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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof

Definitions

• the present invention relates to a process for the manufacture of lubricating base oils from naphthenic feedstocks as well as to lubricating base oils thus prepared.
• naphtenic feedstocks i.e. feeds containing both naphthenic acids and a considerable amount of aromatic compounds can be converted directly (i.e. without the necessity of a pre-treatment) into naphthenic base oils of good quality, having a viscosity index of up to 100 when use is made of certain fluorided nickel-containing catalysts under rather severe process conditions.
• the present invention thus relates to a process for the manufacture of naphthenic base oils having a viscosity index of up to 100 by catalytically converting a naphthenic feedstock at elevated temperature and pressure in the presence of hydrogen, which process is carried out at a hydrogen partial pressure of at least 100 bar in the presence of a fluorided, nickel-containing catalyst also comprising tungsten and/or molybdenum.
• the naphthenic feedstock can, of course, be subjected - if desired - to a neutralization pre-treatment as referred to hereinbefore so as to reduce almost completely the acidic components (whilst substantially leaving the aromatic compounds in the feedstock) but this is not necessary since it is the process according to the present invention which allows a substantial reduction of the initial aromatics content together with complete removal of the acidic components.
• the process according to the present invention can be used advantageously in the manufacture of low viscosity index base oils (which are applied e.g. as base oils for cutting oils and as additive carriers) as well as of medium viscosity index base oils (which are applied e.g. as base oils for refrigerator oils, large engine lubricating oils as well as in white oil manufacture).
• low viscosity index base oils which are applied e.g. as base oils for cutting oils and as additive carriers
• medium viscosity index base oils which are applied e.g. as base oils for refrigerator oils, large engine lubricating oils as well as in white oil manufacture.
• Naphthenic base oils having a low viscosity index can now be prepared in far higher yields and at a much lower polycyclic aromatic components level than is possible when using a conventional hydrotreatment and/or acid/clay treatment. It is now possible to reduce the polycyclic aromatic content to well below 10 %w and often to less than 6 %w, and even less than 3 %w which is of great importance from an environmental point of view.
• Naphthenic base oils having a medium viscosity index can now be prepared in much higher yields by the process according to the present invention than is achievable by using common solvent extraction of neutralized feedstocks, followed, if desired, by a hydrofinishing step.
• Both neutralized and unneutralized naphthenic base oil feedstocks can be suitably applied in the process according to the present invention.
• Preferred feedstocks comprise unneutralized naphthenic distillates since they can be converted in a single operation into valuable naphthenic base oils.
• the naphthenic distillates to be used may contain up to 4 %w of sulphur and up to 0.8 %w of nitrogen compounds.
• the acid number may be as high as 10 mg KOH/g.
• the naphthenic base oil feedstocks to be processed normally contain at least 35 %w of aromatic compounds and often even more then than 65 %w.
• the process according to the present invention has to be carried out at a hydrogen partial pressure of at least 100 bar (104kPa) and preferably at a pressure between 100 and 200 bar. Temperatures between 280 °C and 425 °C can be suitably applied; preference is given to the use of temperatures between 325 and 400 °C, depending to some extent on the base oil feedstock to be processed and the base oil grade to be produced. Normally, the hydrotreatment according to the present invention will be carried out at a space velocity between 0.1 and 5 kg/kg.h, in particular between 0.2 and 2 kg/kg.h.
• the supported catalysts to be used in the process according to the present invention have to contain molybdenum and/or tungsten in addition to nickel.
• the amount of nickel present in the catalyst can suitably vary between 1 and 20 %w, calculated as oxide on total catalyst composition, preference being given to amounts in the range of from 2 to 12 %w.
