US3642610A - Two-stage hydrocracking-hydrotreating process to make lube oil - Google Patents

Two-stage hydrocracking-hydrotreating process to make lube oil Download PDF

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Publication number
US3642610A
US3642610A US855737A US3642610DA US3642610A US 3642610 A US3642610 A US 3642610A US 855737 A US855737 A US 855737A US 3642610D A US3642610D A US 3642610DA US 3642610 A US3642610 A US 3642610A
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United States
Prior art keywords
catalyst
percent
nickel
oil
hydrocracking
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Expired - Lifetime
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US855737A
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English (en)
Inventor
Joseph M Divijak Jr
Maurice K Rausch
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Atlantic Richfield Co
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Atlantic Richfield Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil

Definitions

  • the catalyst composition used in the hydrocracking stage of the present invention can be prepared by adding the nickel, tungsten, molybdenum and boria components to the alumina by the various methods known to the art, for example by impregnation or precipitation and coprecipitation using suitable compounds of the metals and boron.
  • alumina particles containing boria or a material which upon heating yields boria can be mixed with aqueous ammonia solutions containing nickel and tungsten, and/or molybdenum, or other aqueous solutions of water-soluble compounds of nickel and tungsten and/or molybdenum, so that the metal components are absorbed on the base.
  • the solid catalyst employed in the hydrogenation operation is preferably a sulfur-resistant, nonprecious metal hydrogenation catalyst, such as those conventionally employed in the hydrogenation of heavy petroleum oils.
  • suitable catalytic ingredients are tin, vanadium, members of Group VIB in the periodic table, i.e., chromium, molybdenum and tungsten and metals of the iron group, i.e., iron, cobalt and nickel. These metals are present in minor, catalytically effective amounts, for instances, about 2 to 30 weight percent of the catalyst, and may be present in the elemental form or in combined form such as the oxides or sulfides, the sulfide form being preferred.
  • the hydrogenation operation provides additional aromatic saturation, color improvement and stability towards oxidation and corrosion. Additional color improvement can be provided by subjecting the effluent from the hydrogenation operation to treatment with ultraviolet light. The treatment was found to lighten considerably the color of the darker oils, a surprising result since such treatment usually produces the opposite effect.
  • the reactor effluent from the hydrogenation stage may be flashed to recover hydrogen for possible recycle and fed to a steam stripper to remove excess light hydrogenated components.
  • the oil can then be fractionated and the lube fractions dewaxed. This dewaxing step can be carried out, for example, by pressing or by solvent dewaxing using methyl ethyl ketone and toluene as the solvent system.
  • Dewaxing may be carried out prior to the initial hydrocracking step but it is preferred to conduct dewaxing after hydrogenation has been completed. No additional finishing is required. Yields of about 60 to volume percent, based on the raw stock, of V1 oils are not uncommon and finished base oils having viscosity indexes of and higher are obtained in economical yields, e. g., in the range of about 40 volume percent and higher.
  • Deasphalted petroleum residuum was fed to an isothermal reactor unit having a nickel-tungstate on boria-aluminia catalyst in the first or hydrocracking stage and nickel-molybdate on alumina catalyst in the second or hydrogenation stage.
  • the catalysts were macrosize and presulfided.
  • the feedstock employed had the following specifications:
  • Viscosity SUS/210F. 154.4 Pour, F. 1 20+ ASTM color Dark Carbon residue (Con.), wt.% 1.58 10% boiling point 1,000F.
  • Table I lists operating conditions and dewaxed oil inspections for nominal 100 and V1 operations.
  • a process of preparing a mineral hydrocarbon lubricating oil having a viscosity index of at least about 90 on a dewaxed basis which comprises:
  • step (b) Contacting hydrocarbon oil of lubricating viscosity from step (a) with molecular hydrogen under hydrogenation conditions including a temperature of about 550 to 825 F. in the presence of a solid hydrogenation catalyst at a hydrotreating severity such that not more than about 5 volume percent of the feed to step (b) boiling above 600 F. is cracked to material boiling below about 600 F. to produce oil of lubricating viscosity having a viscosity index of at least about 90 and at least about 20 viscosity index number greater than the hydrocarbon oil feedstock passing to step (a).
  • hydrocracking conditions include a hydrogen partial pressure of about 1,000 to 5,000 p.s.i.g., a weight hourly space velocity of about 0.3 to 3 WHSV and a molecular hydrogen to hydrocarbon feed ratio of about 1 ,000 to 5,000 standard cubic feet per barrel of feed.
  • hydrocracking catalyst contains about 2 to 10 weight percent nickel, about 10 to 20 percent of the member selected from the group consisting of tungsten and molybdenum on an oxide basis, and about 2 to 10 percent boria.
  • a process of preparing a mineral hydrocarbon lubricating oil having a viscosity index of at least about on a dewaxed basis which comprises:
  • a Contacting a mineral hydrocarbon oil feedstock of lubricating viscosity at 210 F., at least 90 weight percent of which boils above about l,000 F. and having a viscosity index of about 50 to 80, with molecular hydrogen under hydrocracking conditions including a temperature of about 750 to 850 F., a hydrogen partial pressureof about 1,500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.5 to 2 WHSV and a molecular hydrogen to hydrocarbon feed ratio of about 1,500 to 3,000 standard cubic feet per barrel of feed, in the presence of a catalyst containing about 2 to 10 weight percent nickel, about 10 to 20 percent tungsten on an oxide basis and about 2 to 10 percent boria on an active alumina support, the metals of the catalyst being present in the sulfide form; and Contacting hydrocarbon oil of lubricating viscosity from step (a) with molecular hydrogen under hydrogenation conditions, including a temperature of about 600 to 800 F.,
  • step (b) is fractionated to separate oil of lubricating viscosity and the lubricating oil fraction is dewaxed.
  • step (b) is fractionated to separate oil of lubricating viscosity and the lubricating oil fraction is dewaxed.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (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)
US855737A 1969-09-05 1969-09-05 Two-stage hydrocracking-hydrotreating process to make lube oil Expired - Lifetime US3642610A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US85573769A 1969-09-05 1969-09-05

