie film
Loudspeakers
Credit cards
Water pipes
Fishing boots
Shower curtains
Curtains
Detergents
Rubber cement
Nail polish
Petroleum jelly
Shower doors
Vaporizers
Folding doors
Hearing aids
Permanent press
clothes
Oil filters
Upholstery
Cassettes
House paint
Ammonia
Hair curlers
Eyeglasses
Ice chests
Fertilizers
Toilet seats
Toothbrushes
Wire insulation
Fan belts
Heart valves
Aspirin
Bandages
Guitar strings
Luggage
Artificial turf
Wading pools
Ballpoint pens
Shaving cream
Soap dishes
Life jackets
Garden hose
Plywood adhesive
Milk jugs
Sun glasses
Cold cream
Antihistamines
Slacks
False teeth
Toothpaste
Golf balls
Cortisone
Artificial limbs
Parachutes
Faucet washers
Tool racks
Tennis rackets
Shoe polish
Lipstick
Perfume
Carpeting
Soap dishes
8.2 Consumption of Oil 385
8.2 Consumption of Oil
No other commodity dominates modern society in the way the oil does. Oil not
only drives the global economy, it also controls our life style. Table 8.2 shows the
oil consumption by various countries. World oil consumption increased by 2% in
2003, followed by a 4% increase in 2004. The 4% rise in 2004 was the largest
yearly increase in a quarter-century. This sudden unexpected increase in oil consumption
in 2004 year was due to the rapid growth of oil use in the United States
and East Asia, notably China. In 2005, growth of world oil consumption slowed to
1.5%, partly reflecting the restraining effects of higher prices. Nonetheless, the
level of oil consumption is still high relative to earlier expectations. The demand is
expected to remain strong because its consumption is directly related to the global
economy. As can be seen from the table, although the consumption of oil in the
USA decreased in 2005, the world consumption increased by 1%. The worldwide
crude oil demand for 2006 was estimated to be around 84.83 million barrels a day,
or a growth of about 1.5%. Most of the increase in the output came from the
OPEC (Organization of the Petroleum Exporting Countries) who pumped additional
170,000 barrels a day in April, increasing its output to 30.04 million barrels
a day.
Table 8.2. Oil consumption by the countries (million barrels per day).
share
2002 2003 2004 2005 2006
Change
2006 over
2005 of total
USA 19,761 20,033 20,731 20,802 20,589 •1.3% 24.1%
Canada 2,067 2,132 2,248 2,247 2,222 •1.5% 2.5%
Mexico 1,837 1,885 1,919 1,973 1,972 •0.8% 2.2%
Total North America 23,665 24,050 24,898 25,023 24,783 •1.3% 28.9%
Argentina 364 372 394 421 442 5.1% 0.5%
Brazil 2,063 1,985 1,999 2,047 2,097 2.2% 2.4%
Chile 228 229 229 244 248 1.8% 0.3%
Colombia 222 222 223 225 230 2.7% 0.3%
Ecuador 131 137 141 168 180 7.3% 0.2%
Peru 147 140 151 165 160 •3.9% 0.2%
Venezuela 594 479 518 547 565 3.4% 0.7%
Other S. & Cent. America 1,144 1,160 1,170 1,189 1,230 3.4% 1.5%
Total S. & Cent. America 4,892 4,725 4,826 5,006 5,152 2.9% 6.1%
Austria 271 293 285 295 294 •0.2% 0.4%
Azerbaijan 74 86 92 107 96 •10.7% 0.1%
(Continued)
Year 2006
386 8 Petroleum
Table 8.2. (Continued)
Belgium & Luxembourg 691 748 785 815 837 2.8% 1.1%
Bulgaria 88 103 103 108 110 1.4% 0.1%
Czech Republic 174 185 203 211 208 •1.1% 0.3%
Denmark 200 193 189 195 201 3.1% 0.2%
Finland 226 239 224 233 225 •4.0% 0.3%
France 1,967 1,965 1,978 1,960 1,952 •0.3% 2.4%
Germany 2,714 2,664 2,634 2,605 2,622 0.9% 3.2%
Greece 414 404 435 432 451 4.7% 0.6%
Hungary 140 132 136 159 160 1.1% 0.2%
Iceland 19 18 20 21 20 •5.5% •
Republic of Ireland 182 178 185 196 195 •0.6% 0.2%
Italy 1,943 1,927 1,873 1,819 1,793 •1.1% 2.2%
Kazakhstan 193 183 188 208 221 6.0% 0.3%
Lithuania 53 51 55 58 59 0.4% 0.1%
Netherlands 952 962 1,003 1,070 1,057 w 1.3%
Norway 208 219 210 212 217 2.9% 0.3%
Poland 420 435 460 479 502 5.4% 0.6%
Portugal 338 317 322 331 344 4.9% 0.4%
Romania 226 199 230 223 223 •0.4% 0.3%
Russian Federation 2,606 2,622 2,634 2,628 2,735 4.2% 3.3%
Slovakia 76 71 68 81 82 2.8% 0.1%
Spain 1,526 1,559 1,593 1,619 1,602 •0.9% 2.0%
Sweden 317 332 319 315 312 •0.9% 0.4%
Switzerland 267 259 258 262 269 2.5% 0.3%
Turkey 656 668 688 649 617 •4.7% 0.7%
Turkmenistan 86 95 103 110 117 6.3% 0.1%
Ukraine 278 286 293 294 317 8.1% 0.4%
United Kingdom 1,693 1,717 1,764 1,802 1,781 •1.0% 2.1%
Uzbekistan 130 148 134 139 143 3.0% 0.2%
Other Europe & Eurasia 453 495 518 540 558 3.1% 0.7%
Total Europe & Eurasia 19,726 19,905 20,132 20,314 20,482 1.1% 24.9%
Iran 1,429 1,513 1,575 1,607 1,669 3.7% 2.0%
Kuwait 222 238 266 302 275 •10.4% 0.4%
Qatar 79 77 84 98 110 15.0% 0.1%
Saudi Arabia 1,572 1,684 1,805 1,891 2,005 6.2% 2.4%
United Arab Emirates 320 333 355 376 408 7.8% 0.5%
Other Middle East 1,425 1,393 1,407 1,437 1,455 1.2% 1.8%
Total Middle East 5,047 5,238 5,492 5,712 5,923 3.5% 7.2%
Algeria 222 231 240 251 260 4.3% 0.3%
Egypt 534 550 567 623 612 •2.4% 0.7%
share
2002 2003 2004 2005 2006
Change
2006 over
2005 of total
Year 2006
8.2 Consumption of Oil 387
South Africa 499 512 523 494 499 0.6% 0.6%
Other Africa 1,254 1,274 1,314 1,362 1,419 4.2% 1.7%
Total Africa 2,510 2,567 2,645 2,731 2,790 2.0% 3.4%
Australia 846 851 854 848 886 4.5% 1.0%
Bangladesh 80 83 83 84 86 1.7% 0.1%
China 5,288 5,803 6,772 6,984 7,445 6.7% 9.0%
China Hong Kong SAR 268 269 314 285 273 •4.3% 0.3%
India 2,374 2,420 2,573 2,569 2,575 0.6% 3.1%
Indonesia 1,115 1,132 1,150 1,168 1,031 •11.9% 1.3%
Japan 5,359 5,455 5,281 5,355 5,164 •3.7% 6.0%
Malaysia 489 480 493 477 499 4.6% 0.6%
New Zealand 141 148 150 154 156 1.6% 0.2%
Pakistan 357 321 325 353 372 5.9% 0.5%
Philippines 332 330 336 314 307 •1.9% 0.4%
Singapore 699 668 748 794 853 7.8% 1.1%
South Korea 2,282 2,300 2,283 2,308 2,312 •0.1% 2.7%
Taiwan 999 1,069 1,084 1,113 1,120 0.7% 1.3%
Thailand 766 836 913 918 926 0.7% 1.1%
Other Asia Pacific 504 509 546 571 584 2.0% 0.7%
Total Asia Pacific 21,898 22,674 23,905 24,294 24,589 1.3% 29.5%
TOTAL WORLD 77,737 79,158 81,898 83,080 83,719 0.7% 100.0%
European Union 25 # 14,471 14,546 14,686 14,861 14,865 0.3% 18.2%
European Union 27 # 14,785 14,849 15,019 15,192 15,198 0.3% 18.6%
OECD 58.1%
Former Soviet Union 3,667 3,748 3,783 3,819 3,997 4.7% 4.8%
Other EMEs 26,383 27,121 29,021 29,812 3,0682 2.9% 37.1%
OECD-Organization for Economic Co-operation and Development; EME-Established Market
Economy
sumption of fuel ethanol and biodiesel is also included
^ Less than 0.5; w Less than 0.05%.
# Excludes Estonia, Latvia and Lithuania prior to 1985 and Slovenia prior to 1991.
Annual changes and shares of total are calculated using million tonnes per annum figures. Differences
between these world consumption figures and world production statistics are accounted
for by stock changes, consumption of non-petroleum additives and substitute fuels, and unavoidable
disparities in the definition, measurement or conversion of oil supply and demand data.
Source: Reference [1].
World oil production has been able to meet the consumption so far. The
World oil demand is expected to grow from 84.83 million barrels per day in 2006
to 98 million barrels per day in 2015 and 118 million barrels per day in 2030. This
share
2002 2003 2004 2005 2006
Change
2006 over
2005 of total
Year 2006
* Inland demand plus international aviation and marine bunkers and refinery fuel and loss. Conincrease
in production came mainly from the OPEC countries. However, as shown
in Table 8.3, the oil production of a number of oil exporting countries is declining.
47,687 48,289 49,095 49,448 49,041 "0.9%
388 8 Petroleum
increased demand will continue despite the increase in world oil prices that is
expected to be 35% higher in 2025 than the current price. Much of the growth in
oil consumption is projected for the nations of non-OECD (Organization for Economic
Co-operation and Development) Asia, where strong economic growth is
expected. Non-OECD Asia (including China and India) accounts for 43% of the
total increase in world oil use over the projection period.
Table 8.3. Oil production by various countries in the last several years.
Year
2002 2003 2004 2005 2006
Change
2006 over
2005
2006
share
of total
USA 7,626 7,400 7,228 6,895 6,871 •0.5% 8.0%
Canada 2,858 3,004 3,085 3,041 3,147 4.4% 3.9%
Mexico 3,585 3,789 3,824 3,760 3,683 •2.1% 4.7%
Total North America 14,069 14,193 14,137 13,695 13,700 0.1% 16.5%
Argentina 818 806 754 725 716 •1.3% 0.9%
Brazil 1,499 1,555 1,542 1,715 1,809 5.5% 2.3%
Colombia 601 564 551 554 558 0.7% 0.7%
Ecuador 401 427 535 541 545 0.7% 0.7%
Peru 98 92 94 111 116 3.5% 0.1%
Trinidad & Tobago 155 164 152 171 174 1.5% 0.2%
Venezuela 2,895 2,554 2,907 2,937 2,824 •3.9% 3.7%
Other S. & Cent.
