US3902988A - Production of lubricating oils - Google Patents

Production of lubricating oils Download PDF

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US3902988A
US3902988A US436162A US43616274A US3902988A US 3902988 A US3902988 A US 3902988A US 436162 A US436162 A US 436162A US 43616274 A US43616274 A US 43616274A US 3902988 A US3902988 A US 3902988A
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solvent
dewaxing
fractions
viscosity index
fraction
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Robert Neil Bennett
Colin Leslie Gray
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BP PLC
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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
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • 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

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  • ABSTRACT A range of lubricating oils is produced by splitting a petroleum fraction boiling above 350C into light and heavy fractions. preferably at a cut point of 400500C treating the light fraction or fractions by catalytic dewaxing and solvent extraction and treating the heavy fraction or fractions by catalytic hydrogenation and solvent dewaxing.
  • Part of the heavy fraction may be solvent extracted and solvent dew-axed, and part solvent dewaxed only.
  • the catalytic dejwaxing process uses a mordenite catalyst and the catalytic hydrogenation may produce either high or super-high oils.
  • a process for the production of a range of lubricating oils comprises separating a petroleum fraction boiling above 350C into at least one lighter fraction and at least one heavier fraction. subjecting some or all of the lighter fraction or fractions to a hydro-catalytic dewaxing process and a solvent extraction process for the removal of aromatics and subjecting some or all of the heavier fraction or fractions to a hydrocatalytic viscosity index improvement process and a solvent dewaxing process.
  • lubricating oil as used in this specification includes lubricating oils for any use and also speci ality oils boiling within the lubricating oil boiling range. e.g.. transformer oils.
  • a particular feature of the present invention is that it allows the production of a wide range of oils from light spindle oils to heavy automative oils derived from bright stocks.
  • the cut point between the lighter and heavier fraction or fractions is in the range 450 to 500C.
  • the number of products obtained from the lighter fraction may conveniently be from 2 to 4. for example spindle oils and the two lightest grades of automotive lubricating oils.
  • the lighter fraction or fractions are treated. as indicated above. by the combination of hydrocatalytic dewaxing and solvent extraction to remove aromatics.
  • the processes may be used in either order. but. preferably. the hydro-catalytic dewaxing is first.
  • the sequence may treat a single wider boiling range fraction with subsequent distillation to give the required products. or may treat a series of fractions in blocked operation. the latter being preferred.
  • the preferred hydro-catalytic dewaxing process comprises passing the lighter fraction or fractions over a catalyst comprising one or more hydrogenating components selected from Groups Vla and Vlll of the Periodic Table incorporated with a crystalline mordenite of reduced alkali metal content together with hydrogen at a temperature of from 250 500C and a pressure of from 7 to 200 bars gauge. It may follow the general procedure described and claimed in our UK Pat. Nos.
  • a particular feature and advantage of hydro-catalytic dewaxing is its ability of the process to dewax to low pour points of from -50 to l8C with the present lighter fractions. which normally have pour points of from to C.
  • Such low pour points cannot be obtained by solvent dewaxing except at exorbitant cost and such low pour points have hitherto been obtained by urea dewaxing. itself a relatively expensive process.
  • the wax in these lighter fractions- is crystalline or paraffmie wax. c.g.. n-paraffins or slightly branched paraffins and it is selectively cracked to lower boiling paraffins. particularly C and C paraffins.
  • the selective breakdown of the paraffin wax hydrocarbons. is due to the nature of the mordenite based catalyst which promotes the selective attack of these hydrocarbonsbut not of the other hydrocarbons present in the feedstock.
  • Suitable process conditions for the catalytic dewaxing include. besides a temperature within the range 250 500C and a pressure within the range 7 200 bars gauge as indicated above. a space velocity between 0.1 20.0'v/v/hr. and a gas rateof 90 3.600
  • Preferred catalytic dewaxing conditions are:
  • crystalline mordenite of reduced alkali metal content means. preferably. a mordenite with an alkali metal content of less than 3% wt..
  • the deficiency of alkali metal-cations can be made up with other metal cations for example Group 11 metal cations. particularly magnesium or rare earth metal cations.
  • the mordenite is a decationised mordenite" which means a mordenite havinga deficiency of metal cations.
  • hydrogen mordenite since it is assumed that when metal cations are removed they are replaced by hydrogen ions. However. since it is not possible to detect the presence of hydrogen ions.in zeolites. the precise structure remains in doubt. A cation deficiency can. on the other hand. be readily measured by analysis of the metallic elements present inthe zeolite.
  • the mordenite may be treated with a mineral acid. for example hydrochloric'or sulphuric acid. in order directly to decationise the mordenite.
  • a combination of acid treatment and ammonium treatment-can also be used.
  • the decationised mordenite used in'the present invention has a higher than normal silicazalumina ratio of at least 14:1. ln specific examples ratios of as high as :1 have been obtained and apraetical upper limit may thus be :1. Particularly preferred silica-alumina ratios are-in the range 14:1 to 50:1.
  • the mordenite used in the present invention having a higher than normal silicazalumina ratio is obtained by treatment of a metal cation-containing mordenite, particularly sodium morde'nite, with a strong acid.
  • a metal cation-containing mordenite particularly sodium morde'nite
  • a strong acid for example sulphuric or hydrochloric acid, offrom 5 509/ wt strength and preferably from to wtstrength.
  • a single treatment or two or more successive treatments may be given with acids of the strengths stated above.
  • a convenient method of treatment is to treat the mordenite with acid under reflux for a period of 2 12 hours.
  • the residual metal cation content for example the sodium cation content, should be less than 3% wt of the mordenite and prefera bly less than 1.5% wt of the mordenite.
  • mordenites with higher than normal silica/alumina ratios retain the crystal structure of mordenite and are not significantly altered in terms of physical strength. Stability or crystallinity.
  • the hydrogenating component is preferably a platinum group metal, particularly platinum or palladium, and it is preferably added by ion-exchange.
  • the amount of the platinum group metal is preferably within the range 0.01 to 10% wt., particularly 0.1 to 571 wt;
  • iron group metals, particularly nickel also give useful results and they may be used in amounts similar to the platinum group metals.
  • Mixtures of certain'Gr'oup V1 and V111 metals and compounds may also. be used, e.g. cobalt and molybdenum.
  • the product from the dewaxing may be distilled to remove light ends boiling below the boiling point of the fecdstockfthese being, as previously indicated, mostly C and C paraffins which are useful as petrochemical fe'edstocks or LPG.
  • the product from the dewaxing is then treated with a selective solvent to remove aromatics.
  • the dewaxing reduces the viscosity index, and irrespective of whether the dewaxing precedes the solvent extraction or not, some V1 improvement will usually be necessary to restore at least a part of this VI loss and sometimes to increase it aboveits original level.
