WO2008010799A1 - Procédé de désulfurisation d'hydrocarbures - Google Patents
Procédé de désulfurisation d'hydrocarbures Download PDFInfo
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- WO2008010799A1 WO2008010799A1 PCT/US2006/027987 US2006027987W WO2008010799A1 WO 2008010799 A1 WO2008010799 A1 WO 2008010799A1 US 2006027987 W US2006027987 W US 2006027987W WO 2008010799 A1 WO2008010799 A1 WO 2008010799A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hydrocarbonaceous
- boiling
- stream
- desulfurization
- zone
- Prior art date
Links
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 41
- 230000023556 desulfurization Effects 0.000 title claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 35
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000003921 oil Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000010457 zeolite Substances 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- -1 diesel Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 208000033830 Hot Flashes Diseases 0.000 description 4
- 206010060800 Hot flush Diseases 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052678 stilbite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- hydrodesulfurization processes have been used by petroleum refiners to produce more valuable hydrocarbonaceous streams such as naphtha, gasoline, kerosene and diesel, for example, having lower concentrations of sulfur and nitrogen.
- Feedstocks most often subjected to hydrotreating or desulfurization are normally liquid hydrocarbonaceous streams such as naphtha, kerosene, diesel, gas oil, vacuum gas oil (VGO) and reduced crude, for example.
- hydrodesulfurization severity is selected to produce an improvement sufficient to produce a marketable product or a suitable feedstock for downstream processing.
- Desulfurization is generally accomplished by contacting the hydrocarbonaceous feedstock in a desulfurization reaction vessel or zone with a suitable desulfurization catalyst under conditions of elevated temperature and pressure in the presence of hydrogen to yield a product containing the desired maximum limits of sulfur.
- a suitable desulfurization catalyst under conditions of elevated temperature and pressure in the presence of hydrogen to yield a product containing the desired maximum limits of sulfur.
- the operating conditions and the desulfurization catalysts within the desulfurization reactor influence the quality of the desulfurized products.
- US 5,114,562 Bl discloses a process wherein middle distillate petroleum streams are hydrotreated to produce a low sulfur and low aromatic product in two reaction zones in series.
- the effluent of the first reaction zone is purged of hydrogen sulfide by hydrogen stripping and then reheated by indirect heat exchange.
- the second reaction zone employs a sulfur-sensitive noble metal hydrogenation catalyst.
- the present invention is an improved process for the production of low sulfur hydrocarbonaceous products.
- a first hydrocarbonaceous feedstock comprising hydrocarbon components boiling above 343°C and hydrogen is reacted in a first desulfurization zone to produce a first desulfurization zone effluent which is introduced into a vapor-liquid separator operated at an elevated temperature to provide a vaporous stream comprising lower boiling hydrocarbonaceous compounds and hydrogen and a liquid hydrocarbonaceous stream comprising hydrocarbon components having a reduced concentration of sulfur.
- the vaporous stream comprising lower boiling hydrocarbonaceous compounds, hydrogen, and a second hydrocarbonaceous feedstock comprising hydrocarbon components boiling below 371 0 C are reacted in a hydrocracking zone to produce a hydrocracking zone effluent which is introduced together with a hydrocarbonaceous recycle stream preferably boiling in the range from 149°C to 371 °C to a hydrogenation zone to produce a hydrogenation zone effluent which is fractionated to produce an ultra low sulfur hydrocarbonaceous stream preferably boiling in the range from 149 0 C to 371 0 C.
- the liquid hydrocarbonaceous stream provided by the vapor- liquid separator is fractionated to produce a hydrocarbonaceous recycle stream preferably boiling in the range from 149°C to 371°C and a liquid hydrocarbonaceous stream comprising hydrocarbon components boiling above 371 0 C and having a reduced concentration of sulfur.
- Other embodiments of the present invention encompass further details such as types and descriptions of feedstocks, desulfurization catalysts, hydrocracking catalysts and preferred operating conditions including temperatures and pressures, all of which are hereinafter disclosed in the following discussion of each of these facets of the invention.
- the drawing is a simplified process flow diagram of a preferred embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION
- the first feedstock which is introduced into the first desulfurization zone preferably contains components boiling above 343°C and more preferably boiling above 371 0 C and includes, for example, atmospheric gas oils, vacuum gas oils, cracked gas oils, coker distillates, straight run distillates, solvent deasphalted oils, pyrolysis-derived oils, high boiling synthetic oils and cat cracker distillates.
