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
• • 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
  • C10G2400/10—Lubricating oil

Definitions

• this application pertains to improvements in hydrogenation of lubricating oils. More specifically, this invention relates to the use of combined crude fractions of widely different viscosities or a lube fraction containing components which cumulatively represent a relatively broad spectrum of viscosities in hydrogenation operations whereby improvements in the lubricating oil are obtained, and particularly in regard to UV absorptivity of the heavier fractions thereof.
• Certain lube fractions have been found suitable for many uses for which other lube fractions are not suitable or at least not preferred. Accordingly, some properties thereof are more critical when a particular fraction and a particular use are contemplated.
• a crude is fractionated into a plurality of lubricating oil distillates of varying boiling points and viscosity for the particular end use or end uses contemplated.
• the crudes are appropriately treated in accordance to their type and characteristics as determined by source of same.
• naphthenic crudes for example, they are treated with an alkaline material to remove naphthenic acids which are always found present in such crudes in significant amounts.
• the naphthenic acids are removed according to the procedures of U .8. Patents 2,770,580 and 2,966,456.
• the various fractions are generally hydrogenated to desulfurize, to remove some of the nitrogen present and to selectively hydrogenate the lube oil itself whereby its properties are enhanced.
• Paraffinic base crudes receive a different treatment, but conventional for that type such as deasphalting, dewaxing, etc., prior to the hydrogenation.
• the lube fractions once obtained in conventional fashion are hydrogenated for substantially the same reasons and at substantially the same general conditions as indicated for the naphthenic crudes.
• the hydrocarbon feed components that are blended are to have a viscosity varying in the range of about 50 to about 6000 SUS at 100 F. (or 32 to 200 SUS at 210 F.), and of about 240 to 500 average molecular weight respectively; however, this is not entirely ac curate without further qualification. While the individual components or fractions that blend to form the feed are to fall generally within the foregoing broad range, it is essential that there be substantial amounts of material present which, as isolated fractions, have a SUS viscosity of at least about 1000 SUS at 100 F. and about 360 average molecular weight and below about 6000 SUS at 100 F. and below about 500 average molecular weight respectively.
• the individual components of fractions that are blended or otherwise curnmulatively comprise the charge to the hydrogenation zone must possess viscosity characteristics from each of the foregoing ranges, in addition to the most important requirement of the charge stock, that the mixture or blend have a composite viscosity of about 200 SUS viscosity at 100 F. and about 300 average molecular weight to 1000 SUS viscosity at 100 F. and about 360 average molecular weight as previously set forth, but preferably has viscosity of about 250 SUS at 100 F. and about 325 average molecular weight to about 500 SUS at 100 F. and about 345 average molecular weight.
• the preferred manner of operation is to operate in liquid phase and to pass the charge stock and hydrogen over the hydrogenation catalyst in downward co-current fashion according to the technique which is frequently referred to as the trickle-phase operation, although on occasion it may be preferred to feed the hydrogen in counter-current fashion.
• the hydrogenation catalysts which are suitable are Well known in the art and examples are copper, zinc, magnesium, tin, vanadium, tungsten, chromium, molybdenum, manganese, cobalt, iron, nickel, platinum, etc. or their oxides of sulfides or such or mixtures of such metals or their oxides or sulfides.
• Any of the well-known catalyst carriers may be employed as such carriers as activated carbon, alumina, bauxite, charcoal, clay, kieselguhr, magnesia, pumice, silica, silica-alumina compositions, etc.
• the preferred catalyst are combinations of cobalt and molybdenum and nickel and molybdenum. Said combinations having been presulfided according to well-known techniques so that they are used in the form of the sulfides on alumina as a carrier.
• the temperature range broadly suitable is 450 to 750 F., preferably it is within the range of about 475 to 625 F. and still more preferably, the temperature is about 575 to 625 F.