America 152 153 144 142 140 •1.7% 0.2%
Total S. & Cent.
America 6,619 6,314 6,680 6,897 6,881 •0.4% 8.8%
Azerbaijan 311 313 315 452 654 44.9% 0.8%
Denmark 371 368 390 377 342 •9.3% 0.4%
Italy 106 107 105 117 111 •5.6% 0.1%
Kazakhstan 1,018 1,111 1,297 1,356 1,426 5.6% 1.7%
Norway 3,333 3,264 3,188 2,969 2,778 •6.9% 3.3%
Romania 127 123 119 114 105 •8.0% 0.1%
Russian Federation 7,698 8,544 9,287 9,552 9,769 2.2% 12.3%
Turkmenistan 182 202 193 192 163 •15.2% 0.2%
United Kingdom 2,463 2,257 2,028 1,809 1,636 •9.6% 2.0%
Uzbekistan 171 166 152 126 125 •0.7% 0.1%
Other Europe & Eurasia 501 509 496 469 454 •2.9% 0.5%
Total Europe & Eurasia 16,281 16,965 17,570 17,533 17,563 0.2% 21.6%
8.2 Consumption of Oil 389
Year
2002 2003 2004 2005 2006
Change
2006 over
2005
2006
share
of total
Iran 3,543 4,183 4,248 4,268 4,343 1.2% 5.4%
Iraq 2,116 1,344 2,030 1,833 1,999 9.0% 2.5%
Kuwait 1,995 2,329 2,482 2,643 2,704 2.4% 3.4%
Oman 900 824 756 779 743 •4.6% 0.9%
Qatar 783 917 990 1,045 1,133 8.1% 1.3%
Saudi Arabia 8,928 10,164 10,638 11,114 10,859 •2.3% 13.1%
Syria 548 527 495 458 417 •8.9% 0.5%
United Arab Emirates 2,324 2,611 2,656 2,751 2,969 7.3% 3.5%
Yemen 457 448 420 426 390 •8.7% 0.5%
Other Middle East 48 48 48 34 32 •7.7% w
Total Middle East 21,642 23,395 24,764 25,352 25,589 0.7% 31.2%
Algeria 1,680 1,852 1,946 2,016 2,005 •0.3% 2.2%
Angola 905 862 976 1,233 1,409 14.3% 1.8%
Cameroon 75 68 62 58 63 8.6% 0.1%
Chad - 24 168 173 153 •11.7% 0.2%
Rep. of Congo
(Brazzaville) 231 215 216 246 262 6.7% 0.3%
Egypt 751 749 721 696 678 •2.5% 0.8%
Equatorial Guinea 215 247 343 356 358 0.6% 0.5%
Gabon 295 240 235 234 232 •0.9% 0.3%
Libya 1,375 1,485 1,624 1,751 1,835 4.2% 2.2%
Nigeria 2,103 2,263 2,502 2,580 2,460 •4.9% 3.0%
Sudan 233 255 325 355 397 11.8% 0.5%
Tunisia 75 68 72 74 69 •7.1% 0.1%
Other Africa 63 71 75 72 68 •5.3% 0.1%
Total Africa 8,001 8,398 9,263 9,846 9,990 1.4% 12.1%
Australia 731 624 541 554 544 •2.1% 0.6%
Brunei 210 214 210 206 221 7.1% 0.3%
China 3,346 3,401 3,481 3,627 3,684 1.6% 4.7%
India 801 798 816 784 807 3.1% 1.0%
Indonesia 1,288 1,183 1,152 1,129 1,071 •5.3% 1.3%
Malaysia 757 776 793 767 747 •3.1% 0.9%
Thailand 204 236 223 265 286 8.7% 0.3%
Vietnam 354 364 427 398 367 •8.0% 0.5%
(Continued)
390 8 Petroleum
Table 8.3. (Continued)
2002 2003 2004 2005 2006
Change
2006 over
2005
2006
share
of total
Other Asia Pacific 193 195 186 197 215 8.0% 0.3%
Total Asia Pacific 7,884 7,791 7,829 7,926 7,941 0.1% 9.7%
TOTAL WORLD 74,496 77,056 80,244 81,250 81,663 0.4% 100.0%
European Union 25 # 3,203 2,995 2,774 2,535 2,306 "9.0% 2.8%
European Union 27 # 3,331 3,119 2,893 2,649 2,412 "8.9% 2.9%
OECD 21,422 21,156 20,716 19,825 19,398 "2.2% 23.3%
OPEC 11 29,031 30,884 33,175 34,068 34,202 0.2% 41.7%
OPEC 12 29,936 31,746 34,151 35,301 35,611 0.7% 43.5%
Non-OPEC £ 35,933 35,673 35,661 35,343 35,162 "0.5% 43.0%
Former Soviet Union 9,533 10,499 11,407 11,840 12,299 3.9% 15.3%
* Includes crude oil, shale oil, oil sands and NGLs ( the liquid content of natural gas where this
is recovered separately). Excludes liquid fuels from other sources such as biomass and coal
derivatives.
and Slovenia prior to 1991; £ Excludes Former Soviet Union, includes Angola.
Annual changes and shares of total are calculated using million tonnes per annum figures.
Source: Reference [1].
On the supply side, the production of oil has been constrained by available capacity,
natural disasters, and geopolitical developments. In 2003 and 2004, as oil
consumption and prices rose briskly, Saudi Arabia and other members of OPEC
pumped more oil. OPEC was able to boost production relatively quickly in response
to changing market conditions by utilizing production capacity that had
been idle. By the end of 2004, however, OPEC%s spare production capacity was
greatly diminished (Fig. 8.1). As a consequence, OPEC%s oil production flattened
out over the past year even as oil prices continued to soar. Oil production outside
OPEC also leveled off last year, contrary to earlier expectations for continued
growth. The projected excess oil production capacity of the world is shown in Fig.
8.2
OPEC has maintained excess capacity of only 1 million to 2 million barrels a
day since 2004, down from 4 million in 2001 and 5.6 million in 2002. Although
OPEC%s excess capacity has rebounded from its 2005 low, the gains are largely in
heavy crude oils that can only be processed in specialized refineries. These facilities
are running at full capacity, so the added supplies are not relieving a tight
market. The latest evidence also suggests OPEC is now restraining its output.
Year
^ Less than 0.05; w Less than 0.05%; # Excludes Estonia, Latvia and Lithuania prior to 1985
8.2 Consumption of Oil 391
Fig. 8.1. Excess oil production capacity of OPEC and projection for 2009 (Adapted from [2]).
Fig. 8.2. The excess oil production capacity of the world (Adapted from [3]).
392 8 Petroleum
Forecasting world oil demand and production is becoming challenging. As
shown in Fig. 8.3, among OPEC countries, basically all of the excess production
capacity is with Saudi Arabia. The forecast, therefore, depends to a greater extent
on the decision of Saudi Arabia•s intent on production change.
Fig. 8.3. Excess oil production capacities of OPEC countries (Adapted from [2]).
Recently (July 2, 2008), The U.S. Energy Information Administration has lowered
its estimate for non-OPEC production in 2010 by 1.1 million barrels per day
to 51.8 million barrels per day, from last year•s forecast of 52.9 million. At the
same time, the EIA lowered its 2010 OPEC production forecast by 400,000 barrels
to 37.4 million.
The increased production may not be sufficient to bring down the price of
crude oil. Although the consumption of oil is showing decline in the USA, it is
increasing in other countries, particularly in China. The annual change in the
consumption rate is shown in Fig. 8.4 and the actual consumption is shown in
Fig. 8.5.
However, it is reported by Associated Press (Abbot S, 07/04/2008) that
Saudi Arabia•s state-owned oil company, Aramco, is spending $10 billion to build
the infrastructure to pump 1.2 million barrels of oil per day by next June from the
Khurais field and its two smaller neighbors. This will increase Saudi Arabia•s total
amount of oil production capacity to 12.5 million barrels per day by the end of
2009; up from a little more than 11 million barrels per day now.
8.2 Consumption of Oil 393
Fig. 8.4. Change in world oil consumption (Adapted from [4]).
Fig. 8.5. Oil consumption by the USA and China, and rest of the world (Adapted from [4]).
394 8 Petroleum
The production of oil is not keeping up with the increasing demand. The world
is increasingly becoming dependent on the supply from the OPEC countries. As
can be seen from Fig. 8.6, although a number of non-OPEC countries including
the USA have increased its production, at the same time the production capacity of
a number of major oil producing countries is in a decline.
Fig. 8.6. Non-OPEC oil production growth; changes from the previous year (Adapted from [4]).
8.3 Oil Demand by Sectors
Most of the oil in the world is used by the transportation sector, which accounts
for more than half of the total use. The industrial sector accounts for about 38% of
the oil use, mostly for chemical and petrochemical processes. Consequently, much
of the world$s incremental oil demand is projected for use in the transportation
sector (Fig. 8.7). Unconventional liquids such as gas-to-liquids, coal-to-liquids,
ethanol and biodiesel produced from energy crops are expected to share some of
the increased demand for transportation fuel; however, oil is still expected to be
the major fuel of choice for transportation. An estimate of oil production by various
oil producing countries in the future is given in Table 8.4.
In the USA, oil is mainly used for transportation accounting for about 70% of
the total consumption. The uses of oil in various sectors in the USA are shown in
Fig. 8.8.
8.3OilDemandbySectors395
Annual production Annual growth
Region /Country 2006 2007 2008 2009 2007 2008 2009
OPEC Countries 35.823 35.410 37.096 37.082 0.414 1.687 0.014
North America 15.326 15.344 15.278 15.472 0.019 0.066 0.194
Canada 3.288 3.356 3.416 3.585 0.068 0.060 0.169
Mexico 3.707 3.501 3.189 2.947 0.206 0.313 0.242
United States 8.330 8.487 8.673 8.941 0.157 0.186 0.267
Russia and Caspian Sea 11.890 12.350 12.543 13.071 0.461 0.192 0.528
Russia 9.677 9.876 9.896 10.045 0.199 0.021 0.149
Azerbaijan 0.648 0.849 0.962 1.197 0.201 0.113 0.235
Kazakhstan 1.388 1.445 1.495 1.631 0.057 0.050 0.136
Turkmenistan 0.177 0.180 0.189 0.198 0.003 0.009 0.008
Latin America 4.560 4.597 4.799 5.013 0.037 0.203 0.213
Argentina 0.802 0.791 0.786 0.775 0.012 0.005 0.011
Brazil 2.167 2.277 2.494 2.758 0.110 0.217 0.264
Colombia 0.544 0.543 0.545 0.518 0.001 0.002 0.027
Ecuador 0.537 0.512 0.497 0.482 0.024 0.015 0.015
Other Latin America 0.509 0.473 0.477 0.480 0.036 0.004 0.002
North Sea 4.780 4.544 4.191 4.019 0.236 0.352 0.172
Norway 2.786 2.565 2.398 2.370 0.221 0.168 0.027
United Kingdom 1.602 1.607 1.445 1.301 0.005 0.162 0.144
Other Non-OPEC 12.213 12.309 12.636 12.993 0.096 0.326 0.357
World Total 84.591 84.554 86.543 87.650 -0.038 1.990 1.107
Source: [BP Statistical Review of World Energy 2008, 2].
