EP3087162A1 - Procédé pour produire des distillats moyens - Google Patents
Procédé pour produire des distillats moyensInfo
- Publication number
- EP3087162A1 EP3087162A1 EP14819014.3A EP14819014A EP3087162A1 EP 3087162 A1 EP3087162 A1 EP 3087162A1 EP 14819014 A EP14819014 A EP 14819014A EP 3087162 A1 EP3087162 A1 EP 3087162A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- product
- process according
- recycled
- carried out
- residual fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 238000002309 gasification Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 3
- 239000003054 catalyst Substances 0.000 description 34
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/0463—The hydrotreatment being a hydrorefining
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- 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
- C10G2300/30—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
- C10G2300/4081—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
- 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
- C10G2300/42—Hydrogen of special source or of special composition
Definitions
- the present invention relates to process for
- hydrofinished gasoil is then used as diesel fuel or diesel fuel component.
- Object of the present invention is to provide a process for producing ultra low sulphur middle
- the present invention relates to a process for producing middle distillates from a residual hydrocarbonaceous feedstock, comprising the steps of: (a) deasphalting the residual hydrocarbonaceous feedstock to obtain a deasphalted product of which at least 55 wt% has a boiling point above 550 °C and an asphaltic
- step (b) hydrodemetallizing at least part of the deasphalted product as obtained in step (a) to obtain a
- step (c) hydrotreating at least part of the hydrodemetallized product as obtained in step (b) to obtain a hydrotreated product
- step (d) hydrocracking at least part of the hydrotreated product as obtained in step (c) to obtain a hydrocracked product
- step (e) subjecting at least part of the hydrocracked product as obtained in step (d) to a separation treatment to obtain at least a middle distillate fraction.
- hydrocarbonaceous feedstocks hydrocarbonaceous feedstocks.
- the residual hydrocarbonaceous feedstocks to be used in accordance with the present invention can suitable be residual hydrocarbon oils, such as those obtained in the distillation of crude oils at atmospheric or reduced pressure.
- residual hydrocarbon oils such as those obtained in the distillation of crude oils at atmospheric or reduced pressure.
- hydrocarbonaceous feedstock has a boiling point of above 550 °C. Atmospheric residues or vacuum residues contain however considerable amounts of non-distillable compounds having a high molecular weight such as asphaltenes. It is therefore considered desirable to remove asphaltenes from a residual hydrocarbon oil feed prior to subjecting the residual hydrocarbon oil to subsequent upgrading steps.
- step (a) a residual hydrocarbonaceous feedstock is deasphalted to obtain a deasphalted product of which at least 50 wt% , preferably at least 70 ⁇ 6 , more
- At least 80 wt%, and even more preferably at least 85 wt% has a boiling point above 550 °C and an asphaltic product.
- the deasphalting in step (a) may be carried out in any conventional manner.
- a well known and suitable deasphalting method is solvent deasphalting.
- step (a) the deasphalting in step (a) is preferably carried out by means of a solvent deasphalting treatment.
- paraffinic compounds Commonly applied paraffinic
- C3-8 paraffinic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane or mixtures of two or more of these.
- C3-C5 paraffinic hydrocarbons
- paraffinic hydrocarbons most preferably butane, pentane or a mixture thereof, are used as the extracting solvent.
- the extraction depth increases at increasing number of carbon atoms of the extracting solvent.
- the higher the extraction depth the larger the amount of hydrocarbons being extracted from the residual hydrocarbonaceous feedstock, the smaller and more viscous the asphaltic product will be, whereby the heavier the asphaltenes will be in the asphaltic product to be obtained in step (a) .
- a rotating disc contactor or a plate column can be used with the residual hydrocarbonaceous feedstock entering at the top and the extracting solvent entering at the bottom.
- hydrocarbonaceous feedstock dissolve in the extracting solvent and are withdrawn as the deasphalted product at the top of the apparatus.
- the asphaltenes which are insoluble in the extracting solvent are withdrawn in the form of the asphaltic product at the bottom of the apparatus.
- the conditions under which deasphalting takes place are known in the art.