  • the product Vlis required will normally be within the range 0 to 100, and solvent extraction can produce such Vl's efficiency and economically from such feedstocks.
  • the solvent may be sulphur dioxide/benzene, phenol, glycol, or, preferably, furfural and it may be used in a fixed or rotatingdisc contactor with from 1 to 20 theo- 150C maximum Column top temperature Column base Conventional steps of separation of the extract and raffinate and recovery and recycle of solvent may be employed.
  • the heavier fraction or fractions boiling above the cut point may contain residue possibly together with one or more heavier distillates.
  • This portion of the original feedstock is, as previously indicated, treated by the combination of hydrocatalytic viscosity index improvement and solvent dewaxing.
  • the steps may be used in either order, with, preferably, the viscosity index improvement step first.
  • the feedstock may be treated in bulk with subsequent distillation into product fractions or, preferably, separated first into fractions which are passed through the treatment stages in blocked operation. Preferably it is separated into at least two fractions, one being a vacuum distillate and the other a vacuum residue, parts of which may, if desired, be subsequently reblended.
  • the vacuum residue portion will contain asphaltenes and possibly organo-metallic compounds, and may, therefore, be de-asphalted prior tothe hydro-catalytic treatment step.
  • the de-asphalting solvent may be a low-boiling n-paraffin, particularly propane, which may be used at 20 100C, preferably 40 80C, 5 50 bars gauge, preferably 25 35 bars gauge, and solvent ratios by volume of 1 20:1 preferably 5 13:1.
  • the preferred hydrocatalytic viscosity index improvement step comprises passing the heavier fraction or fractions over a catalyst comprising one or more hydrogenating components selected from Groups Vla and V111 of the Periodic Table on a refractory oxide support together with hydrogen at a temperature of from 340 460C and a pressure of from 210 bars gauge.
  • the hydro-catalytic viscosity index improvement step may be used to give products with moderate viscosity index, e.g., or high viscosity index, e.g., 101 and a particular advantage of its use is this flexibility.
  • High V1 oils are particularly useful not only for certain specialised uses but also in reducing or eliminating the need for viscosity index improvers in multigrade oils, and solvent extractions cannot easily or economically produce such high V1 oils.
  • V1 improvement two general processes are recognised. These are (i) a relatively mild treatment to give a moderate V1 improvement, e.g., 75 to 100 V1 after dewaxing with minimum breakdown and decrease in viscosity. Increase in V1 of the product to bring it up to multigradc oil requirements, if desired, can be achieved by the use of known polymeric V1 improvers (ii) a more severe treatment with extensive breakdown and decrease in viscosity but giving a larger V1 improve ment. e.g., greater than 100V] after dewaxing. A larger amount of lower boiling gas oil, kerosene and gasoline byproducts is obtained with the more severe treatment.
  • the broad ranges of process conditions and the preferred ranges for the two types of process may be chosen from
  • the refractory inorganic oxide support may be one or more oxides of elements of Groups 11, 111 or IV of the Periodic Table. and may contain halogen.
  • the amounts of the components of the support are chosen from the following ranges:
  • the hydrogenating component is preferably one or more of the oxides or sulphides of the Group Vla metals (i.e.. chromium. molybdenum or tungsten) and the iron group metals (i.e.. iron. cobalt or nickel). lf platinum group metals are used they are desirably in metallic form.
  • the amounts of the hydrogenating components may be (iroup Vla metals 2 25%; ⁇ 't (Expressed as metal) lron group metals I wt Platinum group metals 0.l 5% wt
  • Preferred hydrogenating components are from 2 wt of molybdenum (expressed as metal but present as oxide or sulphide) and 1 15% wt of nickel and/or cobalt (again expressed as metal but present as oxide or sulphide).
  • the preferred support has from 90% wt of Al: O; and l0 50% wt of SiO-
  • the type (ii) process preferably uses the same support. the increased severity being obtained from more severe operating conditions. but. if desired. a more acidic support may be used for example one with wt SiO. and 10 40% wt A1 0;, or 85 wt A1 0;, and 5 l5% wt F or C1.
  • viscosity index as used in this specification means that measured by ASTM D2270/64.
  • the product from the hydrocatalytic viscosity index improvement step is then solvent dewaxed.
  • the heavier product fractions are normally required to have pour points of from l8 to -9C which can be efficiently and economically produced with solvents.
  • Solvent de waxing also removes the microcrystalline wax present in these heavier fractions more readily than does catalytic dewaxing.
  • the solvent may be an alkyl ketone. the alkyl groups being the same or different and having 1 4 carbon atoms. Preferred solvents are methyl ethyl ketone. methyl isobutyl ketone or mixtures of the same. An aromatic. cg. benzene or toluene may also be present. preferably in an amount of from 25 75% wt vol of the total solvent. Other suitable solvents are C C, chlorinated hydrocarbons. c.g.. methylene chloride or ethylenc dichloride or C- C alkanes. particularly propane.
  • Solvent:oil ratios may be from 0.5 to 10: l by volume. preferably 1 to 5:1 and the mixture may be chilled to from 5 to 30C.
  • the chilling rate may be from 0.5 to 10C/minute. preferably 2 to 7C/minute.
  • the precipitated wax is removed by filtration and the filter cake is washed with cool solvent usually in a solvent/oil ratio of 0.2:1 8:1.
  • the dewaxed oil is freed from solvent by distillation the solvent being recycled for re-use.
  • the precipitated wax and the wash solvent may be separated intoproduct and solvent fractions by distillation.
  • the present invention therefore. includes a process for the production of a range of lubricating oils comprising separating a petroleum fraction boiling above 350C into at least one lighter fraction and at least two heavier fractions. subjecting the lighter fraction or frac tions to a hydrocatalytic dewaxing process and a solvent extraction process for the removal of aromatics. subjecting at least one of the heavier fractions to a hydrocatalytic viscosity index improvement process and a solvent dewaxing process and subjecting at least one other of the heavier fractions to a solvent extraction process for the removal of aromatics and a solvent dewaxing process.
  • Such a three-stream process is particularly suitable when it is desired to produce both 75 VI and 101 VI products from the heavier fractions.
  • the former being produced from the wholly solvent stream and the latter from the'mix'ed catalytic and solvent route.
  • the feedstock may be separated into three or more heavier fractions. at least one of which is subjected to a hydrocatalytic viscosity index improvement process and a solvent dewaxing process. at least another one of which is subjected to a solvent extraction process for the removal of aromatics and a solvent dewaxing process. and at least another one of which is subjected to a solvent dewaxing process without either a hydrocatalytic viscosity index improvement process or a solvent extraction process for the removal of aromatics.