Table 8.4. Forecast for future oil production by various oil producing countries.
396 8 Petroleum
0
20
40
60
80
100
120
2003 2010 2015 2020 2025 2030
Consumption(millionsbarrelperday)
Year
Commercial
Residential
Electricity
Industrial
Transportation
Fig. 8.7. World oil consumption by sectors (Adapted from [5]).
8.4 Exploration, Drilling, and Production
8.4.1 Exploration and Drilling
The search for oil and gas involved exploration both in land and off-shore, followed
by drilling of exploratory wells. The methodologies for exploration and
drilling techniques have been discussed in Chapter 7.
8.4.2 Production
The basic production steps and well completion are discussed in Chapter 7. The
production techniques for oil only wells are discussed below. The naturally occurring
pressure in the underground reservoir determines if the reservoir is economically
viable. The pressure varies with the characteristics of the trap, the reservoir rock
and the production history.
8.4Exploration,Drilling,andProduction397
Fig. 8.8. US petroleum flow 2007 (million barrels per day). http://www.eia.doe.gov/emeu/aer/diagram2.html.
398 8 Petroleum
For most oil wells, the pressure underground is high enough to force the oil
to the surface. This is called natural lift production methods. Reservoirs in the
Middle East tend to be long-lived on natural lift. As the underground pressure in
the reservoir dissipates due to continuous extraction, the remaining oil is extracted
by means of an artificial lift. A pump powered by gas or electricity is used for this
purpose. The majority of the oil reservoirs in the United States are produced using
some kind of artificial lift.
8.4.2.1 Production by Artificial Lift
The artificial lift methods of producing oil from wells include (1) pumping with
sucker rods (2) gas lift (3) hydraulic subsurface pumps (4) electrically driven centrifugal
well pumps and (5) swabbing.
About 90% of the wells in the United States are equipped with sucker-rod•type
pumps (see Fig. 8.9). This type of pumps is installed at the lower end of the tubing
string and is actuated by a string of sucker rods extending from the surface to the
subsurface pump [6]. The two common variations are mechanical and hydraulic
long-stroke pumping. Other lifting mechanisms are jet pumps, and sonic pumps.
Fig. 8.9. Sucker rod type artificial lift pump for oil production (Printed with permission from [6]).
In the United States, primary production methods, including artificial lift,
account for less than 40% of the total oil production. Once the primary production
methods even with artificial lift become ineffective, the remaining oil is extracted
8.4 Exploration, Drilling, and Production 399
using •secondary• and/or •tertiary• production methods [7•35]. One common
method for secondary production is called water flooding, in which the oil well is
flooded using water to displace oil. Water forces the oil to the drilled shaft or
•wellbore.• Finally, producers may need to turn to •tertiary• or •enhanced• oil
recovery methods. These techniques are often centered on increasing the oil•s
flow characteristics through the use of steam, carbon dioxide and other gases or
chemicals. Secondary production methods account for about 50% and tertiary
recovery is the remaining 10%.
as density and viscosity determine the cost of producing oil. These costs can range
from $2 per barrel in the Middle East to more than $15 per barrel in some fields in
the United States, including capital recovery. Technological advances in exploration,
drilling, production methods have made it possible to produce oil cheaper in
places such as deepwater Gulf of Mexico, where the production cost is about $10
per barrel.
8.4.2.2 Off-Shore Production
Significant advances have been made in the off-shore drilling and production
techniques. In 1978, the greatest off-shore production depth was 300 m. In the
1990s, the crude oil production from the very deep offshore sectors provided stability
to the global oil market. By 1998, the depth of the offshore production well
was about 1,800 m at Petrobras in the Campos Basin in Brazil. Table 8.5 shows
the advances in the deep offshore drilling and production of crude oil.
Table 8.5. Advances in the depth of production from the offshore basins.
Oil field Location Year Depth (m)
Cognac Gulf of Mexico 1978 312 Shell Oil
Jolliet Gulf of Mexico 1989 540 Conoco Inc.
Marlim Campos Basin,
Brazil
1991 752 Petrobras
Marlim 4 Campos Basin,
Brazil
1994 1,027 Petrobras
Mensa Gulf of Mexica 1997 1,650 Shell Oil
Marlim Sul Campos Basin,
Brazil
1997 1,709 Petrobras
Roncador Campos Basin,
Brazil
1999 1,852 Petrobras
Thusder Horse Gulf of Mexico 2001 5,640 (ft) BP and Exxon
Tupi Brazil 2007 >3,000 Petrobras
The reservoir characteristics and the physical properties of the crude oil such
400 8 Petroleum
For oil companies, the next target depth is 3,000 m. Meeting this objective constitutes
a major industry challenge for the next 5•10 years.
8.5 Crude Oil Benchmarking
The physical and chemical properties of crude oils generally differ from one field
to another field. These properties of the crude oils may even differ over the time
from the same field. The quality of the crude oil, i.e., its physical and chemical
consistency, is extremely important as it determines not only the crude oil processing
(refining) techniques and re-processing necessary to achieve the optimal mix
of product output, but also its market price. Price differentials between crude oils
actually reflect the relative ease of refining. Based on the physical characteristics
of the crude oils they are classified into different categories, which are called
Crude Oil Benchmarking [36, 37]. Crude oils of similar quality are often compared
to a single representative crude oil, a "benchmark,# of the quality class for
pricing purposes worldwide. Crude oils are bought and sold in the stock markets
as a commodity. The largest markets are in London, New York and Singapore, but
crude oil and refined products • such as gasoline (petrol) and heating oil • are
bought and sold all over the world.
tent. Less dense (or "lighter#) crudes generally contain higher percentage of light
hydrocarbons. The light hydrocarbons are most desired products as they are higher
value products. Lighter crude can be separated (fractionated) by simple distillation
process. The denser ("heavier#) crude oils require more extensive processing. The
products from simple distillation are generally of lower value and require additional
processing to produce the desired range of products.
Crude oil is considered "sweet# if it contains less than 0.5% sulfur. Sulfur is
low sulfur content and relatively high yields of high-value products such as gasoline,
diesel fuel, heating oil, and jet fuel. A higher sulfur content is undesirable for
both processing and product quality.
Crude oil price Benchmarks were first introduced in the mid-1980s. There are
three official benchmarks:
West Texas Intermediate (WTI)
Brent Blend
Dubai Crude
Recently, two other benchmarking are used for trading and pricing purposes;
New York Mercantile Exchange, and OPEC Basket.
generally present as hydrogen sulfide. Small amounts of carbon dioxide may also
be present in the crude. Light, sweet crudes are preferred by refiners because of their
Benchmarking of crude oils depends mainly on their density and sulfur con-
8.5 Crude Oil Benchmarking 401
8.5.1 West Texas Intermediate (WTI)
WTI is used primarily in the U.S. and is very light and very sweet. Its API
(American Petroleum Institute) gravity is 39.6 (making it a "light# crude oil), and
it contains only about 0.24% of sulfur (making it a "sweet# crude oil). This type of
crude is suitable for producing low-sulfur gasoline and low-sulfur diesel. Although
the production of WTI crude oil is on the decline, it still is the major
benchmark of crude oil in the USA. WTI is generally priced at about a $5 to $6
per-barrel premium to the OPEC Basket price and about $1 to $2 per-barrel premium
to Brent, although on a daily basis the pricing relationships between these
can vary greatly.
8.5.2 Brent Blend
Brent blend is a mixture of crude oil from 15 different oil fields in the Brent and
Ninian systems from the North Sea. Its API gravity is 38.3 (making it a "light#
making it a "sweet# crude oil, but slightly less "sweet# than WTI). Brent blend is
ideal for making gasoline and middle distillates, both of which are consumed in
large quantities in Northwest Europe, where Brent blend crude oil is typically
refined.
Brent blend has become the de facto international oil benchmark. If no other
information is given for a particular crude oil, its price is set in comparison to
Brent Blend when traded at London&s International Petroleum Exchange (IPE) in
value of North Sea Brent ("dated Brent#) is widely used in benchmarking the bulk
of oil from the North Sea, West and North Africa, Russia and Central Asia, as well
as large volumes from the Middle East heading into western markets.
The production of Brent blend, like WTI, is also on the decline, but it remains
the major benchmark for other crude oils in Europe and Africa. Brent blend is
generally priced at about a $4 per-barrel premium to the OPEC Basket price or
about a $1 to $2 per-barrel below WTI, although on a daily basis the pricing relationships
can vary greatly.
8.5.3 Dubai Crude
In the Gulf, Dubai crude is used as a benchmark to price other regional crudes that
are sold to Asia. Dubai crude is a medium heavy, low sulfur crude, typical of the
crude oil, but not quite as "light# as WTI), and sulfur content is about 0.37%
the UK and other European markets. According to the IPE, Brent blend is used to
price two thirds of the worlds internationally traded crude oil supplies. The physical
402 8 Petroleum
grades produced in the Persian Gulf. It is generally sold at a lower price than Brent
blend and WTI.
8.5.4 New York Mercantile Exchange
sweet crude. Oil containing more than 0.5% sulfur by weight is said to be "sour#.
Not only the US domestic crude, but also a number of foreign crudes are traded
based on this benchmarking.
The NYMEX miNY$ crude oil futures contract, designed for investment portcago
Mercantile Exchange) electronic trading platform and clears through the
New York Mercantile Exchange clearinghouse.
The Exchange also lists for trading futures contract for Dubai crude oil; a futures
contract on the differential between the light, sweet crude oil futures contract
and Canadian Bow River crude at Hardisty, Alberta; and futures contracts on the
differentials of the light, sweet crude oil futures contract and four domestic grades
of crude oil: Light Louisiana Sweet, West Texas Intermediate-Midland, West
Texas Sour, and Mars Blend.
8.5.5 OPEC Basket
Baghdad, Iraq, in September 1960, mainly by oil producing countries from Middle
East. The objective was to unify and coordinate members• petroleum policies.
Since 1982, OPEC also sets crude oil production quotas of its member countries.
Current OPEC members include Iran, Iraq, Kuwait, Saudi Arabia, and Venezuela,
Qatar, Indonesia, Libya, the United Arab Emirates, Algeria, and Nigeria. Although
Iraq remains a member of OPEC, Iraqi production has not been a part of any
OPEC quota agreements since March 1998.
OPEC collects pricing data on a "basket# of crude oils from its member countries.
OPEC uses the price of this basket to monitor world oil market conditions.
From January 1, 1987 to June 15, 2005, OPEC calculated an arithmetic average of
and Mexico Isthmus (a non-OPEC oil) to estimate the OPEC basket price.
This average is determined according to the production and exports of each country
and is used as a reference point by OPEC to monitor worldwide oil market
conditions.