• the amounts of molybdenum and tungsten may vary between 10 and 40 %w, calculated as oxide on total catalyst composition, preference being given to amounts in the range between 10 and 30 %w.
• Preferred catalysts contain both nickel and tungsten.
• the metals and/or metal compounds may be incorporated into the supports by any conventional technique, such as impregnation, dry-impregnation, precipitation and combinations thereof. It is also possible to prepare the catalysts by the hydrogel or the xerogel methods as described in British Patent Specifications 1,493,620 and 1,546,398.
• Any suitable support material may be used such as refractory oxides conventionally used for hydrotreating catalysts, such as silica, alumina, magnesia, zirconia and mixtures thereof.
• Silica and alumina are preferred support materials, in particular alumina.
• Natural and synthetic crystalline aluminosilicates such as faujasite, in particular Y-faujasite, and ZSM-5 type carriers can also be applied.
• the catalysts according to the present invention also contain fluorine.
• the amount of fluorine in the catalysts under operating conditions may vary between 0.5 and 10 %w, preferably between 2 and 8 %w, calculated on total catalyst.
• Fluorine can be introduced into the catalyst by one or more of the fluorination techniques known in the art. Preference is given to the introduction of at least part of the fluorine required in the catalyst by means of in-situ fluorination. It is advantageous to incorporate substantially all fluorine required in the catalyst by in-situ fluorination, preferably in the initial stage of the hydrotreatment. It is also possible to supply, either continuously or intermittantly, a small amount of fluorine, e.g.
• the catalysts may also contain other compounds such as phosphorus or boria.
• the catalyst can be applied in the form of spheres or extrudates.
• the extrudates may have different shapes depending on the extrusion equipment used during their preparation.
• An unneutralized naphthenic distillate of South American origin containing 1.73 %w of sulphur, a total nitrogen content of 315 ppm, an aromatics content of 49.8 %w, including 13.7 %w of polycyclic aromatic compounds and having a total acid number of 5.7 (mg KOH/g) was hydrotreated using the catalyst described in Example 1 at 378 °C using the same space velocity as described in said Example.
• a naphthenic base oil having an initial boiling point of 280 °C and a viscosity index of 45 was obtained in 59.2 %w yield, calculated on unneutralized starting material.
• the base oil obtained contained less than 5 ppm of nitrogen and less than 40 ppm of sulphur.
• the total aromatic content had been reduced to less than 7 %w, the amount of polycyclic aromatic compounds being even less than 1 %w.
• An unneutralized naphthenic distillate of South American origin containing 2.35% of sulphur and 1576 ppm of nitrogen, a total aromatics content of 63.9 %w, including 31.5 %w of polycyclic aromatic compounds and having a total acid number of 7.8 was hydrotreated at 380 °C and at a hydrogen partial pressure of 140 bar at a space velocity of 0.6 kg/kg.h.
• a naphthenic base oil having an initial boiling point of 400 °C and a viscosity index of 35.8 was obtained in 59.4% yield, calculated on unneutralized starting material.
• the base oil obtained contained less than 1 ppm of nitrogen and no detectable amounts of sulphur.
• the total aromatics content amounted to 21.8 %w, only 1.8 %w being attributed to poly­cyclic aromatic compounds.

Landscapes

• 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)

Applications Claiming Priority (2)

Publications (3)

Family

ID=10582200

Family Applications (1)

Country Status (8)

Cited By (2)

Families Citing this family (1)

Family Cites Families (8)

• 1985
  • 1985-07-12 GB GB858517657A patent/GB8517657D0/en active Pending
• 1986
  • 1986-06-17 EP EP86201050A patent/EP0208361B1/fr not_active Expired - Lifetime
  • 1986-06-17 DE DE8686201050T patent/DE3682628D1/de not_active Expired - Lifetime
  • 1986-06-20 CA CA000512033A patent/CA1275275C/fr not_active Expired - Fee Related
  • 1986-07-04 NL NL8601742A patent/NL8601742A/nl not_active Application Discontinuation
  • 1986-07-10 BR BR8603227A patent/BR8603227A/pt not_active IP Right Cessation
  • 1986-07-10 JP JP61161014A patent/JPS6215290A/ja active Pending
  • 1986-07-10 ZA ZA865155A patent/ZA865155B/xx unknown

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