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Oil Refining

Oil Refining

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Oil Refining
Oil Refining

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Published by: 5161440 on Feb 21, 2013
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Ó
2012Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim
Oil Refining
G
UNTER
A
LFKE
, Hamburg, Germany
W
ALTHER
W. I
RION
(
RETIRED
),
Formerly Deutsche Shell AG, Hamburg, Germany
O
TTO
S. N
EUWIRTH
(
RETIRED
),
Formerly UK Wesseling, Wesseling, Germany
1. Introduction
. . . . . . . . . . . . . . . . . . . . . . 208
1.1. History
. . . . . . . . . . . . . . . . . . . . . . . . . . 208
1.2. General Aspects of Oil Refining
. . . . . . . 210
2. Crude Oils and Products
. . . . . . . . . . . . 211
2.1. Crude Oil Constituents
. . . . . . . . . . . . . 211
2.2. Classification of Crude Oils
. . . . . . . . . . 213
2.3. Oil Products
. . . . . . . . . . . . . . . . . . . . . . 2142.3.1. Gas Fuels . . . . . . . . . . . . . . . . . . . . . . . . 2142.3.2. Liquid Fuels . . . . . . . . . . . . . . . . . . . . . . 2142.3.3. Nonfuel Applications. . . . . . . . . . . . . . . . 216
3. Oil Rening Processes
. . . . . . . . . . . . . . 216
3.1. Crude Oil Distillation
. . . . . . . . . . . . . . 2163.1.1. Atmospheric Distillation . . . . . . . . . . . . . 2173.1.2. Vacuum Distillation. . . . . . . . . . . . . . . . . 2183.1.3. Crude Oil Desalting. . . . . . . . . . . . . . . . . 219
3.2. Catalytic Cracking (Cat Cracking)
. . . . 220
3.3. Hydrotreating
. . . . . . . . . . . . . . . . . . . . 2233.3.1. Distillate Hydrotreating . . . . . . . . . . . . . . 2243.3.2. Pyrolysis Gasoline Hydrotreating . . . . . . . 2253.3.3. Desulfurizing by Adsorption . . . . . . . . . . 226
3.4. Catalytic Reforming
. . . . . . . . . . . . . . . . 2263.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . 2263.4.2. Semiregenerative Reformer . . . . . . . . . . . 2283.4.3. Fully Regenerative Reformer . . . . . . . . . . 2293.4.4. Continuously Regenerative Reformer . . . . 229
3.5. Hydrocracking
. . . . . . . . . . . . . . . . . . . . 229
3.6. Residue Conversion Processes
. . . . . . . . 2313.6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . 2313.6.2. Fundamentals of Residue Conversion andProcess Options . . . . . . . . . . . . . . . . . . . 2313.6.3. Hydrogen Addition (‘‘H-in’’) Processes . . 2333.6.3.1. Residue Hydrotreating (Demetallization,Desulfurization, Denitrification) . . . . . . . . 2333.6.3.2.Residue Hydrocracking (Hydroconversion) 2333.6.4. Carbon Rejection (‘‘C-out’) Processes . . . . 2363.6.4.1.Thermal Processes (Visbreaking, Coking). . 2363.6.4.2.Catalytic Processes (Residue Cat Cracking) 2383.6.5. Other Processes. . . . . . . . . . . . . . . . . . . . 2383.6.5.1.Extraction of Asphaltenes . . . . . . . . . . . . 2383.6.5.2.Partial Oxidation . . . . . . . . . . . . . . . . . . . 2393.6.6. Process Combinations . . . . . . . . . . . . . . . 240
3.7. Gasoline Upgrading Processes
. . . . . . . . 2413.7.1. Alkylation. . . . . . . . . . . . . . . . . . . . . . . . 2413.7.2. Polymerization . . . . . . . . . . . . . . . . . . . . 2423.7.3. Isomerization . . . . . . . . . . . . . . . . . . . . . 2423.7.4. Production of Ethers (MTBE, ETBE) . . . . 243
3.8. Other Processes
. . . . . . . . . . . . . . . . . . . 2443.8.1. Gas Treating . . . . . . . . . . . . . . . . . . . . . . 2443.8.2. Sulfur Recovery . . . . . . . . . . . . . . . . . . . 244
3.9. Catalysts
. . . . . . . . . . . . . . . . . . . . . . . . 244
4. Environmental Protection in Oil Refining
245
4.1. Introduction
. . . . . . . . . . . . . . . . . . . . . 245
4.2. Manufacturing Emissions
. . . . . . . . . . . 2464.2.1. Hydrocarbons . . . . . . . . . . . . . . . . . . . . . 2464.2.1.1.Hydrocarbons in Air . . . . . . . . . . . . . . . . 2464.2.1.2.Hydrocarbons in Wastewater . . . . . . . . . . 2474.2.1.3.Hydrocarbons in Soil and Groundwater . . 2484.2.2. Sulfur and Nitrogen Compounds . . . . . . . 2484.2.2.1.Sulfur Compounds. . . . . . . . . . . . . . . . . . 2484.2.2.2.Nitrogen Compounds. . . . . . . . . . . . . . . . 2504.2.3. Noise . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
4.3. Consumer Related Emissions
. . . . . . . . . 2504.3.1. Transportation Fuels . . . . . . . . . . . . . . . . 2504.3.1.1.Motor Gasoline . . . . . . . . . . . . . . . . . . . 2514.3.1.2.Diesel Fuel . . . . . . . . . . . . . . . . . . . . . . . 2524.3.2. Marine Fuels . . . . . . . . . . . . . . . . . . . . . 2524.3.3. Fuels for Heat Generation . . . . . . . . . . . . 252
4.4. Cost of Environmental Conservation
. . . 253
5. Integrated Refinery Models
. . . . . . . . . . 254
5.1. Trends of Refinery Structures
. . . . . . . . 254
5.2. Hydroskimming Refinery
. . . . . . . . . . . . 255
5.3. Conversion Concepts
. . . . . . . . . . . . . . . 2565.3.1. Cat Cracking Visbreaking Refinery . . . . 2565.3.2. Hydrocracking Cat Cracking Refinery . . 2565.3.3. Hydrocracking Coking Refinery . . . . . . 2565.3.4. Integration of Existing Refineries . . . . . . . 258
6. Corrosion and Materials
. . . . . . . . . . . . 258
7. Testing and Analysis
. . . . . . . . . . . . . . . 258
7.1. Crude Oil and Product Properties
. . . . . 259
7.2. Testing Methods and Standards
. . . . . . . 259
8. Storage and Transport
. . . . . . . . . . . . . . 259
References
. . . . . . . . . . . . . . . . . . . . . . . 260
DOI: 10.1002/14356007.a18_051.pub2
 