  • All or any of the product fractions may be finished in known manner to improvecolour. oxidation stability or light stability. Thus they may be treated with clay or bauxite, or. preferably. given a mild hydrocatalytic treatment known as hydrofinishing. Such finishing treatments may be less necessary with the lighter catalytically dewaxed fractions.
  • the present invention may be used with a new lubricating oil plant or can be used to expand an existing plant formed of solvent extraction and solvent dewaxing units. It has been found that the addition of two catalytic units to an existing plant of two solvent units gives a reduction of up to 10% in capital cost as compared with adding two further solvent units or one further solvent unit and one catalytic unit. This advantage is in addition to the other advantages of flexibility. usage of individual processes in the most efficient manner and the ability to produce from a single plant. oils ranging from light oils with a viscosity of 22 cSt at l00F (38C) and a pour point of 40C to heavy oils with a viscosity of 1.200 cSt at 100F 38C) and a pour point of 12C.
  • the invention is illustrated with reference to the accompanying drawing which is a flow diagram of a lubricating oil production process according to the present invention.
  • the drawing is based on the expansion ofan existing lubricating oil unit with existing plant indicated by shading.
  • the plant consists of two vacuum distillation columns 1, 2, two propane deasphalting units 3, 4. a catalytic dewaxing unit 5, a catalytic hydrogenating unit 6, a furfural extraction unit 7 and a solvent dewaxing unit 8.
  • Atmospheric residue with an initial boiling point of 250C is fed through lines 9, 10 to the vacuum distillation columns 1. 2. Each column separates the atmospheric residue into light ends boiling below 350C which are taken off overhead through lines ll. 12 for disposal elsewhere, 4 distillate fractions A. B. C. D. and A. B. C. D and a residue fraction E and E. Distillates A. B. C are passed through lines l3, l4, 15 to the catalytic dewaxing unit 5. All or part of distillates A.
  • B and C can also be passed. if desired. to the catalytic dewaxing unit 5 through lines not shown.
  • the catalytically dewaxed distill-ates then pass to the furfural extraction unit 7 and are recovered as A-. B and C products through lines 16, 17 and 18.
  • the distillate C stream is split. part of it. going separately through the furfural extraction unit at different extraction conditions and then, via line 19. for blending with a stream described hereafter.
  • Distillate D goes via line 20 (together with distillate D if desired) to the catalytic hydrogenation unit 6 and then to the solvent dewaxing unit 8 being recovered as product D through line 21 after blending with a portion of distillate C from line 19 and a portion of residue E from line 30.
  • Residue E passes through line 22 to the propane deasphalting unit 3 and is then split into three. Part goes through line 23 to the catalytic hydrogenation unit 6, part goes through line 24 to the furfural extraction unit 7 and part by-passes both units. going direct to the solvent dewaxing unit 8 through line 25.
  • the part going through line 23 is blended with distillate D from line 20 and thus eventually becomes part of product D
  • the part going via line 24 through the furfural extraction unit then passes to the solvent dewaxing unit emerging through line 26 as product E.
  • the part going through line direct to the solvent dewaxing unit emerges as product E through line 27.
  • Residue E is sent via line 28 to the propane deasphalting unit 4. the catalytic hydrogenation unit 6, and the solvent dewaxing unit 8 emerging through line 29 as product E Part of this product. as indicated above.
  • the invention is illustrated by the following example.
  • Example A range of lubricating oils was produced from an atmospheric residue of a Kuwait crude oil using the process scheme described above.
  • the grades produced and the feedstocks used are shown in Table 1 below.
  • the first four grades were produced from the indicated feedstocks by a combination of catalytic dewaxing and furfural extraction.
  • the catalytic dewaxing conditions were Temperatu re "C 320400C Pressure bars gauge (1) Gas recycle rate m"/m 1684 Catalyst 0.57: wt. platinum on mordcnite decationised to a Na content of 0.75% wt. and acid treated to a silicazalumina ratio of 18:1.
  • the recycle gas was scrubbed to reduce the H 5 content to a maximum of 500 ppm vol. of H 5 at the reactor outlet and the NH;; content to less than 5 ppm vol.
  • the hydrogenation conditions were 3.
  • a process as claimed in claim I for the production of a range of lubricating oils comprising separating a petroleum fraction boiling above 350C into at least one lighter fraction and at least two heavier fractions. subjecting the lighter fraction or fractions to said h 5 8 drocatalytic dewaxing process and a solvent extraction process for the removal of aromatics. subjecting at least Tcmpmmm cc (H 3504: one of the heavier fractions to said hydrocatalytic vis- PI'LSSUI'K. bars gauge 13s I38 cosity index improvement process and a solvent devvaxl ll fii mm mHill.
  • T'l m y la 4 A process as claimed in claim 3 wherein the feed- 0 L support stock is separated into three or more heavier fractions. at least one of which is subjected to said hydrocatalytic Th I x d I l5 viscosity index improvement process and a solvent de- C 50 um evmxmg con mom were waxing process. at least another one of which is subjected to a solvent extraction process for the removal Tcmpcmum c mm to of aromatics and a solvent dewaxing process.
  • a process for the production of a range of lubricatvent extraction uses furfural at a solvent:oil ratio of 0.5 ing ils comprising separating a petroleum fraction to Sil by volume and an average temperature Of from O O boiling above 350C.
  • the hyincor from Groups VIA and Y of the P.cno 1c a e drocatalytic viscosity index improvement process conporated with a crystalline mordenite or reduced alkali ditions are a temperature offmm to 420C p 323? hydrogen g g sure of from to 170 bars gauge.
  • vent dewaxing uses an alkyl ketone at a solvent:oil ratio of 0.5 to 10:1 and a temperature of from 5 to -30C. l l l l l

Abstract

A range of lubricating oils is produced by splitting a petroleum fraction boiling above 350*C into light and heavy fractions, preferably at a cut point of 400*-500*C treating the light fraction or fractions by catalytic dewaxing and solvent extraction and treating the heavy fraction or fractions by catalytic hydrogenation and solvent dewaxing. Part of the heavy fraction may be solvent extracted and solvent dewaxed, and part solvent dewaxed only. The catalytic dewaxing process uses a mordenite catalyst and the catalytic hydrogenation may produce either high or super-high oils.

Description

United States Patent 1191 Bennett et al.