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US3642610A true US3642610A (en) 1972-02-15

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US (1) US3642610A (enExample)
JP (1) JPS5035925B1 (enExample)
BE (1) BE754805A (enExample)
BR (1) BR7018882D0 (enExample)
CA (1) CA1016485A (enExample)
DE (1) DE2043849A1 (enExample)
FR (1) FR2060411B1 (enExample)
GB (1) GB1280923A (enExample)
NL (1) NL7011761A (enExample)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870622A (en) * 1971-09-09 1975-03-11 Texaco Inc Hydrogenation of a hydrocracked lubricating oil
US3993557A (en) * 1974-03-27 1976-11-23 Pine Lloyd A Hydrocarbon conversion process employing boria-alumina compositions
US4082866A (en) * 1975-07-28 1978-04-04 Rte Corporation Method of use and electrical equipment utilizing insulating oil consisting of a saturated hydrocarbon oil
US4196408A (en) * 1974-01-14 1980-04-01 Rte Corporation High temperature transformer assembly
US4234434A (en) * 1979-02-14 1980-11-18 Atlantic Richfield Company Stabilization of hydrocracked oils with certain nitrogen-containing aromatic components
US4238316A (en) * 1978-07-06 1980-12-09 Atlantic Richfield Company Two-stage catalytic process to produce lubricating oils
US4263127A (en) * 1980-01-07 1981-04-21 Atlantic Richfield Company White oil process
US4264461A (en) * 1978-11-24 1981-04-28 Atlantic Richfield Company Stabilization of hydrocracked oils with aliphatic amine components
US4294687A (en) * 1979-12-26 1981-10-13 Atlantic Richfield Company Lubricating oil process
US4306985A (en) * 1979-02-14 1981-12-22 Atlantic Richfield Company Stabilization of hydrocracked oils with certain nitrogen containing aromatic components and phenolic components
US4325804A (en) * 1980-11-17 1982-04-20 Atlantic Richfield Company Process for producing lubricating oils and white oils
US4627908A (en) * 1985-10-24 1986-12-09 Chevron Research Company Process for stabilizing lube base stocks derived from bright stock
US4699707A (en) * 1985-09-25 1987-10-13 Union Oil Company Of California Process for producing lubrication oil of high viscosity index from shale oils
US4744884A (en) * 1985-09-25 1988-05-17 Union Oil Company Of California Process for producing lubrication oil of high viscosity index
US5026472A (en) * 1989-12-29 1991-06-25 Uop Hydrocracking process with integrated distillate product hydrogenation reactor
US5122257A (en) * 1986-12-10 1992-06-16 Shell Internationale Research Maatschappij B.V. Process for the manufacture of kerosene and/or gas oils
US20140073826A1 (en) * 2012-09-13 2014-03-13 Chevron U.S.A. Inc. Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock
US9803148B2 (en) 2011-07-29 2017-10-31 Saudi Arabian Oil Company Hydrocracking process with interstage steam stripping
US10882030B2 (en) * 2017-08-25 2021-01-05 Uop Llc Crystalline transition metal tungstate