- a preferred feedstock is a gas oil or other fraction having at least 50% by weight and most usually at least 75% by weight of its components boiling at a temperature between 315°C and 538°C.
- the first feedstock is reacted with hydrogen in a first desulfurization zone containing desulfurization catalyst operated at desulfurization conditions.
- Preferred desulfurization conditions include a temperature from 204 0 C to 482°C and a liquid hourly space velocity of the hydrocarbonaceous feed from 0.1 hr "1 to 10 hr "1 .
- Suitable desulfurization catalysts for use in the present invention are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal, preferably iron, cobalt and nickel, more preferably cobalt and/or nickel and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina.
- Other suitable desulfurization catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. It is within the scope of the present invention that more than one type of desulfurization catalyst be used in the same reaction vessel.
- the Group VIII metal is typically present in an amount ranging from 2 to 20 weight percent, preferably from 4 to 12 weight percent.
- the Group VI metal will typically be present in an amount ranging from 1 to 25 weight percent, preferably from 2 to 25 weight percent.
- Typical desulfurization temperatures range from 204 0 C to 482 0 C with pressures from 2.1 MPa to 17.3 MPa, preferably from 2.1 MPa to l3.9 MPa.
- the resulting effluent from the first desulfurization zone is introduced into a vapor-liquid separator preferably operated at a temperature greater than 288°C to provide a vaporous stream comprising hydrogen, hydrogen sulfide and lower boiling hydrocarbonaceous compounds boiling up to 371 °C and a first liquid hydrocarbonaceous stream comprising hydrocarbon components boiling above 371°C and having a reduced concentration of sulfur.
- This first liquid hydrocarbonaceous stream also contains a portion of hydrocarbons boiling in the range from 149°C to 371 0 C is preferably introduced into a hot flash zone, then a cold flash zone and subsequently fractionated to provide a hydrocarbonaceous recycle stream containing hydrocarbons boiling in the range from 149°C to 371°C and a second liquid hydrocarbonaceous stream comprising hydrocarbon components boiling above 371 0 C and having a reduced concentration of sulfur.
- This second liquid hydrocarbonaceous stream is preferably utilized as a suitable feedstock for a fluid catalytic cracking process.
- the vaporous stream comprising hydrogen, hydrogen sulfide and lower boiling hydrocarbonaceous compounds boiling up to 371 0 C and a second hydrocarbonaceous feedstock comprising hydrocarbon components boiling below 371 0 C is passed to a hydrocracking zone containing hydrocracking catalyst to produce a hydrocracking zone effluent.
- the second hydrocarbonaceous feedstock may be any suitable feedstock boiling below 371 0 C and preferably boils in the range from 177°C to 371 0 C.
- suitable feedstocks for example, include straight run middle distillate, kerosene and diesel boiling range hydrocarbons, coker distillate and light cycle oil.
- the hydrocracking zone may contain one or more beds of the same or different catalyst.
- the preferred hydrocracking catalysts when the preferred products are middle distillates the preferred hydrocracking catalysts utilize amorphous bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components.
- the hydrocracking zone when the preferred products are in the gasoline boiling range, the hydrocracking zone contains a catalyst which comprises, in general, any crystalline zeolite cracking base upon which is deposited a minor proportion of a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
- the zeolite cracking bases are sometimes referred to in the art as molecular sieves and are usually composed of silica, alumina and one or more exchangeable cations such as sodium, magnesium, calcium, rare earth metals, etc. They are further characterized by crystal pores of relatively uniform diameter between 4 and 14 Angstroms. It is preferred to employ zeolites having a relatively high silica/alumina mole ratio between 3 and 12. Suitable zeolites found in nature include, for example, mordenite, stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujasite.
- Suitable synthetic zeolites include, for example, the B, X, Y and L crystal types, e.g., synthetic faujasite and mordenite.
- the preferred zeolites are those having crystal pore diameters between 8-12 Angstroms, wherein the silica/alumina mole ratio is 4 to 6.
- a prime example of a zeolite falling in the preferred group is synthetic Y molecular sieve.
- the natural occurring zeolites are normally found in a sodium form, an alkaline earth metal form, or mixed forms.
- the synthetic zeolites are nearly always prepared first in the sodium form.
- Hydrogen or "decationized" Y zeolites of this nature are more particularly described in US-A-3, 130,006.