14 1 Sept. 2, 1975 1 PRODUCTION OF LUBRICATING OILS [75] Inventors: Robert Neil Bennett, Englefield Green; Colin Leslie Gray, Fleet, both of England [73] Assignee: The British Petroleum Company Limited, London, England [22] Filed: Jan. 24, 1974 [21] Appl. No.: 436,162
[30} Foreign Application Priority Data Feb. 9, 1973 United Kingdom 6388/73 [52] U.S. Cl. 208/80; 208/18; 208/92;
208/111; 208/112 [51} Int. Cl... ClOg 41/00; ClOg 13/02; ClOg 37/04 [58] Field of Search 208/80, 1 ll [56] References Cited UNITED STATES PATENTS 2,960,458 11/1960 Beuthcr ct al. 208/19 3,5 l6,925 6/ 1970 Lawrancc ct al. 208/1 1 1 3,652,448 3/1972 Cummins 208/87 3,732,156 5/1973 Bennett ct a1 208/111 3,755,138 8/1973 Chen 208/33 3,764,518 10/1973 Henke et al. 208/80 3,801 ,496 4/1974 Bcnncr 208/1 1 l FOREIGN PATENTS OR APPLICATIONS 1,088,933 10/1967 United Kingdom 208 111 1,134,014 11/1968 United Kingdom 208 111 1,295,501 11 1972 United Kingdom 208/87 1,295,502 11 /1972 United Kingdom 208/87 Primary E.\'amir1erDelbert E. Gantz Ass-119mm Examiner-G. E. Schmitkons Attorney, Agent, or FirmM0rgan, Finnegan, Pine, Foley & Lee
[57] ABSTRACT A range of lubricating oils is produced by splitting a petroleum fraction boiling above 350C into light and heavy fractions. preferably at a cut point of 400500C treating the light fraction or fractions by catalytic dewaxing and solvent extraction and treating the heavy fraction or fractions by catalytic hydrogenation and solvent dewaxing.
Part of the heavy fraction may be solvent extracted and solvent dew-axed, and part solvent dewaxed only.
The catalytic dejwaxing process uses a mordenite catalyst and the catalytic hydrogenation may produce either high or super-high oils.
9 Claims, 1 Drawing Figure PRODUCTION OF LUBRICATING OILS This invention relates to the production of lubricating oils. and particularly to the production of a wide range of such oils.
The main steps in the production of lubricating oils from petroleum fractions are (a) aromatics removal giving an improved viscosity index and (b) dewaxing giving an improved pour point. Both steps normally use solvents to obtain the desired results, but hydrocatalytie alternatives have also been proposed for both steps. Each of the four processes has its advantages and disadvantages. In the present invention the'four processes are combined in a particular way to make the best use of the potential of each process and to avoid using processes for duties for which they are not suited.
According to the present invention, a process for the production of a range of lubricating oils comprises separating a petroleum fraction boiling above 350C into at least one lighter fraction and at least one heavier fraction. subjecting some or all of the lighter fraction or fractions to a hydro-catalytic dewaxing process and a solvent extraction process for the removal of aromatics and subjecting some or all of the heavier fraction or fractions to a hydrocatalytic viscosity index improvement process and a solvent dewaxing process.
The term lubricating oil as used in this specification includes lubricating oils for any use and also speci ality oils boiling within the lubricating oil boiling range. e.g.. transformer oils. A particular feature of the present invention is that it allows the production of a wide range of oils from light spindle oils to heavy automative oils derived from bright stocks.
Preferably the cut point between the lighter and heavier fraction or fractions is in the range 450 to 500C.
The number of products obtained from the lighter fraction may conveniently be from 2 to 4. for example spindle oils and the two lightest grades of automotive lubricating oils.
The lighter fraction or fractions are treated. as indicated above. by the combination of hydrocatalytic dewaxing and solvent extraction to remove aromatics. The processes may be used in either order. but. preferably. the hydro-catalytic dewaxing is first. The sequence may treat a single wider boiling range fraction with subsequent distillation to give the required products. or may treat a series of fractions in blocked operation. the latter being preferred.
The preferred hydro-catalytic dewaxing process comprises passing the lighter fraction or fractions over a catalyst comprising one or more hydrogenating components selected from Groups Vla and Vlll of the Periodic Table incorporated with a crystalline mordenite of reduced alkali metal content together with hydrogen at a temperature of from 250 500C and a pressure of from 7 to 200 bars gauge. It may follow the general procedure described and claimed in our UK Pat. Nos.
1088933 and 1134014.
A particular feature and advantage of hydro-catalytic dewaxing is its ability of the process to dewax to low pour points of from -50 to l8C with the present lighter fractions. which normally have pour points of from to C. Such low pour points cannot be obtained by solvent dewaxing except at exorbitant cost and such low pour points have hitherto been obtained by urea dewaxing. itself a relatively expensive process.
-The wax in these lighter fractions-is crystalline or paraffmie wax. c.g.. n-paraffins or slightly branched paraffins and it is selectively cracked to lower boiling paraffins. particularly C and C paraffins. The selective breakdown of the paraffin wax hydrocarbons. is due to the nature of the mordenite based catalyst which promotes the selective attack of these hydrocarbonsbut not of the other hydrocarbons present in the feedstock. Suitable process conditions for the catalytic dewaxing include. besides a temperature within the range 250 500C and a pressure within the range 7 200 bars gauge as indicated above. a space velocity between 0.1 20.0'v/v/hr. and a gas rateof 90 3.600
m /m of hydrogen.
Preferred catalytic dewaxing conditions are:
The term crystalline mordenite of reduced alkali metal content" means. preferably. a mordenite with an alkali metal content of less than 3% wt..The deficiency of alkali metal-cations can be made up with other metal cations for example Group 11 metal cations. particularly magnesium or rare earth metal cations. Preferably however the mordenite is a decationised mordenite" which means a mordenite havinga deficiency of metal cations. As alternative term-in the art is hydrogen mordenite. since it is assumed that when metal cations are removed they are replaced by hydrogen ions. However. since it is not possible to detect the presence of hydrogen ions.in zeolites. the precise structure remains in doubt. A cation deficiency can. on the other hand. be readily measured by analysis of the metallic elements present inthe zeolite. A
Natural or freshly prepared synthetic mordenite has the formula:
' off ammonia. leaving behind the hydrogen form or decationised mordenite. According to the second method the mordenite may be treated with a mineral acid. for example hydrochloric'or sulphuric acid. in order directly to decationise the mordenite. A combination of acid treatment and ammonium treatment-can also be used.
Preferably the decationised mordenite used in'the present invention has a higher than normal silicazalumina ratio of at least 14:1. ln specific examples ratios of as high as :1 have been obtained and apraetical upper limit may thus be :1. Particularly preferred silica-alumina ratios are-in the range 14:1 to 50:1.