- deasphalting is carried out at a total extracting solvent to residual hydrocarbon oil ratio of 1.5 to 8 wt/wt, a pressure of from 1 to 60 bara and a temperature of from 40 to 200 C.
- a deasphalting treatment generally causes a
- the metals content of the deasphalted product will be such that the deasphalted product needs to be subjected to a hydrodemetallizing step before it can be subjected to further
- step (b) at least part of the deasphalted product as obtained in step (a) is hydrodemetallized to obtain a hydrodemetallized product.
- step (b) the entire deasphalted product as obtained in step (a) is hydrodemetallized.
- the deasphalted product which is hydrodemetallized in step (b) is a pure and heavy deasphalted product. This means that at least 50 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, and even more preferably at least 85 wt% of the deasphalted product to be treated in step (b) has a boiling point of above 550 °C. Unlike in other hydroconversion processes such as for instance disclosed in EP 1731588 Al, the entire undiluted
- deasphalted product as obtained in step (a) can now be hydrodemetallized in step (b) , and there is no need to dilute the deasphalted product before it can be further processed.
- One of the major advantages of the present invention is the fact that such an undiluted heavy deasphalted product can be further processed, resulting in such a high yield of low sulphur middle distillates.
- the hydrodemetallisation of the deasphalted product in step (b) can be achieved by any well known
- hydrodemetallization treatment wherein the deasphalted product to be hydrodemetallized is passed at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction, through one or more vertically disposed reactors containing a fixed or moving bed of hydrodemetallization catalyst particles.
- the hydrodemetallization can be carried out in a bunker flow reactor, a fixed bed reactor, a fixed bed swing reactor or a movable bed reactor.
- the deasphalted product to be hydrodemetallized is passed at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction, through one or more vertically disposed reactors containing a fixed or moving bed of hydrodemetallization catalyst particles.
- the hydrodemetallization can be carried out in a bunker flow reactor, a fixed bed reactor, a fixed bed swing reactor or a movable bed reactor.
- the deasphalted product to be hydrodemetallized is passed at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction,
- hydrodemetallizing in step (b) is at least partially carried out in a bunker flow or moving bed reactor.
- step (b) suitably use is made of a
- hydrodemetallization catalysts to be used in accordance with the present invention consist of oxidic carriers such as alumina, silica or silica-alumina, on which one or more Group VIB or Group VIII metals or metal compounds may be deposited. Such hydrodemetallization catalysts are commercially available from many catalyst suppliers.
- Particularly suitable hydrodemetallization catalysts are those having as the active agent one of the combinations nickel/molybdenum (NiMo) or cobalt/molybdenum (CoMo) , optionally promoted with phosphorus (P) , on an alumina (A1203) carrier.
- NiMo nickel/molybdenum
- CoMo cobalt/molybdenum
- P phosphorus
- A1203 carrier alumina
- NiMo/A1203 and NiMoP/A1203 catalysts are NiMo/A1203 and NiMoP/A1203 catalysts.
- the hydrodemetallization in step (b) can suitably be carried out at a hydrogen partial pressure of 20-300 bara, preferably 50-210 bara, a temperature of 300-470 °C, preferably 310-440 °C, and a space velocity of 0.1-10 hr -1 , preferably 0.2 to 7 hr ⁇ l .
- the use of the pure and heavy desphalted product in step (b) will result in considerable metals laydown on the hydrodemetallization catalyst (s) to be used in step (b) which in turn results in a very swift deterioration/deactivation of the
- hydrodemetallization catalyst (s) requiring a much more regular and fast replacement of the hydrodemetallization catalyst (s) when compared with known processes in which a diluted and lighther deasphalted product with a lower metals content is subjected to a hydrodemetallization step.
- the hydrodemetallization reactor is
- a bunker flow reactor preferably a bunker flow reactor, a fixed bed swing reactor or a movable bed reactor.
- hydrodemetallization catalyst (s) is (are) regularly replaced for instance every three weeks or two months, whereas in conventional processes the
- hydrodemetallization catalyst (s) (like the hydrotreating and hydrocracking catalysts to be used in steps (c) and (d) in the present process) may not be replaced within a year time.