- Mixed polyvalent metal-hydrogen zeolites may be prepared by ion-exchanging first with an ammonium salt, then partially back exchanging with a polyvalent metal salt and then calcining.
- the hydrogen forms can be prepared by direct acid treatment of the alkali metal zeolites.
- the preferred cracking bases are those which are at least 10 percent, and preferably at least 20 percent, metal-cation- deficient, based on the initial ion-exchange capacity.
- a specifically desirable and stable class of zeolites are those wherein at least 20 percent of the ion exchange capacity is satisfied by hydrogen ions.
- the active metals employed in the preferred hydrocracking catalysts of the present invention as hydrogenation components are those of Group VIII, i.e., iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.
- other promoters may also be employed in conjunction therewith, including the metals of Group VIB, e.g., molybdenum and tungsten.
- the amount of hydrogenating metal in the catalyst can vary within wide ranges. Broadly speaking, any amount between 0.05 percent and 30 percent by weight may be used. In the case of the noble metals, it is normally preferred to use 0.05 to 2 weight percent.
- the preferred method for incorporating the hydrogenating metal is to contact the zeolite base material with an aqueous solution of a suitable compound of the desired metal wherein the metal is present in a cationic form.
- the resulting catalyst powder is then filtered, dried, pelleted with added lubricants, binders or the like if desired, and calcined in air at temperatures of, e.g., 371°-648°C in order to activate the catalyst and decompose ammonium ions.
- the zeolite component may first be pelleted, followed by the addition of the hydrogenating component and activation by calcining.
- the foregoing catalysts may be employed in undiluted form, or the powdered zeolite catalyst may be mixed and copelleted with other relatively less active catalysts, diluents or binders such as alumina, silica gel, silica-alumina cogels, activated clays and the like in proportions ranging between 5 and 90 weight percent.
- diluents may be employed as such or they may contain a minor proportion of an added hydrogenating metal such as a Group VIB and/or Group VIII metal.
- Additional metal promoted hydrocracking catalysts may also be utilized in the process of the present invention which comprises, for example, aluminophosphate molecular sieves, crystalline chromosilicates and other crystalline silicates. Crystalline chromosilicates are more fully described in US-A-4,363,718.
- the hydrocracking is conducted in the presence of hydrogen and preferably at hydrocracking conditions which include a temperature from (232 0 C) to 468 0 C, a pressure from 3548 IcPa to 20785 kPa, a liquid hourly space velocity (LHSV) from 0.1 to 30 hr '1 , and a hydrogen circulation rate from 337 normal m /m ) to 4200 normal m /m .
- the hydrocracking zone effluent and a hydrocarbonaceous recycle stream preferably boiling in the range from 232°C to 371 0 C is preferably passed directly into a hydrogenation zone containing hydrogenation catalyst to produce a hydrogenation zone effluent.
- the hydrogenation catalyst may be selected from any known hydrogenation or desulfurization catalyst. This catalyst may be the same or different from the desulfurization catalyst used in the desulfurization zone and may be selected from known desulfurization catalysts such as those described hereinabove for example. Preferred hydrogenation conditions may be selected from those ranges taught for the desulfurization zone and may be more, less or equal to the severity of reaction conditions selected for the desulfurization zone. [0020] The resulting hydrogenation zone effluent is partially condensed and introduced into a cold vapor-liquid separator operated at a temperature from 21 0 C to 60°C to produce a hydrogen-rich gaseous stream containing hydrogen sulfide and a liquid hydrocarbonaceous stream.
- the resulting hydrogen-rich gaseous stream is preferably passed through an acid gas scrubbing zone to reduce the concentration of hydrogen sulfide to produce a purified hydrogen-rich gaseous steam, a portion of which may then be recycled as desired or required.
- the liquid hydrocarbonaceous steam from the cold vapor-liquid separator is preferably introduced into a cold flash drum to remove dissolved hydrogen and normally gaseous hydrocarbons and subsequently sent to a fractionation zone to produce a low sulfur diesel product stream. It is preferred that the diesel product stream contains less than 50 wppm sulfur, more preferably 10 wppm sulfur.
- the make-up hydrogen may be introduced into the process at any convenient location.
- a feed stream comprising a heavy vacuum gas oil enters the process through line 1 and is admixed with a hydrogen-rich gaseous stream provided via line 28 and the resulting admixture is introduced via line 2 into desulfurization zone 3.