Crude prices on the New York Mercantile Exchange generally refer to light,
futures contract. The contract is available for trading on the CME Globex® (Chifolios,
is the equivalent of 500 barrels of crude, 50% of the size of a standard
The Organization of Petroleum Exporting Countries (OPEC) was founded in
Nigeria Bonny Light, Saudi Arabia Arab Light, Dubai Fateh, Venezuela Tia Juana
seven crude oil streams, including: Algeria•s Saharan Blend, Indonesia Minas,
8.6 Crude Oil Characterization 403
From June 16, 2007, OPEC•s reference basket consists of eleven crude streams
representing the main export crude of all member countries, weighted according to
production and exports to the main markets. The crude oil streams in the basket
are:
1. Saharan Blend (Algeria)
2. Minas (Indonesia)
3. Iran Heavy (Islamic Republic of Iran)
4. Basra Light (Iraq)
5. Kuwait Export (Kuwait)
6. Es Sider (Libya)
7. Bonny Light (Nigeria)
8. Qatar Marine (Qatar)
9. Arab Light (Saudi Arabia)
10. Murban (UAE)
11. BCF 17 (Venezuela)
The API gravity for the new Basket is heavier, at 32.7º compared to 34.6º for
the previous basket of seven crudes. The sulfur content of the new Reference Basket
is 1.77%, making it more sour compared to the previous basket of 1.44%.
8.6 Crude Oil Characterization
tests generally carried out in laboratories. Each crude oil type has unique chemical
characteristics. No crude oil type is identical. Crude oil assays evaluate whole
crude oils and various boiling range fractions of the crude oil. Assay data is used
by refineries to determine if a crude oil feedstock is compatible for a particular
petroleum refinery. The data also provide important information on the yield,
quality, production rate, environmental problems, and marketing. An assay can be
customized to meet specific requirements.
A crude oil assay involves a physical distillation of the crude oil to generate
specific boiling range fractions ("cuts#). Each of the cuts is analyzed for physical
and chemical properties, and basic or detailed information is provided regarding
the whole crude properties and the individual cut qualities. The crude oil assay
consists of the tests given in Table 8.6 along with the ASTM standards used for
these tests. The detail characterization of a typical crude oil is given in Appendix
VIII.
A crude oil assay is the chemical evaluation of crude oil feedstock by various
4048Petroleum
Table 8.6. Various test methods for characterization of petroleum.
Petroleum measurement Unit EN Test IP Test ISO Test ASTM Test same ASTM Test similar
Aromatics % vol nb. GC/MS ASTM D5769
Aromatics dm3
/m3
Aromatics vol% IP 156 ISO 3837 ASTM D1319
Ash Content %m/m EN6245 IP 4 ISO6245 ASTM D482
Benzene dm3
/m3
EN 12177 IP 425 ASTM D3606
Benzene vol%
Carbon Residue (Micro) % m/m EN10370 IP 398 ISO10370 ASTM D4530
Cetane number None EN5165 IP 41 ISO5165 ASTM D613
Cetane Index None EN4264 IP 380 ISO4264 ASTM D4737
CFPP °C EN116 IP 309 ASTM D6371
Cloud Point °C EN23015 IP 219 ISO3015 ASTM D2500
Copper corrosion None EN2160 IP 154 ISO 2160 ASTM D130
Density at 15°C kg/l EN 3675 IP 160 ISO 3675 ASTM D1298
Density at 15°C kg/m3
EN 12185 IP 365 ISO 12185 ASTM D4052
Distillation (Rec. or Evap. Vol%) °C EN 3405 IP 123 ISO 3405 ASTM D86
Distillation, % Evap @ T°C vol%
Distillation, I.B.P °C
Distillation, F.B.P. °C
Distillation, Loss vol%
Distillation, Recovery vol%
Distillation, Residue vol%
Doctor test None IP 30 ASTM D4952
Existent gums g/m3
EN 6246 IP 131 ISO6246 ASTM D381
Existent gums mg/100 mL IP 131 ASTM D381
Flash Point °C EN22719 IP404 ISO2719 D93
Induction period (Oxstab) min. EN7536 IP 40 ISO 7536 ASTM D525
Kinematic Viscosity @ T°C mm2
/s EN3104 IP 71 ISO3104 ASTM D445
Lead mg/L EN 237 IP 428 ASTM D3237
Lubricity um IP 450 ISO12156 ASTM D6079
405
Petroleum measurement Unit EN Test IP Test ISO Test ASTM Test same ASTM Test similar
Mercaptans mg/kg IP 342 ISO 3012 ASTM D3227
Octane No. Motor 0 EN 25163 IP 236 ISO 5163 ASTM D2700
Octane No. Research 0 EN 25164 IP 237 ISO 5164 ASTM D2699
Olefins vol% IP 156 ISO 3837 ASTM D1319
Olefins dm3
/m3
Oxidation Stability g/m3
EN12205 IP 388 ISO12205 ASTM D2274
Oxygen %m/m EN 1601 IP 408 nb. GC OFID ASTM D5599
Oxygenates vol%
Particulate Contamination mg/kg EN12662 IP 440 ASTM D6217
Polycyclic Aromatic Hydrocarbons %m/m EN12916 IP 391 ISO6591
Sulfur % mass or
%m/m
EN8754 IP336 ISO8754 ASTM D4294
Sulfur mg/kg EN14596 IP 447 ISO14596 ASTM D2622
Sulfur mg/kg IP 490 ASTM D5453
Sulfur mg/kg EN 24260 IP 243 ISO4260 nb. Wickbold
Vapor pressure. (RVP, ASVP, DVPE) kPa EN 13016 IP 394 ASTM D5191
Vapor pressure. (RVP, ASVP, DVPE) hPa or mb IP 69 ISO3007 ASTM D323
Vapor pressure. (RVP, ASVP, DVPE) mmHg or
torr
Vapor pressure. (RVP, ASVP, DVPE) kg/m2
Vapor pressure. (RVP, ASVP, DVPE) g/cm2
Water Content %m/m EN 12937 IP 348 ISO 12937 ASTM D6304
8.6CrudeOilCharacterization
406 8 Petroleum
8.7 Crude Oil Refining
Distillation
Catalytic Reforming
Cracking
Treating
8.7.1 Distillation
The crude oil is heated and fed to a distillation column or tower. A number of such
distillation columns are used in a refinery to produce a variety of products. The
columns are operated at various temperatures and pressures. Depending on the
operating pressure of the columns, they are called atmospheric column (Crude
Distillation Unit) or vacuum distillation columns. During distillation, the lightest
materials, such as propane and butane, vaporize and are collected from the top of
the first atmospheric column. Medium weight materials, that include gasoline, jet
and diesel fuels condense in the middle. Heavy materials, called gas oils, condense
in the lower portion of the atmospheric column. The heaviest tar-like material,
called residuum, is referred to as the "bottom of the barrel#, and is collected from
the bottom of the column. Products from the top, middle and bottom of the column
are transferred to different plants for further refining. A schematic diagram of a
refinery for light oils is shown in Fig. 8.10.
The separation of the crude oil into various fractions depends on the temperature
at a particular location of the column. Figure 8.11 shows the typical temperature at
various locations of an atmospheric distillation column and the corresponding
fractions.
The temperature at various locations of the column is maintained by using a
variety of techniques. As can be seen from Fig. 8.12 a companion column is used
along side the main crude distillation unit where a stream is drawn from the crude
distillation column, heated, and again feed back to the crude distillation column.
Also, a number of heaters are used to recover the waste heat and to pre-heat the
crude oil.
of products. These are:
Crude oil must be refined in order to produce finished products [38•49]. There
are four basic operations that all the refineries perform for production of a variety
8.7CrudeOilRefining407
Fig. 8.10. Flow diagram of a crude oil processing refinery (Courtesy of [50]).
408 8 Petroleum
Fig. 8.11. Temperatures and corresponding fractions in the first step of crude oil distillation.
8.7.2 Catalytic Reforming
For use as a gasoline or motor fuel, the octane number of the finished product
octane number of gasoline [51•60]. For motor fuel use, the octane number determines
the quality of the product as it relates to the combustion characteristics of
the fuel. A higher octane number reflects a lower tendency of the hydrocarbon to
undergo a rapid, inefficient detonation in an internal combustion engine. The rapid
detonation is undesirable as it causes knocking sound in the engine. In the USA,
the octane number posted in the gas station is the arithmetic average of the MON
(motor octane number which is measured at high engine speeds) and RON
(research octane number which is measured at low engine speeds). The RON and
MON of some selected hydrocarbons are given in Table 8.7. As can be seen from
the table, aromatics have higher octane number and a greater percentage of them
are desirable in the finished motor fuel products. The light petroleum distillates
(naphtha) are catalytically reformed for the purpose of raising the octane number
should be above 87. Catalytic reforming is one of the method used for increasing
8.7CrudeOilRefining409
Fig. 8.12. The layout of a typical atmospheric crude oil distillation system (Printed with permission from [49]).
410 8 Petroleum
of the hydrocarbon feed stream. Naphtha is contacted with a platinum based catalyst
at elevated temperatures (higher than 200o
C (400o
F)) and hydrogen pressures
ranging from 345 to 3,450 kPa (50•500 psig). The low octane, paraffin-rich naphtha
feed is converted to a high octane aromatic rich liquid product. The byproducts
of the process are hydrogen and light hydrocarbons. The UOP LLC first
introduced the platinum based catalytic reforming unit (called PlatformingTM
process) in 1949. Since then significant improvement has been made, particularly
in the catalyst area. The introduction of bimetallic catalysts allows lower pressure,
higher severity operation: ~1,380•2,070 kPa (200•300 psig) at 95•98 octane
number with typical cycle lengths of 1 year.
Table 8.7. Typical Research Octane Number (RON) and Motor Octane Number (MON) of ome
selected hydrocarbons.
Compounds RON MON
Paraffins
n-Heptane 0 0
2-Methylhexane 42.4 46.3
3-Ethylpentane 65.0 69.3
2,4-Dimethylpentane 83.1 83.8
Aromatics
Toluene 120.1 103.2
Ethylbenzene 107.4 97.9
Isopropylbenzene 113.0 99.3
1-Methyl-3-ethylbenzene 112.1 100.0
1,3,5-trimethylbenzene >120 >120
Source: Reference [49]
Typical composition of the naphtha stream before and after the catalytic
reforming is given in Table 8.8. The catalytically reformed naphthas are blend
with various other streams to obtain the motor fuel with desired octane number.
Table 8.8. Composition of a typical naphtha stream before and after catalytic reformation.