- step (c) at least part of the hydrodemetallized product as obtained in step (b) is hydrotreated to obtain a hydrotreated product.
- step (c) the entire hydrodemetallized product as obtained in step (b) is hydrotreated.
- the hydrotreating of the hydrodemetallized product in step (c) can be achieved by any well known
- hydrotreating process wherein the hydrodemetallized product to be hydrotreated is passed at elevated
- the hydrotreatment can be carried out in a bunker flow reactor, a fixed bed reactor, a fixed bed swing reactor or a movable bed reactor.
- the hydrotreatment in step (c) is carried out in two reaction zones, whereby the hydrodemetallized product is first passed to a first reaction zone in which the hydrodemetallized product is partly hydrotreated after which the partly hydrotreated effluent so obtained is subjected to further
- the first reaction zone and second reaction zone can be arranged in a stacked bed configuration or the two reactions zones can each be arranged in a separate reactor.
- the first reaction zone and the second reaction zone are respectively arranged in a first reactor and a second reactor.
- the first reactor may be a bunker flow reactor and the second reactor may be a fixed bed reactor.
- the hydrotreating catalyst to be used in step (c) can suitably be a desulphurization catalyst.
- desulphurization catalyst may be any organic compound
- Suitable hydrodesulphurization catalysts comprise a Group VIII metal of the Periodic Table and a compound of a Group VIB metal of the Periodic Table as hydrogenation components on a porous catalyst support, usually alumina or amorphous silica-alumina.
- a porous catalyst support usually alumina or amorphous silica-alumina.
- suitable combinations of hydrogenation compounds are cobalt-molybdenum, nickel-molybdenum, nickel-tungsten, and nickel-cobalt-molybdenum.
- a hydrodesulphurization catalyst comprising compounds of nickel and/or cobalt and molybdenum as hydrogenation compounds is preferred.
- the hydrodesulphurization catalyst may further comprise a cracking component such as for example Y zeolite.
- the catalyst is substantially free of a cracking component.
- a catalyst comprising nickel and/or cobalt and molybdenum supported on alumina without a zeolitic cracking compound is particularly preferred.
- step (c) The hydrotreating conditions in step (c) , i.e.
- the temperature used for the hydrotreating in step (c) is in the range of from 280 to 430 °C, more preferably in the range of from 320 to 420 °C, and most preferably in the range of from 330 to 410 °C.
- Suitable hydrotreating pressures are in the range of from 10 to 300 bara.
- the hydrotreating pressure is in the range of from 30 to 250 bara, more preferably in the range of from 80 to 220 bara.
- step (d) at least part of the hydrotreated product as obtained in step (c) is hydrocracked to obtain a hydrocracked product.
- step (d) the entire hydrotreated product as obtained in step (a) is hydrocracked .
- the hydrocracking zone is acidic.
- the hydrocracking is carried out in the
- Suitable hydrocracking catalysts consist of one or more metals from nickel, tungsten, cobalt and molybdenum in
- hydrocracking catalysts which can be suitably applied in the process of the present invention. At least one of the catalysts used in the hydrocracking zone must be acidic, i.e. must contain a silica-alumina and/or zeolitic component.
- the hydrocracking in step (d) can be carried out in a single- or multiple-stage mode of operation.
- a single-stage mode of operation a stacked bed of a hydrodenitrification/first-stage hydrocracking catalyst on top of a conversion catalyst can suitably be used.
- Particularly suitable hydrodenitrification/first-stage hydrocracking catalysts are NiMo/A1203 and
- CoMo/A1203 optionally promoted with phosphorus and/or fluor.
- Preferred conversion catalysts are those based on
- Suitable hydrocracking conditions in step (d) are an operating pressure of 80-250 bara, preferably 90-220 bara, and a temperature of 300-460 °C, preferably 350-430 °C.
- step (e) at least part of the hydrocracked product as obtained in step (d) is subjected to a
- step (e) the entire hydrocracked product as obtained in step (d) is subjected to the separation treatment.