- Hydrogen quench is provided to desulfurization zone 3 via lines 30 and 31.
- a resulting effluent from desulfurization zone 3 is transported via line 4 and introduced into hot vapor-liquid separator 5.
- a gaseous stream comprising hydrogen, hydrogen sulfide and lower boiling range hydrocarbons is removed from hot vapor-liquid separator 5 via line 17 and is admixed with a light cycle oil carried via line 18 and boiling in the middle distillate range, and the resulting admixture is transported via line 19 and introduced into reactor 20 wherein the stream contacts hydrocracking zone 21.
- the resulting effluent from hydrocracking zone 21 is passed directly to hydrogenation zone 22 which is contained in reaction zone 20.
- a resulting effluent from hydrogenation zone 22 is carried via line 23 and introduced into heat-exchanger 24.
- a resulting cooled and partially condensed stream is removed from heat- exchanger 24 via line 25 and introduced into cold vapor-liquid separator 26.
- a hydrogen-rich gaseous stream is removed from cold vapor-liquid separator 26 via line 27 and is introduced into desulfurization zone 3 via lines 28, 29, 30 and 31 as hereinabove described.
- a liquid hydrocarbonaceous stream is removed from cold vapor-liquid separator 26 via line 32 and introduced into cold flash drum 33.
- a gaseous stream comprising hydrogen and normally gaseous hydrocarbons is removed from cold flash drum 33 via line 34.
- a liquid stream comprising diesel boiling range hydrocarbons is removed from cold flash drum 33 via line 35 and introduced into fractionation zone 36.
- An ultra low sulfur diesel stream is recovered from fractionation zone 36 and is removed therefrom via line 38.
- a hydrocarbonaceous stream comprising compounds boiling below the diesel range is removed from fractionation zone 36 via line 37 and recovered.
- a liquid stream is removed from hot vapor-liquid separator 5 via line 6 and introduced into hot flash drum 7.
- a vapor stream comprising hydrogen and lower boiling hydrocarbons is removed from hot flash drum 7 via line 8 and recovered.
- a liquid hydrocarbonaceous stream containing hydrocarbons boiling at a temperature greater than 371°C and diesel boiling range hydrocarbons is removed from hot flash drum 7 via line 9 and is introduced along with a hereinabove described vapor stream provided via line 34 and the resulting admixture is introduced via line 10 into stripping zone 11.
- a stream comprising hydrogen, normally gaseous hydrocarbons and gasoline boiling range hydrocarbons is removed from stripping zone 11 via line 12 and recovered.
- a liquid hydrocarbonaceous stream comprising hydrocarbons boiling at a temperature greater than 371 0 C and diesel boiling range hydrocarbons is removed from stripping zone 11 via line 13 and introduced into fractionation zone 14.
- a stream comprising lower boiling hydrocarbons is removed from fractionation zone 14 via line 15 and recovered.
- a liquid hydrocarbonaceous stream comprising hydrocarbons boiling at a temperature greater than 371°C is removed from fractionation zone 14 via line 17 and recovered.
- a liquid stream comprising diesel boiling range hydrocarbons is removed from fractionation zone 14 via line 16 and is introduced into reaction zone 20 as hereinabove described.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2657780A CA2657780C (fr) | 2006-07-19 | 2006-07-19 | Procede de desulfurisation d'hydrocarbures |
RU2009105660/04A RU2402594C1 (ru) | 2006-07-19 | 2006-07-19 | Способ десульфуризации углеводородов |
EP06787821A EP2041245A4 (fr) | 2006-07-19 | 2006-07-19 | Procédé de désulfurisation d'hydrocarbures |
CN200680055639.3A CN101506334B (zh) | 2006-07-19 | 2006-07-19 | 一种烃脱硫的方法 |
PCT/US2006/027987 WO2008010799A1 (fr) | 2006-07-19 | 2006-07-19 | Procédé de désulfurisation d'hydrocarbures |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2006/027987 WO2008010799A1 (fr) | 2006-07-19 | 2006-07-19 | Procédé de désulfurisation d'hydrocarbures |
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WO2008010799A1 true WO2008010799A1 (fr) | 2008-01-24 |
