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
  • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/10—Lubricating oil
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S208/00—Mineral oils: processes and products
  • Y10S208/02—Molecular sieve

Definitions

• McCorquodale, Jr. and Harold M. Dixon ABSTRACT A process for increasing the V.l. ofa light lube fraction approximating the viscosity range of a 100 Neutral oil which has been hydrocracked as part of a relatively widerange lube fraction wherein the light lube fraction is isolated and rehydrocracked in the absence of heavier fractions.
• Neutral oil derived from hydrocracked lubricating oil product by subjecting said isolated fraction to a second hydrocracking treatment.
• the lube stocks that are hydrocracked are also subjected before and after the hydrocracking to many of the conventional refining operations. Among these is the substantially final step of fractionating or distilling the lube stock into various fractions according to viscosity which can then be blended to obtain a particular desired viscosity.
• the first fraction typically has an S.U.S. viscosity of about 100 and 100 F. and a boiling range of about 700 to 800 F. This is usually referred to in the industry as 100 Neutral.
• hydrocracking processes have greatly enhanced the viscosity index of the lubricating oil stocks so treated, on occasion at least certain fractions and especially the lighter fractions (e.g., 100 Neutral) are somewhat lower in viscosity index than the heavier fractions.
• the lighter fractions be of substantially the same V.I. as the heavier fractions.
• the lighter and first fractions comprise about one-third of the total finished lube product. Therefore, it is quite important that it have a fully satisfactory character such as viscosity index. It would be highly advantageous to provide a method for enhancing the viscosity index of the lighter fractions of hydrocracked lube oil product. It is therefore a primary object to prepare lubricating oils in high yields and having a high V.I. and particularly the lighter fractions or 100 Neutral product of a finished lube stock. It is another object to accomplish the V.I. enhancement without undue adverse effects on the other properties of the oil. It is still a further object to accomplish the objects of this invention in a relatively economical fashion. Other objectives will become apparent from the comments found herein.
• a paraffinic-base lube oil stock which has been hydrocracked over a hydrocracking catalyst at a temperature above about 650 F. under high pressure is fractionated into a first cut boiling in the range of about 700to 800 F. and a viscosity of about I at 100F., and said hydrocracked fraction boiling in the range of about 700to 800 F. is then separately rehydrocracked under substantially the same conditions as the total charge in the first step, and finally the rehydrocracked product fraction is recovered.
• the rehydrocracked fraction has an enhanced V.I.
• a deasphalted residuum having a V.I. in the range of about 75 and 100 and a viscosity at 210 F. in the range of about to 200 S.U.S. is treated with hydrogen at a temperature between about 650and 825 F. but preferably between about 735and 825 F. at a pressure of at least about 1,500 p.s.i. but more usually and preferably above about 2,500 and at a space velocity between about 0.2 and 4.0 but more usually about 0.4 and 1.5.
• the treatment with hydrogen is carried out in the presence of a catalyst having both aromatic saturation and ring-scission activity, which broadly comprises a sulfide of any metal of Group VI, left-hand column, of the periodic system mixed with an iron group metal, for example, a nickel sulfide and tungsten sulfide catalyst in about a l:l to 4:] metal ratio.
• a catalyst having both aromatic saturation and ring-scission activity which broadly comprises a sulfide of any metal of Group VI, left-hand column, of the periodic system mixed with an iron group metal, for example, a nickel sulfide and tungsten sulfide catalyst in about a l:l to 4:] metal ratio.
• the product from the hydrogen treatment is subjected to dewaxing (when necessary) and is then distilled to yield components most of which directly, or upon blending with each other, meet the SAE specifications for a multigrade lubricating oil and have a V.I. of about and
• U.S. Pat. No. 2,960,548 teaches that in order to obtain suitable yields of multigrade oils having the desired viscosity it is essential to employ as the charge to the hydrocracking reactor residual-type charge stocks; however, in the present invention at least, vacuum distillates, Duo-sol extracted residuum, residuums extracted with a solvent having preferential solubility for aromatics such as furfural and phenol, or blends of the foregoing are also suitable.
• the procedures for carrying out the extraction can be found in copending application Ser. No. 743,915 filed July 3, 1968, by Rene F. Kress.
• the charge should have an initial boiling point at above about 650 F. and preferably about above 700 F.
• the residuum starting material can be any residuum obtained by atmospheric or vacuum distillation, or the like, of any petroleum or residual fraction thereof which after deasphalting, preferably with a low-boiling hydrocarbon such as propane, propylene, or butane, has a V.I. of 75 to 100 and a viscosity at 210 F. of about 45 to 200 S.U.S. but is preferably above 50 S.U.S and still more preferably at least about 90 S.U.S.
• the residuum may be prepared by vacuum distillation of a Pennsylvania, Mid-Continent, West Texas, Kuwait. etc., crude. Unlike U.S. Pat. No.
• 2,960,458, deasphalting with agents such as sulfuric acid, phenol, sulfur dioxide, etc., in the present invention does not necessarily result in removal of components which upon hydrogenation have desirable properties for a multigrade oil product.
• these materials are employed for asphalt removal, the product produced in some cases is of as good or better quality; and the yield of multigrade oils is the same or even better in some cases.
• a higher carbon residue will result in undesirable shortening of the life of the catalyst under the relatively severe hydrogen treatment conditions employed to produce the multigrade oil. For this reason, it is usually preferred to employ charge stocks having a low-carbon 2 such as below about 2 (Conradson). However, higher carbon residue charge stock may be used if catalyst life is not of great importance or if a rugged catalyst is used.