- the separation treatment is step (e) can suitably a fractionating treatment which is carried out at a
- a heavy residual fraction Beside of the middle distillate fraction to be obtained in step (e) there can also be obtained a heavy residual fraction.
- a heavy residual fraction Suitably, at least 80% of the heavy residual fraction also obtained in the separation
- step (e) has a boiling point above 370 °C.
- at least 90% of the heavy residual fraction also obtained in the separation treatment in step (e) has a boiling point above 370 °C.
- At least part of a heavy residual fraction also obtained in step (e) may be recycled to step (a) . In this way an improved yield of middle distillates can be obtained.
- said heavy fraction could also be suitably applied as a feed for a fluidised bed catalytic cracking (FCC) unit or as a feedstock for lubricating oil manufacture.
- FCC fluidised bed catalytic cracking
- step (e) In order to achieve an optimum middle distillates yield, it is preferred that at least a part of the heavy fraction obtained in step (e) is again subjected to hydrocracking to improve the yield of middle distillates. Hence, in a preferred embodiment at least part of a heavy residual fraction which is also obtained in step (e) is recycled to step (d) . In another preferred embodiment of the present invention at least part of the heavy residual fraction also obtained in step (e) is recycled to step (a) and at least part of the heavy residual fraction also obtained in step (e) is recycled to step (d) . In this way the yield of middle distillates is further improved.
- step (e) At least part of a heavy residual fraction also obtained in step (e) is subjected to a further hydrocracking step (f) , and at least part of the hydrocracked product as obtained in such a step (f) is recycled to step (e) .. Also this embodiment ensures that an optimal yield of middle distillates will be established.
- step (e) At least part of the heavy residual fraction also obtained in step (e) is also recycled to step (a) to improve the middle distillate yield even further .
- the hydrocracking in step (d) and/or step (f) is carried out in two or more reaction zones.
- the two or more reaction zones are arranged in a stacked bed configuration.
- the asphaltic product as obtained in step (a) may be used in several ways. It can for instance be combusted for cogeneration of power and steam. Alternatively, it can be partially combusted for clean fuel gas production, cogeneration of power and steam, hydrogen manufacture or hydrocarbon synthesis. Still another option is
- step (a) at least part of the asphaltic product as obtained in step (a) is subjected to a gasification step (g) to obtain hydrogen and carbon monoxide.
- a gasification step (g) is a partial combustion step.
- step (g) At least part of the hydrogen as obtained in step (g) is recycled to at least one of steps (b) , (c) , (d) and (f) .
- the middle distillate fraction as obtained in step (e) comprises middle distillates which contain less than 10 ppmwt of sulphur.
- the middle distillates contain less than 8 ppmwt of sulphur, more preferably less than 6 ppmwt of sulphur, and most preferably less than 5 ppmwt of sulphur.
- Figure 1 depicts the process according to the present invention
- Figure 2 depicts a preferred
- Figure 3 depicts a further preferred embodiment of the process according to the present invention.
- an atmospheric or reduced pressure hydrocarbon oil residue is passed via a line 1 into a deasphalting unit 2 in which a deasphalted product and an asphaltic product are obtained. At least part of the deasphalted product is passed via a line 3 into a deasphalting unit 2 in which a deasphalted product and an asphaltic product are obtained. At least part of the deasphalted product is passed via a line 3 into a deasphalting unit 2 in which a deasphalted product and an asphaltic product are obtained. At least part of the deasphalted product is passed via a line 3 into a
- hydrodemetallization unit 5 and the asphaltic product is withdrawn from the deasphalting unit 2 via a line 4. At least part of the hydrodemetallized product as obtained in hydrodemetallization unit 5 is passed via a line 6 to hydrotreating unit 7. At least part of the hydrotreated product as obtained in the hydrotreating unit 7 is then passed to a hydrocracking unit 9 via a line 8. At least part of the hydrocracked product as obtaind in the hydrocracking unit 9 is passed via a line 10 to a
- Figure 2 is an extension of Figure 1 in that in the fractionating unit 11 also a heavy residual fraction is obtained which is withdrawn via a line 13 from the fractionating unit 11 and at least part of the heavy residual fraction is recycled to the deasphalting unit 2.
