EP0271265A1 - Verfahren für die Senkung der Steck- und Trübungspunkte von Schmierölen aus Hydrocrackern - Google Patents

Verfahren für die Senkung der Steck- und Trübungspunkte von Schmierölen aus Hydrocrackern Download PDF

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Publication number
EP0271265A1
EP0271265A1 EP87310494A EP87310494A EP0271265A1 EP 0271265 A1 EP0271265 A1 EP 0271265A1 EP 87310494 A EP87310494 A EP 87310494A EP 87310494 A EP87310494 A EP 87310494A EP 0271265 A1 EP0271265 A1 EP 0271265A1
Authority
EP
European Patent Office
Prior art keywords
pour point
zsm
lube
point
dewaxing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87310494A
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English (en)
French (fr)
Inventor
William Everett Garwood
David Lee Vannauker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
ExxonMobil Oil Corp
Original Assignee
Mobil Oil AS
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil AS, Mobil Oil Corp filed Critical Mobil Oil AS
Publication of EP0271265A1 publication Critical patent/EP0271265A1/de
Withdrawn legal-status Critical Current

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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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen

Definitions

  • the lube oil have a low pour point so that it can be used at low temperature. Excessive thickening at low temperatures is unacceptable.
  • the present invention is concerned with an improved process for dewaxing heavy hydrocracked lubes, which is more economical than conventional solvent dewaxing procedures or catalytic dewaxing procedures and which produces hydrocracked lube oils having low pour and cloud points.
  • the present process employs the use of a conventional solvent dewaxing step, but only to slightly reduce the pour point of the treated stock and obtain a product having an intermediate pour point.
  • the product of intermediate pour point is unsuitable for use as a low temperature lubricant at this stage.
  • this intermediate product is then hydrodewaxed with ZSM-23 zeolite to yield a product having both low pour point and low cloud point.
  • U. S. Patent No. 3,255,138 claims a process for preparing low pour point lube oils by first solvent dewaxing and then hydrodewaxing over a ZSM-5-type zeolite containing a hydrogenation component.
  • U. S. Patent Nos. 4,283,271 and 4,283,272 claim energy efficient all-catalytic lube processes using dewaxing catalysts, such as ZSM-5 and ZSM-11, in the dewaxing step.
  • the present invention provides A process for preparing low pour point and low cloud point lube oils from a hydrocracked petroleum feedstock characterized by solvent dewaxing to obtain a lube oil having a pour point of -12 to 10°C (10 to 50°F) and thereafter subjecting the solvent dewaxed product to catalytic hydrodewaxing in the presence of added hyddrogen with a catalyst comprising ZSM-23 and a hydrogenation component to obtain a product having a pour point of less than -7°C (20°F).
  • the feeds comprises a hydrocracked heavy hydrocracked lube oils boiling above 343°C (650°F) and particularly between 343 and 704°C (650°C and 1300°F).
  • the feed is then mildly solvent dewaxed, lube stock until it has a pour point of -12 to 10°C (10° to 50°F), and preferably from -7 to 7°C (20° to 45°F).
  • the solvent dewaxing step is conventional. Suitable solvents include methyl ethyl ketone-toluene, methyl ethyl ketone-methyl isobutyl ketone and the like.
  • the products from the solvent dewaxing step are high quality waxes which are recovered and an intermediate pour point stock which is then hydrodewaxed over ZSM-23 zeolite.
  • Zeolite ZSM-23 is described in U. S. Patent Nos. 4,076,842 and 4,104,151.
  • the hydrogenation component may be associated with the ZSM-23, e.g., a metal (s) from Group VIII of the Periodic Table of Elements, alone or in combination, with a Group VI metal.
  • a metal s
  • Non-limiting examples of the metals from Group VIII for this purpose include platinum, palladium, iridium, ruthenium, cobalt and nickel.
  • the Group VI metals are chromium, molybdenum and tungsten.
  • the ZSM-23 may be incorporated with a matrix or binder of a material resistant to the temperature and other process conditions.
  • Useful matrix materials include both synthetic and naturally occurring substances, as well as inorganic materials, such as clay, silica and/or metal oxides.
  • the latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is haloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used as mined or after calcination, acid treatment or chemical modification.
  • Matrix materials such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-­ magnesia and silica-magnesia-zirconia may also be used.
  • the matrix can be in the form of a cogel.
  • the proportions of ZSM-23 and matrix, on an anhydrous basis, may vary widely, with the zeolite content ranging from 1 to 99 wt %, and more usually 5 to 80 wt % of the dry composite.
  • the hydrogenation component if any may be on the zeolite or on the matrix or both.
  • the chargestock in all the examples is a hydrocracked brightstock having the following properties: Gravity, °API 30.2 g/cc 0.8751 Pour Point, °F/°C +120/49 KV at 100°C, cs 25.63
  • the chargestock is processed over 1% Ni/ZSM-5 extrudate (sulfided in situ ), at 2900 kPa (400 psig), 1 LHSV, 450 nm3/m3 (2500 SCFB H2 at several temperatures, with the following results:
  • the cloud point of 17°C (+62°F) is unacceptably high.
  • a cloud point 5-6°C (about 10°F) above the pour point is considered acceptable.
  • hydrocracked brightstock is subjected to conven tional solvent dewaxing employing conventional solvent ratios, which are as follows on a volume-to-volume basis:
  • the hydrocracked brightstock is solvent dewaxed as in Example 2, except at a temperature of -7°C (+20°F), with results as follows:
  • the cloud point at the target pour of 12°C (+10°F) is acceptable, and the overall lube yield from the two steps is 73 wt %, compared to 65 wt % for solvent dewaxing alone (Example 2), and 59 wt % for hydrodewaxing alone (Example 1).
  • Example 3 The same 7°C (+45°F) pour point solvent dewaxed stock de scribed in Example 3 is processed over 1 wt % Pd/ZSM-23 extrudate (H2 treated in situ at 482°C (900°F) for 1 hour) at 2900 kPa (400 psig), 0.5 LHSV, 450 nm3/m3 (2500 SCFB H2) at several temperatures, with the following results:
  • Fig. 1 shows lube yield versus pour point for the brightstock solvent dewaxed to 7°C (+45°F) pour point.
  • Fig. 2 shows viscosity index versus pour point for the same stock.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP87310494A 1986-12-04 1987-11-27 Verfahren für die Senkung der Steck- und Trübungspunkte von Schmierölen aus Hydrocrackern Withdrawn EP0271265A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93780786A 1986-12-04 1986-12-04
US937807 1986-12-04