Compounds Composition of Typical
Naphtha
(wt%) (wt%)
Aromatics
Benzene 1.45 3.72
Toluene 4.06 13.97
Ethylbenzene 0.52 3.13
p-Xylene 0.92 3.39
m-Xylene 2.75 7.47
o-Xylene 0.87 4.83
Composition
Reformate
8.7 Crude Oil Refining 411
Compounds Composition of Typical
Naphtha
(wt%) (wt%)
C9+Aromatics 3.31 36.05
Total Aromatics 13.88 72.56
Total Olefins 0.11 0.82
Paraffins and Napthenes
Propane 0.79 0.00
Isobutane 1.28 0.14
n-Butane 3.43 0.94
Isopentane 5.62 2.52
n-Pentane 6.19 1.74
Cyclopentane 0.64 0.10
C6 Isoparaffins 6.00 3.91
n-Hexane 5.3 1.74
Methylcyclopentane 2.58 0.28
Cyclohexane 3.26 0.03
C7-Isoparaffins 4.55 7.70
n-Heptane 4.65 2.22
C7 Cyclopentanes 2.77 0.33
Methylcyclohexane 7.57 0.04
C8 Isoparaffins 4.24 2.86
n-Octane 3.43 0.62
C8-Cyclopentanes 1.52 0.14
C8 Cyclohexanes 5.23 0.06
C9 Naphthenes 3.63 0.04
C9-Paraffins 5.93 0.90
C10 Naphthenes 1.66 0.04
C10-Paraffins 3.41 0.24
C11 Naphthenes 1.04 0.00
C11-Paraffins 0.53 0.03
Total Paraffins 55.35 25.56
Total Naphthenes 30.7 1.06
Source: Reference [49]
The objective of catalytic reforming is to produce lighter aromatics so that the
octane number of the product stream increases. A number of reaction steps take
place before the final products are obtained. The reaction steps are shown in
Fig. 8.13 and the process flow diagram is shown in Fig. 8.14.
Composition
Reformate
412 8 Petroleum
Fig. 8.13. Steps involved in catalytic reforming for production of light aromatics (Adapted from
Catalysts play an important role in the reforming process. Although platinum is
the best catalyst, the cost of platinum makes the process very expensive. A number
of non-platinum based catalysts have been developed. Also, zeolite was found
to be an excellent support material for a number of active materials such as zinc
8.7.3 Cracking
fuel; gasoline, jet fuel, and diesel. However, among these three, the greatest demand
is for gasoline. The middle distillate, gas oil and residuum are converted
into gasoline, jet and diesel fuels in a series of processing plants called cracking
There are three applications of the cracking processes and are given in Table 8.9.
Table 8.9. Various objectives of catalyst cracking units.
Applications Feedstock Products
Gas oil cracking Vacuum gas oils Motor gasoline, LCO and
LPG
Resid cracking Atmospheric resid VGO and
vacuum resides
Motor gasoline, LCO, and
LPG
Cracking for petrochemicals Light olefins-C2, C3, C4
and aromaticsresides
Vacuum gas oils and added
UOP, CCR platforming process for motor fuel production [61]).
[62•76]. Several modifications to the process have been made to improve its efficiency
[77•81].
The objective of the refinery is to maximize the production of transportation
units, in which heavy hydrocarbon molecules break down into smaller, lighter ones.
8.7CrudeOilRefining413
Fig. 8.14. Flow diagram of a catalytic reforming unit (Adapted from UOP, CCR platforming process for motor fuel production [61]).
414 8 Petroleum
Three basic cracking processes are used in the refinery to produce transportation
fuels.
Fluid Catalytic Cracking (FCC)
Hydrocracking
Coking (Thermal Cracking)
8.7.3.1 Fluid Catalytic Cracking (FCC)
In this process, heavy fractions of vacuum gas oil and resid (boiling point > 344°C
(650°F)) are heated at 1,000°F under a vacuum in the presence of a catalyst to
produce more valuable products such as Liquefied Petroleum Gas (LPG), gaso(CCU)
and a catalyst regeneration unit (CRU) is shown in Fig. 8.15. Catalysts
The reaction products and catalyst are separated in the catalyst/vapor separator.
The vapor stream is further cleaned in a cyclone to remove any carried-over catalyst
and fed to the main fractionators and the gas plant for separation of the products.
The spent catalysts are regenerated by burning off the deposited coke from
the catalyst surface and are fed back to the base riser of CCU. Typical CCU undergoes
100•400 such cycles a day.
line, and diesel fuels [82•131]. A schematic diagram of a catalytic cracking unit
Fig. 8.15. A typical fluid catalytic cracking unit. (From Letzsch W (2006), Fluid catalytic cracking,
contact the oil near the base of CCU riser where most of the reactions takes place.
Chapter 6, Handbook of Petroleum Processing, Eds. Jones DSJ, Pujado PR, Springer, 2006).
8.7 Crude Oil Refining 415
The chemical reactions that take place during cracking may be described by the
following reactions. The basic reaction paths during fluid catalytic cracking are
shown below. The process can be terminated at any point depending on the
desired products.
CokeLPGGasolineDieselsidReorOilGas
Paraffin Paraffin + Olefin
CnH2n+2 CpH2p+2 + CmH2m
C10H22 (Decane) C6H14 (Hexane) + C4H8 (Butylene)
8.7.3.2 Gas Oil Catalytic Cracking
The design and operation of catalytic cracking unit for gas oil is shown in Fig. 8.16.
A gas oil cracking unit consists of a feed injection system, reactor riser, riser termination
system, and vapor quenching system. The feed, which is in the liquid
form, is vaporized upon injection and is contacted with the catalyst. The regenerated
and recycled catalyst from the catalyst regenerator is hot; the feed injection
system should cool it down as quickly as possible before its contact with the feed.
The other feature of the injection system is that it should provide plug flow of the
feed. Various feed injection systems, reactor with riser and quench system, and
catalyst regenerators are developed to improve the efficiency of the system.
Fig. 8.16. A gas oil cracking unit (From UOP Fluid catalytic cracking unit (FCC) and related
processes, UOP [61]).
416 8 Petroleum
8.7.3.3 Resid Catalytic Cracking
Refineries are under increasing pressure to process high boiling point feeds and
crude oils with high levels of contaminant metals. Reside catalytic cracking process
was developed to further process high boiling residue. One of the main issues
was development of catalysts. A catalyst should have the following characteristics
in order to be effective and economical.
Capability to passivity contaminant metals such as nickel and vanadium
Capable of cracking higher boiling range molecules
A high activity and stability
hydro-thermal stability, up to a temperature of 1,600o
F, three-dimensional structure,
average pore diameter of 7.5 A, high activity and selectivity. Elite Type Y
activity, and inertness in the presence of high concentrations of nickel and vanadium.
A number of companies produce catalysts for RFCC (Resid Fluid Catalytic
Cracking) units with varying composition and characteristics.
Although the basic design is the same, resid catalytic cracking units differ
based on a specific task that needs to be carried out. The feed injection system
should be capable of handling heavier feed which requires more steam for proper
dispersion of the feed into the reactor. The main difference of a RFCC with other
FCC is in the design of the regenerator. The regenerator should be designed such a
way that the regenerated catalyst is cooled down before recycling back to the
cracking unit. Either a single stage regenerator with a catalyst cooler or a twostage
regenerator is used. Currently most of the RFCC units employ two-stage
regenerator. It not only cools down the catalyst, but a two-stage regenerator produces
CO rather than CO2. This can reduce or even eliminate the need for any heat
removal system. Another advantage is that most of the hydrogen (about 80•85%
of initial hydrogen content) in the coke can be burnt off in the first stage of the
regenerator leaving no carbon on the catalyst surface. The moisture produced during
combustion of hydrogen tends to deactivate the catalyst. Therefore, catalysts
should be hydro-thermally stable. A typical resid cracker is shown in Fig. 8.17.
Fluid catalytic cracking is one of the main processes for upgrading the product
quality and yield. Significant efforts have been directed towards research and
role. A number of researchers focused their attention on development of new cataZSM
based catalysts are explored heavily recently due to its high temperature staonly
extend the life time of the catalyst, but also reduce the operating costs. The
The catalyst generally used for resid cracking is elite Type Y because of its high
resid catalysts offer low production of coke and preservation of elite integrity and
process development [82•96]. The catalysts used in the FCC units play a major
lysts or modification of existing catalysts [97•112]. Among various catalysts,
bility and capability to retain activity [113•118]. One of issues with the FCC
process is the regeneration of catalysts for repeated use [119•124]. This will not
riser design of FCC units is important for product quality and yield [125•131].
8.8 Cracking for Light Olefins and Aromatics 417
8.8 Cracking for Light Olefins and Aromatics
One of the main objectives of cracking heavier feedstock is to produce light olefins,
mainly propylene. The demand for propylene as a petrochemical feedstock has
increased significantly in recent years.
In 2006, worldwide production of propylene for chemical uses amounted to
almost 70,000 metric tons and was valued at roughly $80 billion. Consumption of
propylene worldwide is expected to grow at an average annual rate of about 5%
over the 5-year period from 2006 to 2011.
The major use of propylene is in the production of polypropylene; almost 61%
the major consumers of propylene are shown. Other uses of propylene include
production of acrylonitrile, oxo chemicals, propylene oxide, cumene, isopropyl
alcohol and polygas chemicals. Since propylene is an established market, no significant
new chemical uses are expected to emerge in the future.
logies, PETEM 2004).
Fig. 8.17. A resid catalytic cracking unit developed by Axens IFP group (From Roux R (2004) A
new separator helps FCC adapt to a new refinery-petrochemical role. Axens IFP Group Technoof
the world$s propylene was used for polypropylene production in 2006. In Fig. 8.18
418 8 Petroleum
Fig. 8.18. Consumption of propylene in various regions of the world and by some selected
countries.
Three major cracking processes; Deep Catalytic Cracking (DCC), Fluid Catalytic
Cracking (FCC), and Steam Cracking (SC) are currently used for production
Table 8.10. Although the total product yield by SC is higher than DCC or FCC,
the combined aromatic and olefin fractions is higher for DCC process. A schematic
diagram of DCC process is shown in Fig. 8.19. The basic operation is the
same as that of a gas-oil cracking unit. A number of feedstock can be used in DCC
units including vacuum gas oil (VGO), hydrotreated VGO, coker gas oil, and
atmospheric resid. Two processes have been developed recently; PetroFCC by
UOP and Maxofin by Kellogg Brown & Root-Halliburton to increase the propylene
yield from heavy feeds.
of propylene [134•141]. Various products yield by these processes is given in
8.8 Cracking for Light Olefins and Aromatics 419
Table 8.10. Yield of products by three cracking processes.
Components DCC FCC SC
Paraffins 14.3 28.6 3.5
Olefins 32.4 35.3 13.3
Naphthenes 5.0 9.8 4.1
Aromatics 48.3 26.3 79.1
Aromatics Breakdown
Benzene 1.9 0.6 37.1
Toluene 9.4 2.4 18.9
C8 15.6 6.7 13.5
C9 12.1 12.5 5.4
C10
+
9.3 4.1 4.2
Total 48.3 26.3 79.1
Source: Reference [49].