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3788972A (en) * 1971-11-22 1974-01-29 Exxon Research Engineering Co Process for the manufacture of lubricating oils by hydrocracking
FR2487220A1 (fr) * 1980-07-23 1982-01-29 Shell France Catalyseur et procede pour la preparation d'une huile lubrifiante a partir d'une fraction d'huile minerale a point d'ebullition eleve

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2779713A (en) * 1955-10-10 1957-01-29 Texas Co Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions
US2917448A (en) * 1956-11-15 1959-12-15 Gulf Research Development Co Hydrogenation and distillation of lubricating oils
US3444071A (en) * 1965-03-31 1969-05-13 Shell Oil Co Process for the hydrogenative cracking of a hydrocarbon oil to produce lubricating oil
US3506565A (en) * 1968-07-31 1970-04-14 Chevron Res Process for the production of high viscosity index lubricating oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2779713A (en) * 1955-10-10 1957-01-29 Texas Co Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions
US2917448A (en) * 1956-11-15 1959-12-15 Gulf Research Development Co Hydrogenation and distillation of lubricating oils
US3444071A (en) * 1965-03-31 1969-05-13 Shell Oil Co Process for the hydrogenative cracking of a hydrocarbon oil to produce lubricating oil
US3506565A (en) * 1968-07-31 1970-04-14 Chevron Res Process for the production of high viscosity index lubricating oils

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870622A (en) * 1971-09-09 1975-03-11 Texaco Inc Hydrogenation of a hydrocracked lubricating oil
US4196408A (en) * 1974-01-14 1980-04-01 Rte Corporation High temperature transformer assembly
US3993557A (en) * 1974-03-27 1976-11-23 Pine Lloyd A Hydrocarbon conversion process employing boria-alumina compositions
US4082866A (en) * 1975-07-28 1978-04-04 Rte Corporation Method of use and electrical equipment utilizing insulating oil consisting of a saturated hydrocarbon oil
US4238316A (en) * 1978-07-06 1980-12-09 Atlantic Richfield Company Two-stage catalytic process to produce lubricating oils
US4264461A (en) * 1978-11-24 1981-04-28 Atlantic Richfield Company Stabilization of hydrocracked oils with aliphatic amine components
US4234434A (en) * 1979-02-14 1980-11-18 Atlantic Richfield Company Stabilization of hydrocracked oils with certain nitrogen-containing aromatic components
US4306985A (en) * 1979-02-14 1981-12-22 Atlantic Richfield Company Stabilization of hydrocracked oils with certain nitrogen containing aromatic components and phenolic components
US4294687A (en) * 1979-12-26 1981-10-13 Atlantic Richfield Company Lubricating oil process
US4263127A (en) * 1980-01-07 1981-04-21 Atlantic Richfield Company White oil process
US4325804A (en) * 1980-11-17 1982-04-20 Atlantic Richfield Company Process for producing lubricating oils and white oils
US4699707A (en) * 1985-09-25 1987-10-13 Union Oil Company Of California Process for producing lubrication oil of high viscosity index from shale oils
US4744884A (en) * 1985-09-25 1988-05-17 Union Oil Company Of California Process for producing lubrication oil of high viscosity index
US4627908A (en) * 1985-10-24 1986-12-09 Chevron Research Company Process for stabilizing lube base stocks derived from bright stock
US5122257A (en) * 1986-12-10 1992-06-16 Shell Internationale Research Maatschappij B.V. Process for the manufacture of kerosene and/or gas oils
US5026472A (en) * 1989-12-29 1991-06-25 Uop Hydrocracking process with integrated distillate product hydrogenation reactor
US9803148B2 (en) 2011-07-29 2017-10-31 Saudi Arabian Oil Company Hydrocracking process with interstage steam stripping
US20140073826A1 (en) * 2012-09-13 2014-03-13 Chevron U.S.A. Inc. Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock
US8927796B2 (en) * 2012-09-13 2015-01-06 Chevron U.S.A. Inc. Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock
US20150087872A1 (en) * 2012-09-13 2015-03-26 Chevron U.S.A. Inc. Base Oil Upgrading by Co-Feeding a Ketone or Beta-Keto-Ester Feedstock
US9115327B2 (en) * 2012-09-13 2015-08-25 Chevron U.S.A. Inc. Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock
US10882030B2 (en) * 2017-08-25 2021-01-05 Uop Llc Crystalline transition metal tungstate

Also Published As

Publication number Publication date
BR7018882D0 (pt) 1973-02-27
NL7011761A (enExample) 1971-03-09
DE2043849A1 (de) 1971-03-11
FR2060411A1 (enExample) 1971-06-18
JPS5035925B1 (enExample) 1975-11-20
BE754805A (fr) 1971-02-15
CA1016485A (en) 1977-08-30
FR2060411B1 (enExample) 1973-11-23
GB1280923A (en) 1972-07-12

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