• the hydrogen partial pressure range broadly suitable is about 100 to 4000 p.s.i.g., but preferably, the pressure employed is about 500 to 2000 p.s.i.g., and more preferably, 1000 to 1500 p.s.i.g.
• the hydrogen employed is preferably a hydrogen stream containing at least about 70 percent hydrogen; however, any hydrogen-rich refinery stream may be em ployed.
• the hydrogen stream is employed in an amount varying from about to 1000 s.c.f./barrel of lubricating oil, and more preferably, about 50 to 300 s.c.f. on the same basis.
• the space rates may vary over a wide range depending on the design of the reactor and the residence time desired, but generally, such space rates will vary between about 0.25 to volumes of liquid charge per volume of catalyst bed per hour.
• any recycle of material is to be considered in determining the foregoing figure.
• Gas recycle may be employed for example, as set forth in US. 2,918,425 or liquid may be recycled either internally (i.e., before any purification) or according to conventional recycle techniques of recovering unconverted partially converted or reacted material and returning same to the reactor.
• the oil is then fractionated into a plurality of lubricating oil distillates of varying boiling points and viscosity.
• the propertie are for all practical purposes substantially the same as those the same fractions have if hydrogenated separately. There is at least one important exception, however, and this involves an improved UV absorptivity at 260 mg of the fraction or those fractions with a viscosity above about 1000 SUS at 100 F. and about 360 average molecular weight.
• the fractions may be further treated according to the needs of the particular end use intended. For example, they may be extracted with solvents such as furfural, methyl ethyl ketone, etc. They may be instead or in addition treated with clays and/or sulfuric acid.
• a Grade A crude mix (a naphthenic base crude) of about 0.89 viscosity-gravity constant was caustic distilled according to the procedure of US Patent 2,770,580.
• a blend of the fractions were prepared with a viscosity of about 340 at F. and about 47 at 210 F.
• This blend and hydrogen were continuously fed to a conventional trickle-phase hydrogenation reactor in conventional fashion and was hydrogenated in a continuous operation over a presulfided nickel-molybdenum on alumina catalyst at a pressure of about 1000 p.s.i.g and at temperature of about 600 F.
• Fresh feed with a UV absorptivity of about 11.2 was charged at a rate of about 0.5 volume of feed per volume of catalyst per hour and liquid product was recycled at a rate to provide a total liquid space rate of about 4.0 volumes of liquid per volume of catalyst per hour.
• a make-up stream of 100 percent hydrogen at a rate of approximately 235 s.c.f./bbl. was required.
• the hydrogenated product was fractionated to provide three separate fractions (see the table below, left-hand side).
• the heaviest fraction with a viscosity of about 2800 SUS at 100 F. and an average molecular weight of about 396 exhibited the most improvement in UV as compared to separate hydrogenation. This fraction had a UV absorptivity of 4.1.
• a process according to claim 1 wherein said hydrogenation with hydrogen over a hydrogenation catalyst is conducted at a temperature within the range of about 450 to 750 F. and at a pressure within the range of about 100 p.s.i.g. to about 4000 p.s.i.g.
• a process according to claim 2 wherein said hydrogen employed is a refinery hydrogen stream of at least about 70 percent hydrogen.
• oil charge has a composite viscosity in the range of about 250 SUS at 100 F. and about 325 molecular weight to about 500 SUS at 100 F. and about 345 molecular weight.
• said hydrogenation catalyst is a nickel-molybdenum on alumina catalyst obtained by sulfiding a nickel oxide-molybdenum oxide mixture on alumina wherein nickel oxide is present in an amount equal to about 3 percent and molybdenum oxide is present in an amount equal to about percent, sodium oxide is present in about 0.02 percent by weight and the remainder is alumina.

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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)
• Lubricants (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24353379

Family Applications (1)

Country Status (6)

Cited By (4)

Citations (5)

• 1966
  • 1966-10-21 US US588324A patent/US3425932A/en not_active Expired - Lifetime
• 1967
  • 1967-08-31 GB GB39886/67A patent/GB1137340A/en not_active Expired
  • 1967-09-22 DE DE19671644953 patent/DE1644953A1/de active Pending
  • 1967-10-11 BR BR193743/67A patent/BR6793743D0/pt unknown
  • 1967-10-12 NL NL6713883A patent/NL6713883A/xx unknown
  • 1967-10-20 BE BE705448D patent/BE705448A/xx unknown

Patent Citations (5)

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