It has been found that certain decationisation treatments remove aluminium as well as the expected metal cations and desirably therefore the mordenite used in the present invention having a higher than normal silicazalumina ratio is obtained by treatment of a metal cation-containing mordenite, particularly sodium morde'nite, with a strong acid. for example sulphuric or hydrochloric acid, offrom 5 509/ wt strength and preferably from to wtstrength. A single treatment or two or more successive treatments may be given with acids of the strengths stated above.
A convenient method of treatment is to treat the mordenite with acid under reflux for a period of 2 12 hours.
In the decationised mordenitc the residual metal cation content, for example the sodium cation content, should be less than 3% wt of the mordenite and prefera bly less than 1.5% wt of the mordenite.
It should be emphasised that mordenites with higher than normal silica/alumina ratios retain the crystal structure of mordenite and are not significantly altered in terms of physical strength. Stability or crystallinity.
The hydrogenating component is preferably a platinum group metal, particularly platinum or palladium, and it is preferably added by ion-exchange. The amount of the platinum group metal is preferably within the range 0.01 to 10% wt., particularly 0.1 to 571 wt; However, iron group metals, particularly nickel, also give useful results and they may be used in amounts similar to the platinum group metals. Mixtures of certain'Gr'oup V1 and V111 metals and compounds may also. be used, e.g. cobalt and molybdenum.
250 '"'600 C before use to remove any water and to eliminate any ligands attached to the hydrogenation componentj The product from the dewaxing may be distilled to remove light ends boiling below the boiling point of the fecdstockfthese being, as previously indicated, mostly C and C paraffins which are useful as petrochemical fe'edstocks or LPG.
The product from the dewaxing is then treated with a selective solvent to remove aromatics. The dewaxing reduces the viscosity index, and irrespective of whether the dewaxing precedes the solvent extraction or not, some V1 improvement will usually be necessary to restore at least a part of this VI loss and sometimes to increase it aboveits original level. With the lighter fractions being treated the product Vlis required will normally be within the range 0 to 100, and solvent extraction can produce such Vl's efficiency and economically from such feedstocks.
The solvent may be sulphur dioxide/benzene, phenol, glycol, or, preferably, furfural and it may be used in a fixed or rotatingdisc contactor with from 1 to 20 theo- 150C maximum Column top temperature Column base Conventional steps of separation of the extract and raffinate and recovery and recycle of solvent may be employed.
The heavier fraction or fractions boiling above the cut point may contain residue possibly together with one or more heavier distillates. This portion of the original feedstock is, as previously indicated, treated by the combination of hydrocatalytic viscosity index improvement and solvent dewaxing. The steps may be used in either order, with, preferably, the viscosity index improvement step first. The feedstock may be treated in bulk with subsequent distillation into product fractions or, preferably, separated first into fractions which are passed through the treatment stages in blocked operation. Preferably it is separated into at least two fractions, one being a vacuum distillate and the other a vacuum residue, parts of which may, if desired, be subsequently reblended.
The vacuum residue portion will contain asphaltenes and possibly organo-metallic compounds, and may, therefore, be de-asphalted prior tothe hydro-catalytic treatment step. The de-asphalting solvent may be a low-boiling n-paraffin, particularly propane, which may be used at 20 100C, preferably 40 80C, 5 50 bars gauge, preferably 25 35 bars gauge, and solvent ratios by volume of 1 20:1 preferably 5 13:1.
The preferred hydrocatalytic viscosity index improvement step comprises passing the heavier fraction or fractions over a catalyst comprising one or more hydrogenating components selected from Groups Vla and V111 of the Periodic Table on a refractory oxide support together with hydrogen at a temperature of from 340 460C and a pressure of from 210 bars gauge.
The hydro-catalytic viscosity index improvement step may be used to give products with moderate viscosity index, e.g., or high viscosity index, e.g., 101 and a particular advantage of its use is this flexibility. High V1 oils are particularly useful not only for certain specialised uses but also in reducing or eliminating the need for viscosity index improvers in multigrade oils, and solvent extractions cannot easily or economically produce such high V1 oils.
Thus within the context of hydrocatalytic treatment for V1 improvement, two general processes are recognised. These are (i) a relatively mild treatment to give a moderate V1 improvement, e.g., 75 to 100 V1 after dewaxing with minimum breakdown and decrease in viscosity. Increase in V1 of the product to bring it up to multigradc oil requirements, if desired, can be achieved by the use of known polymeric V1 improvers (ii) a more severe treatment with extensive breakdown and decrease in viscosity but giving a larger V1 improve ment. e.g., greater than 100V] after dewaxing. A larger amount of lower boiling gas oil, kerosene and gasoline byproducts is obtained with the more severe treatment.
The broad ranges of process conditions and the preferred ranges for the two types of process may be chosen from The refractory inorganic oxide support may be one or more oxides of elements of Groups 11, 111 or IV of the Periodic Table. and may contain halogen. Preferably the amounts of the components of the support are chosen from the following ranges:
The hydrogenating component is preferably one or more of the oxides or sulphides of the Group Vla metals (i.e.. chromium. molybdenum or tungsten) and the iron group metals (i.e.. iron. cobalt or nickel). lf platinum group metals are used they are desirably in metallic form.
The amounts of the hydrogenating components may be (iroup Vla metals 2 25%; \\'t (Expressed as metal) lron group metals I wt Platinum group metals 0.l 5% wt Preferred hydrogenating components are from 2 wt of molybdenum (expressed as metal but present as oxide or sulphide) and 1 15% wt of nickel and/or cobalt (again expressed as metal but present as oxide or sulphide).
For the type (i) process the preferred support has from 90% wt of Al: O; and l0 50% wt of SiO- The type (ii) process preferably uses the same support. the increased severity being obtained from more severe operating conditions. but. if desired. a more acidic support may be used for example one with wt SiO. and 10 40% wt A1 0;, or 85 wt A1 0;, and 5 l5% wt F or C1.
The precise choice and number of heavier fractions treated will depend on the VI improvement required. The greater the VI improvement the greater the drop viscosity and. preferably, at least a proportion of vacuum residue is used with the type (ii) process. Vacuum distillate and/or residue fractions may be used with the type (i) process.
The term viscosity index as used in this specification means that measured by ASTM D2270/64.
In addition to some breakdown to products boiling below 350C there may be conversion of sulphur and nitrogen compounds to H. S and NH At least the latter is desirably removed. by scrubbing with water, from any gas recycled and products boiling below 350C are desirably removed by distillation.
The product from the hydrocatalytic viscosity index improvement step is then solvent dewaxed. The heavier product fractions are normally required to have pour points of from l8 to -9C which can be efficiently and economically produced with solvents. Solvent de waxing also removes the microcrystalline wax present in these heavier fractions more readily than does catalytic dewaxing.