Fig. 8.19. Schematic diagram of a deep catalytic cracking unit (From W. Letzsch, Fluid catalytic
cracking, Chapter 6, Handbook of Petroleum Processing, Eds. DSJ Jones and PR Pujado,
The PetroFCC process flow diagram is shown in Fig. 8.20 and the cracking unit
is shown in Fig. 8.21. Most of the technologies employed in PetroFCC are adopted
from their UOP-FCC units. The spent catalyst is recycled back to the feed riser
following regeneration. Interestingly, according to UOP, the spent catalyst is less
active, but more selective than the clean regenerated catalyst. The operational
conditions of PetroFCC for enhanced olefin productions are; hydrocarbon pressure:
10•30 psia, temperature: 1,000•1,150o
F, and shape selective additives:
10•25 wt% of catalyst. The yield of various olefins from PetroFCC is compared
with FCC in Table 8.11.
Springer, 2006 [132]).
4208Petroleum
Fig. 8.20. The process flow diagram of a PetroFCC unit.
8.8 Cracking for Light Olefins and Aromatics 421
1 Separator vessel 15 Cyclone
2 Regenerator 16 Conduit
3 Blending vessel 17 Outlet
4 Vertical riser 18 Dipleg conduit
5 Nozzle 19 Catalyst Bed
6 Regenerator sandpipe 20 Opening to stripping zone
7 Control valve 21 Stripping zone
8 Recycle conduit 22 Line
9 Control valve 23 Coked catalyst conduit
10 Conduit 24 Control valve
11 Inlet to riser 25 Inlet
12 Swirl arm arrangement 26 Cyclone
13 Outlet 27 Vessel outlet
14 Chamber
Fig. 8.21. Cracking unit assembly for PetroFCC unit.
422 8 Petroleum
Table 8.11. Comparison of yields of various olefins between PetroFCC and FCC processes.
Compounds PetroFCC FCC
Propylene 22 4.7
Butylene 14 ~6
Ethylene 6 ~1
Gasoline 28 53.5
Source: Reference [49].
Maxofin process is designed to maximize propylene production. The main
reactor is shown in Fig. 8.22. It has a stacked reactor-regenerator configuration. A
special ZSM-5 additive is used along with the FCC catalyst to enhanced propylene
selectivity. The yield from the Maxofin process for a gas oil feed operating at
three different modes is given in Table 8.12.
7,128,827 [142]).
Fig. 8.22. The main reactor of the Maxofin process. (From Tallman MJ, Santner C, Miller RB
(2006) Integrated catalytic cracking and steam pyrolysis process for olefins- US Patent
8.9 Delayed Coking Unit (Coker) 423
Table 8.12. Yields from Maxofin unit.
Max C3= Intermediate Max Fuels
Recycle Yes No No
ZSM-5 Yes Yes No
Riser Temp, oC 538/593 538 538
Yields (wt%)
C2 Minus 7.6 2.3 2.2
Ethylene 4.3 2.0 0.9
Propylene 18.4 14.4 6.2
Butylene 12.9 12.3 7.3
Gasoline 18.8 35.5 49.8
Coke 8.3 6.4 5.9
Conversion 86.4 87.7 85.4
Source: Reference [49].
8.9 Delayed Coking Unit (Coker)
In a Delayed Coking Unit (Coker), low-value residuum is converted to high-value
light products, producing petroleum coke as a by-product by using mainly heat
when the residuum is held in a coke drum at a high temperature for a period of
time. Only solid coke remains and must be drilled out from the coke drums. A
schematic diagram of the Coker from the UOP is shown in Fig. 8.23.
Fig. 8.23. A delayed coking unit developed by UOP.
[143•150]. The large residuum molecules are cracked into smaller molecules
424 8 Petroleum
8.10 Hydrocracking
Hydrocracking utilizes hydrogen gas and a catalyst to modify the residue feed
and hydrogen immediately saturates any olefins that are formed. Hydrocracking
can produce LPG, naphtha, kerosene and distillates and a range of products
depending on the type of feed to the unit.
It proceeds by two main reactions: hydrogenation of higher unsaturated hydrocarbons
followed by cracking them to the required fuels. The process is carried out
by passing oil feed together with hydrogen at high pressure (1,000•2,500 psig, or
7•17 MPa) and moderate temperatures (500•750°F or 260•400°C) into a reactor
with a bifunctional catalyst, comprising an acidic solid and a hydrogenating metal
component. Gasoline of high octane number is produced, both directly and
through a subsequent step such as catalytic reforming; jet fuels may also be manufactured
simply by changing conditions with the same catalysts.
Generally, the process is used as an adjunct to catalytic cracking. Oils, which
are difficult to convert in the catalytic process because they are highly aromatic
and cause rapid catalyst decline, can be easily handled by hydrocracking process.
The low cracking temperature and the high hydrogen pressure, which decreases
catalyst fouling, make the process more favorable. The most important components
in any feed are the nitrogen-containing compounds, since these are severe
poisons for hydrocracking catalysts and must be almost completely removed.
The products from hydrocracking units are composed of either saturated or
aromatic compounds; no olefins are found. In making gasoline, the lower paraffins
formed in the reaction have high octane numbers. The remaining gasoline has
excellent properties as a feed to catalytic reforming, producing a highly aromatic
gasoline, which easily attains 100 octane number. Another attractive feature of
hydrocracking is the low yield of gaseous components, such as methane, ethane,
and propane, which are less desirable than gasoline.
A hydrocracking unit may have either a single stage once-through, single stage
with recycle, or a two-stage flow scheme. Among these flow schemes both single
stage with recycle and two-stage recycle are widely used in the industry.
8.10.1 Single Stage with Recycle
The flow diagram of a single stage with recycle unit is shown in Fig. 8.24. The
fresh feed is mixed with the recycled oil, preheated and passed downward through
the reactor over the catalyst bed along with hydrogen. The effluent from the
reactor goes through a series of separator to recover various product fractions and
stream into various products [151•172]. Only carbon•carbon bonds are broken
8.10 Hydrocracking 425
hydrogen. The recovered hydrogen together with the make up hydrogen is recycled
reactor using amorphous catalyst. However most of the units use a pretreatment
and a cracking catalyst configuration. The stream first passes through the pretreatment
catalyst where organic sulfur and nitrogen are converted to hydrogen
sulfide and ammonia, respectively. No attempt is made to remove hydrogen sulfide
and ammonia from the feed stream at this point. The product from the first
catalyst bed is passed over the hydrocracking catalyst in the second stage of the
reactor where most of the hydrocracking takes place. Hydrogen sulfide and
ammonia have little effect on the conversion or yield of the final product. The
catalyst for hydrocracking consists of sulfided molybdenum and nickel on alumina
support. The reactor operates in the temperature range of 570•800°F (300•425°C)
and hydrogen pressures between 1,250 and 2,500 psig (85•170 bar).
Fig. 8.24. Single stage hydrocracking unit. (From W. Letzsch, Fluid catalytic cracking, Chapter
8.10.2 Two-Stage Process
In the two stage process, the hydrotreatment is carried out in the first stage. Preheated
feedstock, along with recycled hydrogen is sent to the first-stage reactor,
where sulfur and nitrogen compounds are converted to hydrogen sulfide and
ammonia over a catalyst. Limited hydrocracking also occurs. A schematic diagram
of the two-stage process is shown in Fig. 8.25.
6, Handbook of Petroleum Processing, Eds. DSJ Jones and PR Pujado, Springer, 2006 [132]).
back to the reactor. Both the pre-treatment and cracking are achieved in the same
426 8 Petroleum
The product stream from the first stage is cooled and liquefied, and thus separates
hydrogen sulfide and ammonia. The liquid stream is run through a hydrocarbon
separator where it is fractionated with the unconverted oil and is recycled
to the second stage. The hydrogen is recycled to the feedstock. Depending on the
products desired, the stream is separated into gasoline components, jet fuel, and
gas oil fractions. The bottom products are again mixed with a hydrogen stream
and charged to the second stage. A higher temperature and pressure is used in the
second reactor. The product from the second stage is separated from the hydrogen
and charged to the fractionator. Since hydrogen sulfide and ammonia are not present
in the feed stream to the second stage reactor, various noble metal or base
metal sulfide can be used for hydrocracking. Typical reactions that take place during
8.11 Hydrotreatment
The main objective of hydrotreatment is to remove various undesired compounds
fications or for use as feedstocks elsewhere in the refinery. The product quality
specifications are driven by environmental regulations. A hydrotreatment facility
is designed to employ a wide range of operating conditions due to the variation of
the type of feed, desired cycle length, and expected quality of the finished product.
The following fractions are generally hydrotreated:
such as sulfur, nitrogen, olefins, and aromatics from the petroleum fractions [174•
184]. Hydrotreatment is also used to upgrade and to meet the strict product speciFig.
8.25. Two stage hydrocracking unit. (Adapted from 2006 Refining Processes Handbook,
Hydrocarbon Processing, Gulf Publishing Co. Houston, USA [173]).
hydrocracking are given in the handbook [173].
8.11 Hydrotreatment 427
Naptha: Pretreatment of the feed prior to catalytic reforming to remove sulfur,
nitrogen and metals. The trace metals present in the stream would poison (deactivate)
the noble metal catalysts used in the reforming units.
Kerosene and Diesel: Hydrotreatment of this fraction removes sulfur, saturates
olefins and some aromatics in the fraction. This upgrades kerosene and diesel
in terms of its product quality and stability.
Lube oil: Hydrotreatment improves its viscosity index, color and stability.
FCC Feed: Removal of sulfur and nitrogen compounds through hydrotreatment
improves yield, reduces emissions, and extends catalyst life.
Resids: Hydrotreatment removes sulfur compounds and improves its quality as
feedstocks.
Although hydrotreatment is used for a variety of applications as described
above, the basic flow diagram of the hydrotreatment plant is common. The two
major sections of the plant are a high-pressure reactor system (Fig. 8.26) and a
low-pressure fractionation system (Fig. 8.27).
The typical operating conditions of a hydrotreatment plant are as follows:
LHSV: 0.2•8.0
H2 circulation rate: 300•4,000 SCFB (50•675 Nm3
/m3
)
H2 partial pressure: 200•2,000 psia (14•138 bar)
SOR temperature: 550•700o
F (290•370o
C)
(LHSV: Liquid Hourly Space Velocity)
The feed and recycled gas (reactants) streams are heated to the desired
temperature before introducing them to the top of the reactor. As the reactants
flow downward through the catalyst bed, the hydrogenation reactions take place.
The effluents from the reactor are forwarded to the fractionation sections where
the stream is separated to desired products. The gaseous effluent from the reactor
contains H2 2 2
Hydrotreatment catalysts come in different shapes and sizes as shown in
Fig. 8.28, however, their basic characteristics are similar. The active component of
the catalyst is generally molybdenum sulfide, which is about 25 wt%, of the total
mass. The active component is dispersed on an inert support such as -alumina.
A promoter, which may be up to 25 wt%, is added to the catalyst to enhance the
activity of molybdenum sulfide. Both cobalt•molybdenum (Co•Mo) and nickel•
molybdenum (Ni•Mo) have been used as a promoter.
and H S. The H S is removed from the stream before recycling back
to the feed stream. Typical chemical reactions that take place in the reactor are given
in [173].