1. Introduction
1.1. History
Crude oil or petroleum, and a limited number of oil derivatives such as asphalt, pitch, and naph-tha have been known and sporadically usedsince medieval times in the Orient, Europe,and America. However, it was not until the19th century that significant oil processingstarted.The first commercial oil operations can bedated back to the 1850s, with production com-mencing in Russia, Romania, and the UnitedStates [1]. The first successfully purpose-drilledoil well in 1859 in Pennsylvania was the begin-ning of the modern oil industry, since it stimu-lated fast development in the search, production,and refining of oil.Subsequently, small and simple oil refinerieswere built and operated in direct vicinity of thePennsylvanian oil fields and on the east coast of the United States, where former coal distillationprocesses were modified for oil processing.These first distilling units worked in
batch oper-ation
and produced a small number of oilfractions.Batch distillation was later combined witha thermal cracking step in order to increase thedistillate yield. In this crack distillation, theheavier part of the oil was heated further andcracked until coke remained as residue in thestill. The lower sections of the vessels wereequipped with fired heating tubes to improveheat transfer.Important progress in oil processing wasachieved in Russia with the
continuous crudedistillation
process which was introduced in arefinery in Baku in 1875. The continuousprinciple worked with a battery of stills, ar-ranged in series, with stepwise gravity over-flow of the oil throughout the battery. The stillswere heated up to successively increasingtemperatures, so that each still could producea distillate fraction corresponding to its tem-perature level. This continuous process systemoffered the possibility for mass production atreduced manpower requirements, and utiliza-tion of the residual heat for preheating thecrude oil feed.During the first five decades of oil refining thepredominantproductwaskerosene(lampoil),andonlysmallamountsofotherproducts,suchasfueloil, pitch, and lubricating oil, were marketable.The lubricating oils were produced by vacuumdistillation(UnitedStates,inthe1870s)andsteamdistillation (Russia, in the 1880s). The lightestand heaviest fractions of the crude oil distillation,
Abbreviations used in this article:
BTX: benzene – toluene – xyleneCC: catalytic crackerCR: circulating refluxDAO: deasphalted oilDEA: diethanolamineDIPA: diisopropyl amineETBE: ethyl
tert 
-butyl etherFCC: fluid-bed catalytic crackingGO: gas oilIBP: initial boiling pointICR: intermediate circulating refluxHC: hydrocracking, hydrocarbonsHDN: hydrodenitrificationHDS: hydrodesulfurizationHGO: heavy gas oilHT: hydrotreatingLCR: lower circulating refluxLGO: light gas oilLHSV: liquid hourly space velocityLPG: liquefied petroleum gasMEA: monoethanolamineMON: motor octane numberMTBE: methyl
tert 
-butyl etherOPEC: Organization of the Petroleum Export-ing CountriesRON: research octane numberSDA: solvent deasphaltingTAME:
tert 
-amyl methyl etherTBP: true boiling pointTIP: total isomerization processUCR: upper circulating refluxVB: visbreakerVGO: vacuum gas oil
208 Oil Rening Vol. 25
 