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PCT/US2006/027987 WO2008010799A1 (fr) | 2006-07-19 | 2006-07-19 | Procédé de désulfurisation d'hydrocarbures |
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Country | Link |
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EP (1) | EP2041245A4 (fr) |
CN (1) | CN101506334B (fr) |
CA (1) | CA2657780C (fr) |
RU (1) | RU2402594C1 (fr) |
WO (1) | WO2008010799A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014011967A1 (fr) * | 2012-07-13 | 2014-01-16 | Lyondell Chemical Technology, L.P. | Procédé perfectionné de réduction de couleur de diesel à teneur ultra faible en soufre |
WO2016093777A1 (fr) * | 2014-12-11 | 2016-06-16 | Türkiye Petrol Rafinerileri A. S. | Procédé de production de diesel |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2657780C (fr) * | 2006-07-19 | 2012-02-07 | Uop Llc | Procede de desulfurisation d'hydrocarbures |
RU2387700C1 (ru) * | 2008-09-22 | 2010-04-27 | ООО "ЛУКОЙЛ-Нижегороднефтеоргсинтез" | Способ получения дизельного топлива |
MX356615B (es) * | 2011-04-15 | 2018-06-06 | Aditya Birla Science & Tech Co Ltd | Un proceso para la separacion y purificacion de sulfuro de sodio. |
FR2984916B1 (fr) * | 2011-12-23 | 2014-01-17 | IFP Energies Nouvelles | Procede ameliore de conversion d'une charge lourde en distillat moyen faisant appel a un pretraitement en amont de l'unite de craquage catalytique |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US6296758B1 (en) * | 1998-09-29 | 2001-10-02 | Uop Llc | Hydrocracking process |
US6379533B1 (en) * | 2000-12-18 | 2002-04-30 | Uop Llc | Hydrocracking process for production of LPG and distillate hydrocarbons |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US5447621A (en) * | 1994-01-27 | 1995-09-05 | The M. W. Kellogg Company | Integrated process for upgrading middle distillate production |
US6179995B1 (en) * | 1998-03-14 | 2001-01-30 | Chevron U.S.A. Inc. | Residuum hydrotreating/hydrocracking with common hydrogen supply |
AU2001247166A1 (en) * | 2000-02-11 | 2001-08-20 | Catalytic Distillation Technologies | Process for the desulfurization of petroleum feeds |
US6444116B1 (en) * | 2000-10-10 | 2002-09-03 | Intevep, S.A. | Process scheme for sequentially hydrotreating-hydrocracking diesel and vacuum gas oil |
US6793804B1 (en) * | 2001-11-07 | 2004-09-21 | Uop Llc | Integrated hydrotreating process for the dual production of FCC treated feed and an ultra low sulfur diesel stream |
CA2657780C (fr) * | 2006-07-19 | 2012-02-07 | Uop Llc | Procede de desulfurisation d'hydrocarbures |
-
2006
- 2006-07-19 CA CA2657780A patent/CA2657780C/fr not_active Expired - Fee Related
- 2006-07-19 EP EP06787821A patent/EP2041245A4/fr not_active Withdrawn
- 2006-07-19 CN CN200680055639.3A patent/CN101506334B/zh not_active Expired - Fee Related
- 2006-07-19 RU RU2009105660/04A patent/RU2402594C1/ru active
- 2006-07-19 WO PCT/US2006/027987 patent/WO2008010799A1/fr active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6296758B1 (en) * | 1998-09-29 | 2001-10-02 | Uop Llc | Hydrocracking process |
US6379533B1 (en) * | 2000-12-18 | 2002-04-30 | Uop Llc | Hydrocracking process for production of LPG and distillate hydrocarbons |
Non-Patent Citations (1)
Title |
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See also references of EP2041245A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014011967A1 (fr) * | 2012-07-13 | 2014-01-16 | Lyondell Chemical Technology, L.P. | Procédé perfectionné de réduction de couleur de diesel à teneur ultra faible en soufre |
WO2016093777A1 (fr) * | 2014-12-11 | 2016-06-16 | Türkiye Petrol Rafinerileri A. S. | Procédé de production de diesel |
Also Published As
Publication number | Publication date |
---|---|
CN101506334B (zh) | 2012-10-03 |
EP2041245A4 (fr) | 2010-08-04 |
RU2009105660A (ru) | 2010-08-27 |
EP2041245A1 (fr) | 2009-04-01 |
CA2657780C (fr) | 2012-02-07 |
CN101506334A (zh) | 2009-08-12 |
RU2402594C1 (ru) | 2010-10-27 |
CA2657780A1 (fr) | 2008-01-24 |
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