4288Petroleum
Fig. 8.26. The high pressure reactor system for hydrotreatment (W. Letzsch, Fluid catalytic cracking, Chapter 6, Handbook of Petroleum Processing, Eds.
DSJ Jones and PR Pujado, Springer, 2006).
8.11Hydrotreatment429
Fig. 8.27. The low pressure fractionation system of the hydrotreatment unit (W. Letzsch, Fluid catalytic cracking, Chapter 6, Handbook of Petroleum Processing,
Eds. DSJ Jones and PR Pujado, Springer, 2006).
430 8 Petroleum
Fig. 8.28. Various shapes of hydrotreatment catalysts. (From W. Letzsch, Fluid catalytic cracking,
Chapter 6, Handbook of Petroleum Processing, Eds. DSJ Jones and PR Pujado, Springer,
2006).
8.12 Gasoline Reforming
Gasoline reforming is referred to altering the composition of gasoline to achieve a
ferent parts of the refinery are further processed to ensure the product quality
specifications. Three major processes are used for gasoline reforming:
Alkylation
Catalytic olefin condensation
Isomerization
8.12.1 Alkylation
Alkylation of motor fuel is carried out to produce highly branched C5•C12
isoparaffins (also called alkylate) which are valuable gasoline blending component.
Alkylate is an ideal blendstock for making high octane fuel, especially as the
alternatives, such as lead additives, are banned and other additives such as MTBE
and aromatics are under scrutiny in many countries due to various environmental
and health concerns. In this process, C3•C5 olefins along with isobutane are converted
to C5•C12 isoparaffins using an acid catalyst. Either a liquid or a solid acid
may be used as a catalyst. A number of catalysts including H2SO4, HF, H2SO4HSO3F,
HF-BF3, AlCl3-HCl, trifluoromethane sulfonic acid chloride, Pt-alumina,
BF3 on alumina, zeolites, and ion exchanged resins have been proposed for the
higher octane rating [185•201]. Various gasoline or motor fuel fractions from dif-
8.12 Gasoline Reforming 431
2 4
alkylation are most common in the refineries. Recently, UOP has developed
a solid catalyst alkylation process (AlkyleneTM
) that is available for commercial
applications. Typical reactions are shown below. The majority of alkylate produced
today comes from two routes: sulfuric and hydrofluoric acid catalyzed alkylation.
The typical alkylation reactions are shown below.
8.12.1.1 Hydrofluoric Acid Alkylation Process
The basic operating principle of sulfuric and hydrofluoric alkylation processes is
rather similar. However, sulfuric acid is not as active as hydrofluoric acid as catalyst
for the alkylation reaction.
Sulfuric acid alkylation reaction should be carried out at a very low temperature
to maintain a low reactor temperature. The sulfuric acid consumption rate
A schematic flow diagram of the UOP HF Alkylation process is shown in
Fig. 8.29. The UOP design is a forced acid and water cooled system. In this process,
water is used to remove the heat of reaction. Therefore, the acid requirement
is not dependent on the heat removal and the acid use could be reduced significantly.
The mixing between the hydrocarbon and the acid is accomplished using
a pump, which at the same time can provide necessary inlet pressure for feed
nozzles. The feed is introduced in the alkylation reactor as fine droplets. The
enhanced dispersion and contact of hydrocarbon and acid contribute an additional
0.2•0.7 octane to the alkylate product. In the last 6 years UOP has licensed 6 new
HF units.
8.12.1.2 Sulfuric Acid Alkylation Process
ExxonMobil introduced the stirred auto-refrigerated sulfuric acid alkylation process
to maximize the yield. A simplified flow diagram of the process is shown in
Fig. 8.30.
alkylation reactions. Among these catalysts, HF [202•206] and H SO [207•219]
during alkylation reaction is over hundred times that of HF.
4328Petroleum
Fig. 8.29. The UOP hydrofluoric acid catalyzed alkylation process (2006 Refining Processes Handbook, Hydrocarbon Processing, 2006 [173]).
8.12GasolineReforming433
Fig. 8.30. Sulfuric acid catalyzed alkylation process flow diagram (2006 Refining Processes Handbook, Hydrocarbon Processing, 2006 [173]).
434 8 Petroleum
recycle refrigerant, are introduced to the reactor system. An emulsion is created
through thorough mixing of reactants and the acid catalyst. The olefins and isobutane
react very quickly to form alkylate and release reaction heat. The reaction
heat is removed by the auto-refrigeration system by vaporizing some isobutane
from the reaction mixture. Just like any other refrigeration system, the iso-butane
vapor is compressed, condensed, and returned to the reactor as recycle refrigerant.
From the reactor, the emulsion is routed to the settler, where the acid is separated
from the hydrocarbon phase, then recycled back to the reactor. The hydrocarbon
stream is washed with water to remove acidic components and is fed to the deisobutanizer.
The deisobutanizer bottom stream is split further into normal butane
and alkylates products.
A comparison of the two alkylation processes is given in Table 8.13. The HF
catalyzed process is cheaper to sulfuric acid process.
Table 8.13. A comparison of alkylation processes.
Process Parameters Alkylene +
Butamer*
HF+
Butamer*
Onsite Regeneration
H2SO4 +Butamer*
Total feed from FCC, BPSD 7, 064 7, 064 7, 064
C5+ Alkylate 8, 000 7, 990 7, 619
C5+ Alkylate RON 95.0 95.2 95.0
MON 92.9 93.3 92.2
(R+M)/2 94.0 84.3 93.6
C5+ Alkylate D-86, o
F
50% 213 225 216
90% 270 290 296
Economics
Variable cost of Production, $/bbl** 2.57 0.82 1.37
Fixed cost of production 1.88 2.43 3.53
Total cost of production 4.45 3.25 4.90
EEC, SMM 46.5 40.5 63.3
All cases include a butamer to maximize feed utilization
Raw materials are not included
8.12.2 Isomerization Process
Isomerization of n-butane, n-pentane and n-hexane is carried out into their respective
isoparaffins so that substantially higher octane number products are produced.
In this process, the olefin-recycle isobutane mixture, along with recycle acid and
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Isomerization process can also provide additional feedstock for alkylation unit
since it converts n-butane into isobutene.
There are two distinct isomerization processes; butane (C4) and pentane/hexane
(C5/C6). Butane isomerization produces feedstock for alkylation. Aluminum chloride
catalyst and hydrogen chloride are universally used for the low-temperature
processes. Platinum or another metal catalyst is used for the higher-temperature
processes. In a low-temperature process, the reactor operates at 230•340°F and
200•300 psi. Hydrogen is removed in a high-pressure separator and hydrogen
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heated in a reactor. The feed next goes to the isomerization reactor where the paraffins
are isomerized to isoparaffins in the presence of another catalyst. The reacin
Fig. 8.31.
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Listing of Standards
European Standard
EN 116: Diesel and domestic heating fuels • Determination of cold filter plugging point
EN 237: Liquid petroleum products • Petrol • Determination of low lead concentrations by
atomic absorption spectrometry
EN 1601: Liquid petroleum products • Unleaded petrol • Determination of organic oxygenate
compounds and total organically bound oxygen content by gas chromatography
(O-FID)
EN 2160: Petroleum products • Corrosiveness to copper • Copper strip test (ISO 2160:1998)
EN 3104: Petroleum products • Transparent and opaque liquids • Determination of kinematic
viscosity and calculation of dynamic viscosity (ISO 3104:1994)
EN 3405: Petroleum products - Determination of distillation characteristics at atmospheric
pressure (ISO 3405:2000)
EN 3675: Crude petroleum and liquid petroleum products • Laboratory determination of
density • Hydrometer method (ISO 3675:1998)
EN 4264: Petroleum products - Calculation of cetane index of middle-distillate fuels by the
four-variable equation (ISO 4264:2007)
EN 5165:Petroleum products • Determination of the ignition quality of diesel fuels •
Cetane engine method (ISO 5165:1998). EN ISO 5165:1998
EN 6245:Petroleum products • Determination of ash (ISO 6245:2001) EN ISO 6245:2002
EN 6246: Petroleum products • Gum content of light and middle distillate fuels • Jet
evaporation method (ISO 6246:1995)
EN 7536: Petroleum products • Determination of oxidation stability of gasoline • Induction
period method (ISO 7536:1994)
EN 8754: Petroleum products • Determination of sulfur content • Energy-dispersive X-ray
fluorescence spectrometry (ISO 8754:2003)
EN 10370: Petroleum products • Determination of carbon residue • Micro method (ISO
10370:1993). EN ISO 10370:1995
EN 12177: Liquid petroleum products • Unleaded petrol • Determination of benzene content
by gas chromatography. EN 12177:1998/AC:2000
EN 12185: Crude petroleum and petroleum products • Determination of density • Oscillating
U-tube method (ISO 12185:1996)
EN 12205: Petroleum products • Determination of the oxidation stability of middledistillate
fuels (ISO 12205:1995)
EN 12662: Liquid petroleum products • Determination of contamination in middle distil-