namelygasolineandresidue,werenotusedatthattime and had to be burnt.From the beginning of the 20th century,a complete shift in product demand occurredbecause of the fast expansion of electricity andmotorization. The availability of electricitygreatly diminished the demand for lamp oil,whereas the increase in motor vehicles increasedthe need for gasoline, which soon became thepriority product.The increasing gasoline demand initiated thedevelopmentof 
thermalcracking processes
.TheBurton process, which came into operation ca.1912, produced up to 30% of cracked gasolinefrom paraffinic gas oil feedstocks.During World War I the requirements for avariety of oil products, in particular gasoline andfuel oils, rose dramatically, and the demandcontinued to increase in the 1920s and 1930s.Gasoline again showed the highest growth rates.In the same period the bitumens (asphalts)(
!
Asphalt and Bitumen) became a desired andimportant product group,owing to theexpansionof road construction.By the mid 1920s a new generation of 
improved thermal cracking processes
emerged,of which the Dubbs process gained supremeimportance. The gas oil or residue feed washeated in a cracking furnace, and the crackingreactionswerecompletedinreactionchambersinwhich coke was formed as residual product. Theyield of cracked gasoline could be as high as50%. However, with the advent of the
Houdrycatalyticcrackingprocess
duringthesecondhalf of the 1930s, the thermal cracking capacitieswere largely replaced by catalytic cracking unitswhich took the lead in gasoline production in thenext two decades.The catalytic cracking process proved thatthe octane quality of cracked gasolines thatcontain unsaturated hydrocarbons was superiorto that of distilled (straight-run) gasolines.Hence, the straight-run naphthas were increas-ingly processed in
thermal reformers
at highcracking temperatures, to add a higher portionof unsaturated hydrocarbons to the motorgasoline.In the late 1930s the first
catalytic reforming processes
were developed with improved gaso-line quality by simultaneous desulfurization andincrease in octane number. These
hydroforming
processes used molybdenum-on-alumina cata-lysts in the presence of hydrogen at high temper-ature and pressure.With the introduction of 
platinum catalysts
inthe late 1940s, the catalytic reforming processwas greatly improved: high quality gasolineswere produced in higher yields, and hydrogenwas formed as byproduct.A desulfurization step (
hydrotreating
) wasinstalledupstreamofthereformer,usingcobalt –molybdenum catalysts and hydrogen from thecatalytic reforming process in order to removesulfur from the gasoline feedstock. Sulfur wouldotherwise poison the noble metal catalyst in thereforming process. Owing to their quality andyield advantages, catalytic reforming unitsreplaced the thermal reforming capacities in arelatively short period of time.In the 1930s the United States and the SovietUnion were the main oil producers and suppliedsufficient gasoline products for their own needs.The consumer countries in the rest of the worldhad to rely on the oil supplies from a number of producing countries, chiefly from South andCentral America (Venezuela, Mexico) and theMiddle East (Iraq, Saudi Arabia).The largest expansion of the oil industrytook place within the three decades after WorldWar II. Between 1950 and 1980, a fivefoldincrease in oil demand occurred worldwide.The formation of political and economic blocsin ‘‘eastern’’ and ‘‘western’’ hemispheres andthe foundation of the OPEC (Organization of the Petroleum Exporting Countries) in 1960were significant for international oil trade anddistribution.Oil refining underwent a rapid developmentinitially in the highly industrialized regions of North America, Western and Eastern Europe,Eastern Asia, and Australia, and later, in thewake of increasing populations and energydemands, also in many developing countries inLatin America, Africa, and Asia. Finally, largerefinery plants were also built in the OPECcountriesfortheexportofproductsattheexpenseof crude oil exports.The two worldwide crude oil price increasesin 1973 1974 and 1979 1980 promptedchanges in oil consumption, which caused theoil industry to develop processes with increasedyields and a reduction of refinery capacities,
Vol. 25 Oil Rening 209

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