- Figure 3 is an extension of Figure 2 in that in the fractionating unit 11 also a heavy residual fraction is obtained which is withdrawn via a line 13 from the fractionating unit 11 and at least part of the heavy residual fraction is recycled via a line 14 to the hydrocracking unit 9 and/or at least part of the heavy residual fraction is recycled via a line 15 to the hydrodemetallization unit 5 and/or at least part of the heavy residual fraction is recycled via a line 16 to the deasphalting unit 2.
- Figure 4 is an extension of Figure 1 in that in the fractionating unit 11 also a heavy residual fraction is obtained which is withdrawn via a line 13 from the fractionating unit 11 and at least part of the heavy residual fraction is passed via the line 13 to a
- hydrocracking unit 14 At least part of the hydrocracked product as obtained in the hydrocracking unit 14 is recycled to fractionating unit 11 via lines 15 and 16 and at least part of the heavy residual fraction as obtained in the fractionating unit 11 is recycled via lines 15 and 17 to the deasphalting unit 2.
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Abstract
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PL14819014T PL3087162T3 (pl) | 2013-12-24 | 2014-12-22 | Sposób wytwarzania średnich destylatów |
EP14819014.3A EP3087162B1 (fr) | 2013-12-24 | 2014-12-22 | Procédé de production de distillats intermédiaires |
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EP13199599 | 2013-12-24 | ||
PCT/EP2014/079095 WO2015097199A1 (fr) | 2013-12-24 | 2014-12-22 | Procédé pour produire des distillats moyens |
EP14819014.3A EP3087162B1 (fr) | 2013-12-24 | 2014-12-22 | Procédé de production de distillats intermédiaires |
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EP (1) | EP3087162B1 (fr) |
KR (1) | KR102444109B1 (fr) |
CN (2) | CN105849237A (fr) |
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CN110114445A (zh) | 2016-12-28 | 2019-08-09 | 国际壳牌研究有限公司 | 用于生产中间馏出物的方法 |
US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
US10655074B2 (en) | 2017-02-12 | 2020-05-19 | Mag{hacek over (e)}m{hacek over (a)} Technology LLC | Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil |
WO2023227639A1 (fr) * | 2022-05-25 | 2023-11-30 | Shell Internationale Research Maatschappij B.V. | Procédé de production de distillats moyens |
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MX9502237A (es) * | 1994-05-19 | 1997-02-28 | Shell Int Research | Proceso para la conversion de un aceite residual de hidrocarburo. |
EP0697455B1 (fr) * | 1994-07-22 | 2001-09-19 | Shell Internationale Research Maatschappij B.V. | Procédé de préparation d'une cire hydrogénée |
EP1731588A1 (fr) * | 2005-06-08 | 2006-12-13 | Shell Internationale Researchmaatschappij B.V. | Procédé de valorisation d'huile brute |
US9284502B2 (en) * | 2012-01-27 | 2016-03-15 | Saudi Arabian Oil Company | Integrated solvent deasphalting, hydrotreating and steam pyrolysis process for direct processing of a crude oil |
KR101716986B1 (ko) * | 2012-06-05 | 2017-03-15 | 사우디 아라비안 오일 컴퍼니 | 전체 원유를 탈아스팔트 및 탈황시키기 위한 통합 공정 |
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- 2014-12-22 EP EP14819014.3A patent/EP3087162B1/fr active Active
- 2014-12-22 CN CN201480070805.1A patent/CN105849237A/zh active Pending
- 2014-12-22 KR KR1020167019992A patent/KR102444109B1/ko active IP Right Grant
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CN105849237A (zh) | 2016-08-10 |
WO2015097199A1 (fr) | 2015-07-02 |
PL3087162T3 (pl) | 2019-09-30 |
CN113214866A (zh) | 2021-08-06 |
KR102444109B1 (ko) | 2022-09-15 |
EP3087162B1 (fr) | 2019-04-10 |
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