The solvent may be an alkyl ketone. the alkyl groups being the same or different and having 1 4 carbon atoms. Preferred solvents are methyl ethyl ketone. methyl isobutyl ketone or mixtures of the same. An aromatic. cg. benzene or toluene may also be present. preferably in an amount of from 25 75% wt vol of the total solvent. Other suitable solvents are C C, chlorinated hydrocarbons. c.g.. methylene chloride or ethylenc dichloride or C- C alkanes. particularly propane.
The oil is mixed with solvent and is usually heated to cnusre complete solution and is then chilled to precipitate the wax. Solvent:oil ratios may be from 0.5 to 10: l by volume. preferably 1 to 5:1 and the mixture may be chilled to from 5 to 30C. The chilling rate may be from 0.5 to 10C/minute. preferably 2 to 7C/minute.
The precipitated wax is removed by filtration and the filter cake is washed with cool solvent usually in a solvent/oil ratio of 0.2:1 8:1. The dewaxed oil is freed from solvent by distillation the solvent being recycled for re-use. Similarly the precipitated wax and the wash solvent may be separated intoproduct and solvent fractions by distillation.
While the invention. in its broadest aspect. splits the feedstock into two main streams. further sub-division is possible with a third stream taking a wholly solvent route. a fourth stream being subjected only to solvent dewaxing and possibly a fifth stream taking a wholly catalytic route.
The present invention. therefore. includes a process for the production of a range of lubricating oils comprising separating a petroleum fraction boiling above 350C into at least one lighter fraction and at least two heavier fractions. subjecting the lighter fraction or frac tions to a hydrocatalytic dewaxing process and a solvent extraction process for the removal of aromatics. subjecting at least one of the heavier fractions to a hydrocatalytic viscosity index improvement process and a solvent dewaxing process and subjecting at least one other of the heavier fractions to a solvent extraction process for the removal of aromatics and a solvent dewaxing process.
Such a three-stream process is particularly suitable when it is desired to produce both 75 VI and 101 VI products from the heavier fractions. the former being produced from the wholly solvent stream and the latter from the'mix'ed catalytic and solvent route.
In a further embodiment the feedstock may be separated into three or more heavier fractions. at least one of which is subjected to a hydrocatalytic viscosity index improvement process and a solvent dewaxing process. at least another one of which is subjected to a solvent extraction process for the removal of aromatics and a solvent dewaxing process. and at least another one of which is subjected to a solvent dewaxing process without either a hydrocatalytic viscosity index improvement process or a solvent extraction process for the removal of aromatics.
All or any of the product fractions may be finished in known manner to improvecolour. oxidation stability or light stability. Thus they may be treated with clay or bauxite, or. preferably. given a mild hydrocatalytic treatment known as hydrofinishing. Such finishing treatments may be less necessary with the lighter catalytically dewaxed fractions.
The present invention may be used with a new lubricating oil plant or can be used to expand an existing plant formed of solvent extraction and solvent dewaxing units. It has been found that the addition of two catalytic units to an existing plant of two solvent units gives a reduction of up to 10% in capital cost as compared with adding two further solvent units or one further solvent unit and one catalytic unit. This advantage is in addition to the other advantages of flexibility. usage of individual processes in the most efficient manner and the ability to produce from a single plant. oils ranging from light oils with a viscosity of 22 cSt at l00F (38C) and a pour point of 40C to heavy oils with a viscosity of 1.200 cSt at 100F 38C) and a pour point of 12C.
The invention is illustrated with reference to the accompanying drawing which is a flow diagram of a lubricating oil production process according to the present invention. The drawing is based on the expansion ofan existing lubricating oil unit with existing plant indicated by shading.
1n the drawing. the plant consists of two vacuum distillation columns 1, 2, two propane deasphalting units 3, 4. a catalytic dewaxing unit 5, a catalytic hydrogenating unit 6, a furfural extraction unit 7 and a solvent dewaxing unit 8.
Atmospheric residue with an initial boiling point of 250C is fed through lines 9, 10 to the vacuum distillation columns 1. 2. Each column separates the atmospheric residue into light ends boiling below 350C which are taken off overhead through lines ll. 12 for disposal elsewhere, 4 distillate fractions A. B. C. D. and A. B. C. D and a residue fraction E and E. Distillates A. B. C are passed through lines l3, l4, 15 to the catalytic dewaxing unit 5. All or part of distillates A.
B and C can also be passed. if desired. to the catalytic dewaxing unit 5 through lines not shown. The catalytically dewaxed distill-ates then pass to the furfural extraction unit 7 and are recovered as A-. B and C products through lines 16, 17 and 18. Before the furfural extraction unit. the distillate C stream is split. part of it. going separately through the furfural extraction unit at different extraction conditions and then, via line 19. for blending with a stream described hereafter.
Distillate D goes via line 20 (together with distillate D if desired) to the catalytic hydrogenation unit 6 and then to the solvent dewaxing unit 8 being recovered as product D through line 21 after blending with a portion of distillate C from line 19 and a portion of residue E from line 30. Residue E passes through line 22 to the propane deasphalting unit 3 and is then split into three. Part goes through line 23 to the catalytic hydrogenation unit 6, part goes through line 24 to the furfural extraction unit 7 and part by-passes both units. going direct to the solvent dewaxing unit 8 through line 25. The part going through line 23 is blended with distillate D from line 20 and thus eventually becomes part of product D The part going via line 24 through the furfural extraction unit then passes to the solvent dewaxing unit emerging through line 26 as product E. The part going through line direct to the solvent dewaxing unit emerges as product E through line 27.
Residue E is sent via line 28 to the propane deasphalting unit 4. the catalytic hydrogenation unit 6, and the solvent dewaxing unit 8 emerging through line 29 as product E Part of this product. as indicated above.
is blended with product D" through line 30.
The invention is illustrated by the following example.
I Example A range of lubricating oils was produced from an atmospheric residue of a Kuwait crude oil using the process scheme described above. The grades produced and the feedstocks used are shown in Table 1 below.
Table 1 Feedstoc k Grade Transformer oil Vacuum Gas Oil 205 A cut 33/100 B cut 1 10/75 C cut 22/125 C cut l 10/95 5071 DAO. 507! D cut 550/ DAO 750/85 DAO TBP Cut Boiling Range Viscosity (determined by GLC) cSt at 210F) A 330 460 3.9 B 360 495 6.1 C 350 580 9.4 D 14.4
Where blends of cuts were used. the percentages were by volume. The residue was deasphalted using propane as solvent to give deasphalted oil (DAO) hav ing a viscosity of 36.5 cSt at 210F.
The first four grades were produced from the indicated feedstocks by a combination of catalytic dewaxing and furfural extraction.