lates
217. Mosher AD (1996) Effluent refrigerated sulfuric acid alkylation. Petroleum and Coal
218. Prochukhan KY, Islamov ER, Nefedova IV, et al. (1999) New method for sulfuric acid
219. Pryor P, Graves D (2001) Improvements in sulfuric acid alkylation technology.
References 447
EN 12916: Petroleum products • Determination of aromatic hydrocarbon types in middle
distillates • High performance liquid chromatography method with refractive index
detection
EN 12937: Petroleum products • Determination of water • Coulometric Karl Fischer titration
method (ISO 12937:2000)
EN 13016-1: Liquid petroleum products • Vapour pressure • Part 1: Determination of air
saturated vapour pressure (ASVP) and calculated dry vapour pressure equivalent
(DVPE)
EN 13016-2: Liquid petroleum products • Vapour pressure • Part 2: Determination of
absolute pressure (AVP) between 40 C and 100 C
EN 14596: Petroleum products • Determination of sulfur content • Wavelength-dispersive
X-ray fluorescence spectrometry (ISO 14596:2007)
EN 22719: Petroleum products and lubricants; determination of flash point; PenskyMartens
closed cup method (ISO 2719:1988)
EN 23015: Petroleum products • Determination of cloud point (ISO 3015:1992)
EN 24260: Petroleum products and hydrocarbons • Determination of sulfur content •
Wickbold combustion method (ISO 4260:1987)
EN 25163: Motor and aviation-type fuels • Determination of knock characteristics • Motor
method
EN 25164: Methods of test for petroleum and its products. Motor fuels. Determination of
knock characteristics. Research method (1994)
Institute of Petroleum Standards
IP 4: Petroleum products • Determination of Ash IP 30 (2005)
IP 40: Petroleum products • Determination of oxidation stability of gasoline • Induction
period method (1997)
IP 41: Petroleum products • Determination of the ignition quality of diesel fuels • Cetane
engine method (1999)
IP 69: Petroleum products • Determination of vapour pressure • Reid method (2001)
IP 71: Section 1: Petroleum products •Transparent and opaque liquids • Determination of
kinematic viscosity and calculation of dynamic viscosity. (1995) Section 2: Glass
capillary kinematic viscometers • Specifications and operating instructions (1997)
IP 123: Petroleum products • Determination of distillation characteristics at atmospheric
pressure (2001)
IP 131: Petroleum products • Gum content of light and middle distillate fuels • Jet evaporation
method (1999)
IP 154: Petroleum products • Corrosiveness to copper • Copper strip test (2000)
IP 156: Determination of hydrocarbon types in petroleum products • Fluorescent indicator
adsorption method (2008)
IP 160: Crude petroleum and liquid petroleum products • Laboratory determination of density
• Hydrometer method IP 219 Cloud Point of Petroleum Products (1999)
IP 236: Petroleum products • Determination of knock characteristics of motor and aviation
fuels • Motor method (2006)
IP 237: Petroleum products • Determination of knock characteristics of motor fuels •
Research method (2006)
IP 243: Petroleum products and hydrocarbons • Determination of sulfur content • Wickbold
combustion method (1994)
IP 309: Diesel and domestic heating fuels • Determination of cold filter plugging point
(1999)
448 8 Petroleum
IP 336: Petroleum products • Determination of sulfur content • Energy-dispersive-X-ray
fluorescence method (2004)
IP 342: Petroleum products • Determination of thiol (mercaptan) sulfur in light and middle
distillate fuels • Potentiometric method (2000)
IP 365: Crude petroleum and petroleum products • Determination of density • Oscillating
U-tube method (1997)
IP 380: Petroleum products • Calculation of cetane index of middle distillate fuels by the
four-variable equation (2008)
IP 388: Petroleum products • Determination of the oxidation stability of middle-distillate
fuels (1997)
IP 391: Petroleum products • Determination of aromatic hydrocarbon types in middle distillates
• High performance liquid chromatography method with refractive index detection
(2007)
IP 394: Liquid petroleum products • Vapour pressure • Part 1: Determination of air saturated
vapour pressure (ASVP) (2008)
IP 398: Petroleum products • Determination of carbon residue • Micro method (1996)
IP 408: Liquid petroleum products • Unleaded petrol • Determination of organic oxygenate
compounds and total organically bound oxygen content by gas chromatography
(O-FID) (1998)
IP 425: Liquid petroleum products • Unleaded petrol • Determination of benzene content
by gas chromatography (2001)
IP 428: Liquid petroleum products • Petrol • Determination of low lead concentrations by
atomic absorption spectrometry (2006)
IP 440: Liquid petroleum products • Determination of contamination in middle distillates
(1999)
IP 447: Petroleum products • Determination of sulfur content • Wavelength-dispersive
X-ray fluorescence spectrometry (2008)
IP 450: Diesel fuel • Assessment of lubricity using the high-frequency reciprocating rig
(HFRR) • Part I: Test Method (2000)
IP 490: Petroleum products • Determination of sulfur content of automotive fuels • Ultraviolet
fluorescence method (ISO 20846:2004) (2005)
International Organization for Standards (ISO)
ISO 2160: Petroleum products • Corrosiveness to copper • Copper strip test Edition: 3
(1998)
ISO 2719: Determination of flash point • Pensky-Martens closed cup method Edition: 3
(2002)
ISO 3007: Petroleum products and crude petroleum • Determination of vapour pressure •
Reid method (1999)
ISO 3012: Petroleum products • Determination of thiol (mercaptan) sulfur in light and
middle distillate fuels • Potentiometric method (1999)
ISO 3015: Petroleum products • Determination of cloud point (1992)
ISO 3104: Petroleum products • Transparent and opaque liquids • Determination of kinematic
viscosity and calculation of dynamic viscosity (1994)
ISO 3405: Petroleum products • Determination of distillation characteristics at atmospheric
pressure (2000)
ISO 3675: Crude petroleum and liquid petroleum products • Laboratory determination of
density • Hydrometer method (1998)
References 449
ISO 3837: Liquid petroleum products • Determination of hydrocarbon types • Fluorescent
indicator adsorption method (1993)
ISO 4260: Petroleum products and hydrocarbons • Determination of sulfur content •
Wickbold combustion method (1987)
ISO 4264: Petroleum products and hydrocarbons • Determination of sulfur content Wickbold
combustion method (2007)
ISO 5163: Petroleum products • Determination of knock characteristics of motor and aviation
fuels • Motor method (2005)
ISO 5164: Petroleum products • Determination of knock characteristics of motor fuels •
Research method (2005)
ISO 5165: Petroleum products • Determination of the ignition quality of diesel fuels •
Cetane engine method (1998)
ISO 6245: Petroleum products • Determination of ash (2001)
ISO 6246: Petroleum products • Gum content of light and middle distillate fuels • Jet
evaporation method (1995)
ISO 7536: Petroleum products • Determination of oxidation stability of gasoline • Induction
period method (1994)
ISO 8754: Petroleum products • Determination of sulfur content • Energy-dispersive X-ray
fluorescence spectrometry (2003)
ISO 10370: Petroleum products • Determination of carbon residue • Micro method (1993)
ISO 12156: Diesel fuel • Assessment of lubricity using the high-frequency reciprocating rig
(HFRR) • Part 1: Test method. (2007) Diesel fuel • Assessment of lubricity using the
high-frequency reciprocating rig (HFRR) • Part 2: Limit (2006)
ISO 12185: Crude petroleum and petroleum products • Determination of density • Oscillating
U-tube method (1996)
ISO 12205: Petroleum products • Determination of the oxidation stability of middledistillate
fuels (1995)
ISO 12937: Petroleum products • Determination of water • Coulometric Karl Fischer titration
method (2000)
ISO 14596: Petroleum products • Determination of sulfur content • Wavelength-dispersive
X-ray fluorescence spectrometry (2007)
American Society for Testing and Materials (ASTM)
ASTM D86 07 Standard Test Method for Distillation of Petroleum Products at Atmospheric
Pressure
ASTM D93 06 Standard Test Methods for Flash Point by Pensky-Martens Closed Cup
Tester
ASTM D130 -04 Standard Test Method for Corrosiveness to Copper from Petroleum Products
by Copper Strip Test
ASTM D323 06 Standard Test Method for Vapor Pressure of Petroleum Products (Reid
Method)
ASTM D381 04 Standard Test Method for Gum Content in Fuels by Jet Evaporation
ASTM D445 04 Standard Test Method for Kinematic Viscosity of Transparent and Opaque
Liquids (and the Calculation of Dynamic Viscosity)
ASTM D482 07 Standard Test Method for Ash from Petroleum Products
ASTM D525 01 Standard Test Method for Oxidation Stability of Gasoline (Induction
Period Method)
450 8 Petroleum
ASTM D613 05 Standard Test Method for Cetane Number of Diesel Fuel Oil
ASTM D1298 99 Standard Test Method for Density, Relative Density (Specific Gravity),
or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer
Method
ASTM D1319 03 Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products
by Fluorescent Indicator Adsorption
ASTM D1319 03e1 Standard Test Method for Hydrocarbon Types in Liquid Petroleum
Products by Fluorescent Indicator Adsorption
ASTM D2274 03 Standard Test Method for Oxidation Stability of Distillate Fuel Oil
(Accelerated Method)
ASTM D2500 05 Standard Test Method for Cloud Point of Petroleum Products
ASTM D2622 08 Standard Test Method for Sulfur in Petroleum Products by Wavelength
Dispersive X-ray Fluorescence Spectrometry
ASTM D2699 07 Standard Test Method for Research Octane Number of Spark-Ignition
Engine Fuel
ASTM D2700 07 Standard Test Method for Motor Octane Number of Spark-Ignition
Engine Fuel
ASTM D3227 04 Standard Test Method for (Thiol Mercaptan) Sulfur in Gasoline,
Kerosine, Aviation Turbine, and Distillate Fuels (Potentiometric Method)
ASTM D3237 -06 Standard Test Method for Lead in Gasoline by Atomic Absorption Spec-
troscopy
ASTM D3606 07 Standard Test Method for Determination of Benzene and Toluene in Finished
Motor and Aviation Gasoline by Gas Chromatography
ASTM D4052 96(2002)e1 Standard Test Method for Density and Relative Density of
Liquids by Digital Density Meter ASTM D4530 07 Standard Test Method for
Determination of Carbon Residue (Micro Method)
ASTM D4294 08 Standard Test Method for Sulfur in Petroleum and Petroleum Products by
Energy Dispersive X-ray Fluorescence Spectrometry
ASTM D4737 04 Standard Test Method for Calculated Cetane Index by Four Variable
Equation
ASTM D4952 02(2007) Standard Test Method for Qualitative Analysis for Active Sulfur
Species in Fuels and Solvents (Doctor Test)
ASTM D5191 07 Standard Test Method for Vapor Pressure of Petroleum Products (Mini
Method)
ASTM D5453 08 Standard Test Method for Determination of Total Sulfur in Light
Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by
Ultraviolet Fluorescence
ASTM D5769 04 Standard Test Method for Determination of Benzene, Toluene, and Total
Aromatics in Finished Gasolines by Gas Chromatography/Mass Spectrometry
ASTM D6079 04 Standard Test Method for Evaluating Lubricity of Diesel Fuels by the
High-Frequency Reciprocating Rig (HFRR)
ASTM D6371 05 Standard Test Method for Cold Filter Plugging Point of Diesel and Heating
Fuels
Problems 451
ASTM D5599 00 Standard Test Method for Determination of Oxygenates in Gasoline by
Gas Chromatography and Oxygen Selective Flame Ionization Detection
ASTM D6217 98(2003)e1 Standard Test Method for Particulate Contamination in Middle
Distillate Fuels by Laboratory Filtration
ASTM D6304 04 Standard Test Method for Determination of Water in Petroleum Products,
Lubricating Oils, and Additives by Coulometric Karl Fisher Titration
Problems
1. In Table 8.1 is given a list of products which are manufactured from petroleum based
products. Is there any alternative route for their manufacturing? Do you think the
prices and quality of these products will be the same? What impact will this have on
our society.
2. What is crude oil benchmarking? Why it is necessary?
3. Why is it important to characterize crude oil?
4. Is crude oil essential for all types of transportation? Which sector of the transportation
system could be run without petroleum and how?
5. What are various processes involved in the processing of crude oil and what are their
objectives?
6. Why is crude petroleum separated into various fractions?
7. How dependent is the United States on foreign oil?
8. How many barrels of oil does the United States consume per year?
9. How much oil is produced in Alaska and where does it go?
10. How much petroleum does the United States import?
11. Why don$t fuel prices change as quickly as crude oil prices?
12. Do we have enough oil worldwide to meet our future needs?
13. How many gallons of gasoline does one barrel of oil make?
14. What are the differences between various types of crude oil prices?
15. What are the differences among •crude oil•, •petroleum products•, and •petroleum•?
16. What are the products and uses of petroleum?
17. When was the last refinery built in the United States?
18. Define the octane number? Why is it important?
19. Write a report on the energy requirements for operating a refinery.
20. Write a report on the wastes generated from processing of crude oil.
21. What is the difference between gasoline and diesel fuel?