• charge stock having a V.I. of 75 to 100 is essential in obtaining a reasonable yield ofa multigrade lubricating oil; i.e., a V.I. of above about 100 is produced in good yield only if a charging material of at least about 75 V.I. is employed. It will result in drastically lower yields if a lower than 75 V.I. charge stock is used.
• the viscosity at 210 F. is not absolutely required as the viscositymay be as low as about 45 S.U.S. but preferably is above about 50 S.U.S. at,2 F.
• the only important difference in using a feed having a viscosity below about 90 S.U.S. at 210 F. is the product viscosity and product distribution.
• a feed having a viscosity below about 90 S.U.S. for example, about 60 S.U.S.
• a full range of the conventionally desired blend stocks will not be obtained.
• this invention is most advantageously and preferably employed with feeds having a viscosity of about 90 to 200 S.U.S. at 210F.
• the lighter or l00 Neutral fraction obtained from the foregoing hydrocracking procedure does not exceed about I00 V.l. or is even less.
• the lighter fractions V.l. is desirably higher, according to the present invention, it alone is rehydrocracked at the foregoing conditions employed in the first hydrocracking step.
• the preferred conditions in the initial hydrocracking treatment are especially preferred in rehydrocracking the 100 Neutral fraction. in order to provide fullness of disclosure, the conditions for the rehydrocracking of the No. l distillate fraction will now be set forth although they are the same as the initial hydrocracking conditions employed for the total original feedstock.
• the procedure comprises charging the No. l distillate with hydrogen at a temperature between about 650and 825 F., preferably between 700and 800 F., and most preferably in the range of about 735to 775 F., a pressure above 1,500 psi. but more usually and preferably about 2,500, and a space velocity between about 0.2 and 4.0 but more usually about 0.4 and 1.5.
• the treatment with hydrogen is carried out in the presence of a catalyst having both aromatic saturation and ring-scission activity, which broadly comprises a sulfide of any metal of Group Vl, left-hand column, of the periodic system mixed with an iron group metal, for example, a nickel sulfide and tungsten sulfide catalyst, in about a 1:1 to 4:1 metal ratio.
• a catalyst having both aromatic saturation and ring-scission activity which broadly comprises a sulfide of any metal of Group Vl, left-hand column, of the periodic system mixed with an iron group metal, for example, a nickel sulfide and tungsten sulfide catalyst, in about a 1:1 to 4:1 metal ratio.
• Other variations of the hydrocracking process are well known or suggested in the art and are to be considered included within the scope of this invention. Examples of such are those described in U.S. Pat. No. 2,917, 448 to Beuther et al.; U.S. Pat. No. 3,046,218
• a charge stock of grade B solvent lube crude mix was charged to a crude still and fractionated into approximately 70 percent and 30 percent of overhead and bottoms, respectively.
• the bottoms had an initial boiling point at 650 F. at atmospheric pressure.
• the bottoms were charged to a vacuum still and fractionated to produce a gas oil, a distillate stock, and a residual asphalt stock, the latter two having initial boiling points of about 695 F. and 750 F., respectively.
• the residual stock was deasphalted and extracted by the Duo-Sol process (which employs propane'and a mixture of phenalcresol as solvents) at approximately 130F.
• the raffinate from the deasphalter and the distillate'stock from the vacuum still when combined had the following properties:
• Viscosity index The foregoing mixture was charged to a hydrocracker, and said material was hydrocracked in the preferred manner described in U.S. Pat. No. 2,960,458, i.e., at the preferred conditions and using a preferred nickel-tungsten sulfide catalyst set therein.
• a hydrogen stream comprising gas and hydrogen, of which about 85 percent was hydrogen, was used in the hydrocracking reaction.
• the crude hydrocracked product was charged to a stripper or atmospheric still and fractionated to produce gas, naphtha, and fuel oil, and a waxy lube of initial boiling point of approximately 700F.
• a process comprising hydrocracking a lube oil charge stock boiling above about 650 F., at from about 735 to 825 F and a hydrogen partial pressure of at least 1,500 p.s.i. to produce a hydrocrackate, separating a fraction boiling at from about 700 to 800 F. from said hydrocrackate and separately secondly, hydrocracking said fraction substantially by itself at from about 735 to 775 F. and a hydrogen partial pressure of at least about 1,500 p.s.i. and recovering from said second step recovering a lube oil having an enhanced viscosity index and boiling in the range of about 700 to 800 F., wherein the space velocity in both hydrocracking steps is from 0.4 to 1.5.
• the catalyst in both hydrocracking steps is a combination of at least two members of the group consisting of nickel sulfide, tungsten sulfide, cobalt sulfide, and molybdenum sulfide,
• the catalyst in both hydrocracking steps is a combination of nickel sulfide and tungsten sulfide in a metal ratio of from 1:1 to 4:1 nickel:tungsten supported on an alumina carrier.

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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)

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ID=25119032

Family Applications (1)

Country Status (8)

Cited By (3)

Families Citing this family (1)

Citations (5)

• 1968
  • 1968-11-29 US US780241A patent/US3617484A/en not_active Expired - Lifetime
• 1969
  • 1969-10-31 GB GB53447/69A patent/GB1270439A/en not_active Expired
  • 1969-11-11 NL NL6916947.A patent/NL160870C/xx not_active IP Right Cessation
  • 1969-11-17 BR BR214224/69A patent/BR6914224D0/pt unknown
  • 1969-11-20 JP JP44092558A patent/JPS4949006B1/ja active Pending
  • 1969-11-28 FR FR696941080A patent/FR2024536B1/fr not_active Expired
  • 1969-11-28 BE BE742422D patent/BE742422A/xx unknown
  • 1969-11-28 DE DE1959869A patent/DE1959869C3/de not_active Expired

Patent Citations (5)

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