The catalytic dewaxing conditions were Temperatu re "C 320400C Pressure bars gauge (1) Gas recycle rate m"/m 1684 Catalyst 0.57: wt. platinum on mordcnite decationised to a Na content of 0.75% wt. and acid treated to a silicazalumina ratio of 18:1.
The recycle gas was scrubbed to reduce the H 5 content to a maximum of 500 ppm vol. of H 5 at the reactor outlet and the NH;; content to less than 5 ppm vol.
The yields from the catalytic dewaxing and the furfural treatment. and the amount of furfural used are shown in Table 2.
TABLE 2 Catalytic Dewaxing Furfural Extraction Dewaxed Chemical Gas Gasoline Furfural Extraction (iradc Lube Hydrogen Yield Yield Treatment Yield Yield Consumption wt. 9? wt. "/1 vol. '71 wt. 91 wt. scf/brl. C,C C -.l 17C 'lransformcr Oil 70 300 26.0 4.0 55 20S 82 200 14.0 4.0 80 75 33/100 82.. 230 12.5 5.0 400 48 I 10/75 I The remaining four grades were produced from the indicated fcedstocks b a combination of hydrogenation and solvent dew-axing.
The hydrogenation conditions were 3. A process as claimed in claim I for the production of a range of lubricating oils comprising separating a petroleum fraction boiling above 350C into at least one lighter fraction and at least two heavier fractions. subjecting the lighter fraction or fractions to said h 5 8 drocatalytic dewaxing process and a solvent extraction process for the removal of aromatics. subjecting at least Tcmpmmm cc (H 3504: one of the heavier fractions to said hydrocatalytic vis- PI'LSSUI'K. bars gauge 13s I38 cosity index improvement process and a solvent devvaxl ll fii mm mHill. 0 l ti ing process and subjecting at least one other of the (mum, if I M C and p M MU m heavier fractions to a solvent extraction process for the i on silica alumina. having a removal of aromatics and a solvent dewaxing process.
T'l m y la 4. A process as claimed in claim 3 wherein the feed- 0 L support stock is separated into three or more heavier fractions. at least one of which is subjected to said hydrocatalytic Th I x d I l5 viscosity index improvement process and a solvent de- C 50 um evmxmg con mom were waxing process. at least another one of which is subjected to a solvent extraction process for the removal Tcmpcmum c mm to of aromatics and a solvent dewaxing process. and at s nm, a m least another one of which is subjected to a solvent desilwm i' i' Kslmw 2O waxing process without either a hydrocatalytic viscosity index improvement process or a solvent extraction The yields from the processes are shown in Table 3. process for the removal of aromatics.
TABLE 3 Hydrogenation Data Dewaxing Data Waxy Chemical Gas Gasoline Middle Product Grade Lube Hydrogen Yield Yield Distillate Yield Yield Consumption 71 wt. 71 wt. Yield 7: wt. '/r wt. scf/brl C;,l77( /r wt.
l77-37lC ll0/95 i i.0 720 5.3 4.8 i2.5 83.5 550/95 90.7 500 3.! 0.3 6.8 83.5 750 x5 96.0 330 1.2 0.4 2.5 83.5 22/125 47.0 1150 6.5 ll.l 36.6 75.0
We claim: 5. A process as claimed in claim 1 wherein the soll. A process for the production of a range of lubricatvent extraction uses furfural at a solvent:oil ratio of 0.5 ing ils comprising separating a petroleum fraction to Sil by volume and an average temperature Of from O O boiling above 350C. into at least one lighter fraction 15 to 150 C and at least one heavier fraction, subjecting at least a A P Q f m whcrem the y- Portion of the lighter fraction to a hydro-catalytic depg i g fig c "1011s ig t I I d a Solvent extraction recess Said ature 0 rom to a pressure 0 rom o B g S gg rocess Com i assin 200 bars gauge. a space velocity of from 0.5 to 10 y Iii-Cd y g p g p v/v/hr and a hydrogen gas rate of from 900 to 2.700 the lighter fraction or fractions over a catalyst comprismx/mu mg one or more hydrogcnatmg m g l l 7. A process as claimed in claim 1 wherein the hyincor from Groups VIA and Y of the P.cno 1c a e drocatalytic viscosity index improvement process conporated with a crystalline mordenite or reduced alkali ditions are a temperature offmm to 420C p 323? hydrogen g g sure of from to 170 bars gauge. a space velocity of g l 5 il zi g ggs a 50 from 0.5 to 2 v/v/hr and a hydrogen gas rate of 360 to J g 1.800 m/m to give a dewaxed product viscositv index heavier fraction to a hydro-catalytic viscosity index rmf f t 3 provement process and a solvent dewaxing process, 0 g p us'claimed in chim 1 Whcmin the y said hydro-catalytic viscosity index improvement prodrocatal tic viscosit index im rovement rocess confi 3;: ggi i figf gg g: 55 ditions ai e a temperature of fro in 380 to 420C at presy l g G d sure of from to 210 bars gauge. a space velocity of [mung components Se ecte 5 roupz A an from 0 2 t0 2 v/v/hr and '1 hydrogen gas rate of from z l r* ra tor oxi e su ort toi of pulodlc T lble on i b c y pp 360 to 1.800 m/m" to give a dewaxed product viscositv gcther with hydrogen at a temperature of from d A f t th I 0 340460C. and apressure offrom 70-210 bars gauge. g iA Th l 1 h th I process as c aime in c aim w erein e so 2. A process as claimed in claim 1 wherein the cut point between the lighter and heavier fractions is in the range 450-500C.
vent dewaxing uses an alkyl ketone at a solvent:oil ratio of 0.5 to 10:1 and a temperature of from 5 to -30C. l l l l

Claims (9)

1. A PROCESS FOR THE PRODUCTION OF A RANGE OF LUBRICATING OILS COMPRISING SEPARATING A PETROLEUM FRACTION BOILING ABOVE 350*C, INTO AT LEAST ONE LIGHTER FRACTION AND AT LEAST ONE HEAVIER FRACTION, SUBJECTING AT LEAST A PORTION OF THE LIGHTER FRACTION TO A HYDRO-CATALYTIC DEWAXING PROCESS AND A SOLVENT EXTRACTION PROCESS, SAID HYDRO-CATALYTIC DEWAXING PROCESS COMPRISING PASSING THE LIGHTER FRACTION OR FRACTIONS OVER A CATALYST COMPRISING ONE OR MORE HYDROGENATING COMPONENTS SELECTED FROM GROUPS VIA AND VIII OF THE PERIODIC TABLE INCORPORATED WITH A CRYSTALLINE MORDENITE OR REDUCED ALKALI METAL CONTENT TOGETHER WITH HYDROGEN AT A TEMPERATURE OF FROM 250*-500*, AND A PRESSURE OF FROM 7 TO 200 BARS GAUGE AND, SUBJECTING AT LEAST A PORTION OF A HEAVIER FRACTION TO A HYDRO-CATALYTIC VISCOSITY INDEX IMPROVEMENT PROCESS AND A SOLVENT DEWAXING PROCESS, SAID HYDRO-CATALYTIC VISCOSITY INDEX IMPROVEMENT PROCESS COMPRISING PASSING THE HEAVIER FRACTION OR FRACTIONS OVER A CATALYST COMPRISING ONE OR MORE HYDROGENATING COMPONENTS SELECTED FROM GROUPS VIA AND VIII OF THE PERIODIC TABLE ON A REFRACTORY OXIDE SUPPORT TOGETHER WITH HYDROGEN AT A TEMPERATURE OF FROM 340*-460*C, AND A PRESSURE OF FROM 70-210 BARS GAUGE.
2. A process as claimed in claim 1 wherein the cut point between the lighter and heavier fractions is in the range 450*-500*C.
3. A process as claimed in claim 1 for the production of a range of lubricating oils comprising separating a petroleum fraction boiling above 350*C into at least one lighter fraction and at least two heavier fractions, subjecting the lighter fraction or fractions to said hydrocatalytic dewaxing process and a solvent extraction process for the removal of aromatics, subjEcting at least one of the heavier fractions to said hydrocatalytic viscosity index improvement process and a solvent dewaxing process and subjecting at least one other of the heavier fractions to a solvent extraction process for the removal of aromatics and a solvent dewaxing process.
4. A process as claimed in claim 3 wherein the feedstock is separated into three or more heavier fractions, at least one of which is subjected to said hydrocatalytic viscosity index improvement process and a solvent dewaxing process, at least another one of which is subjected to a solvent extraction process for the removal of aromatics and a solvent dewaxing process, and at least another one of which is subjected to a solvent dewaxing process without either a hydrocatalytic viscosity index improvement process or a solvent extraction process for the removal of aromatics.
5. A process as claimed in claim 1 wherein the solvent extraction uses furfural at a solvent:oil ratio of 0.5 to 5:1 by volume and an average temperature of from 15* to 150*C.
6. A process as claimed in claim 1 wherein the hydrocatalytic dewaxing process conditions are a temperature of from 265* to 430*C, a pressure of from 40 to 200 bars gauge, a space velocity of from 0.5 to 10 v/v/hr and a hydrogen gas rate of from 900 to 2,700 m3/m3.
7. A process as claimed in claim 1 wherein the hydrocatalytic viscosity index improvement process conditions are a temperature of from 340* to 430*C, a pressure of from 70 to 170 bars gauge, a space velocity of from 0.5 to 2 v/v/hr and a hydrogen gas rate of 360 to 1,800 m3/m3 to give a dewaxed product viscosity index of from 75 to 100.
8. A process as claimed in claim 1 wherein the hydrocatalytic viscosity index improvement process conditions are a temperature of from 380* to 460*C a pressure of from 120 to 210 bars gauge, a space velocity of from 0.2 to 2 v/v/hr and a hydrogen gas rate of from 360 to 1,800 m3/m3 to give a dewaxed product viscosity index of greater than 100.
9. A process as claimed in claim 1 wherein the solvent dewaxing uses an alkyl ketone at a solvent:oil ratio of 0.5 to 10:1 and a temperature of from -5* to -30*C.
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US4100056A (en) * 1976-12-27 1978-07-11 Sun Oil Company Of Pennsylvania Manufacture of naphthenic type lubricating oils
US4181595A (en) * 1977-01-24 1980-01-01 The British Petroleum Company Limited Production of lubricants
US4229282A (en) * 1979-04-27 1980-10-21 Mobil Oil Corporation Catalytic dewaxing of hydrocarbon oils
US4259170A (en) * 1979-09-14 1981-03-31 Mobil Oil Corporation Process for manufacturing lube base stocks
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USRE30529E (en) * 1979-09-24 1981-02-24 Sun Oil Company Of Pennsylvania Manufacture of naphthenic type lubricating oils
US4622130A (en) * 1985-12-09 1986-11-11 Shell Oil Company Economic combinative solvent and catalytic dewaxing process employing methylisopropyl ketone as the solvent and a silicate-based catalyst
US4678556A (en) * 1985-12-20 1987-07-07 Mobil Oil Corporation Method of producing lube stocks from waxy crudes
US7513989B1 (en) * 1997-07-15 2009-04-07 Exxonmobil Research And Engineering Company Hydrocracking process using bulk group VIII/Group VIB catalysts
GB2374348B (en) * 2000-12-05 2003-07-23 Chevron Usa Inc Process for preparing lubes with high viscosity index valves
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AU780765B2 (en) * 2000-12-05 2005-04-14 Chevron U.S.A. Inc. Process for preparing lubes with high viscosity index values
GB2374348A (en) * 2000-12-05 2002-10-16 Chevron Usa Inc Production of lube base stocks by catalytic and solvent dewaxing
US20040055931A1 (en) * 2000-12-19 2004-03-25 Van Beijnum Johannes Process to prepare a spindle oil, light machine oil and a medium machine oil base oil grade from the bottoms fraction of a fuels hydrocracking process
US7347928B2 (en) * 2000-12-19 2008-03-25 Shell Oil Company Process to prepare a spindle oil, light machine oil and a medium machine oil base oil grade from the bottoms fraction of a fuels hydrocracking process
US6699385B2 (en) * 2001-10-17 2004-03-02 Chevron U.S.A. Inc. Process for converting waxy feeds into low haze heavy base oil
CN108473891A (en) * 2015-12-28 2018-08-31 埃克森美孚研究工程公司 Bright stock is produced by low severity residual oil depitching
US10808185B2 (en) 2015-12-28 2020-10-20 Exxonmobil Research And Engineering Company Bright stock production from low severity resid deasphalting
US10947464B2 (en) 2015-12-28 2021-03-16 Exxonmobil Research And Engineering Company Integrated resid deasphalting and gasification
US11060040B2 (en) 2016-12-29 2021-07-13 Exxonmobil Research And Engineering Company Base stocks and lubricant compositions containing same

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SE385127B (en) 1976-06-08
BE810780A (en) 1974-08-08
FR2217409B1 (en) 1979-10-19
NL7401338A (en) 1974-08-13
ATA99174A (en) 1976-12-15
JPS49112904A (en) 1974-10-28
AU6502274A (en) 1975-07-31
CA1012915A (en) 1977-06-28
DE2405116A1 (en) 1974-08-15
AT338397B (en) 1977-08-25
GB1402821A (en) 1975-08-13
FR2217409A1 (en) 1974-09-06

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