Publications (1)

Publication Number Publication Date
EP0271265A1 true EP0271265A1 (de) 1988-06-15

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ID=25470438

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87310494A Withdrawn EP0271265A1 (de) 1986-12-04 1987-11-27 Verfahren für die Senkung der Steck- und Trübungspunkte von Schmierölen aus Hydrocrackern

Country Status (5)

Country Link
EP (1) EP0271265A1 (de)
JP (1) JPS63154794A (de)
AU (1) AU8205187A (de)
BR (1) BR8706594A (de)
ZA (1) ZA879145B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005436A1 (en) * 1993-08-12 1995-02-23 Aktsionernoe Obschestvo Otkrytogo Tipa 'yaroslavnefteorgsintez' Process for obtaining distillation oils
RU2220186C2 (ru) * 2001-06-15 2003-12-27 Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" Способ гидрооблагораживания и каталитической депарафинизации компонентов минеральных масел и система катализаторов для его осуществления

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6962651B2 (en) * 2003-03-10 2005-11-08 Chevron U.S.A. Inc. Method for producing a plurality of lubricant base oils from paraffinic feedstock
WO2006055306A1 (en) * 2004-11-15 2006-05-26 Exxonmobil Research And Engineering Company A lubricant upgrading process to improve low temperature properties using solvent dewaxing follewd by hydrodewaxing over a catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755138A (en) * 1969-10-10 1973-08-28 Mobil Oil Corp Lube oils by solvent dewaxing and hydrodewaxing with a zsm-5 catalyst
US4104151A (en) * 1976-11-08 1978-08-01 Mobil Oil Corporation Organic compound conversion over ZSM-23
EP0016554A1 (de) * 1979-03-26 1980-10-01 Mobil Oil Corporation Herstellung eines Schmierölvorrates mit hohem Viskositätsindex
EP0092376A2 (de) * 1982-04-19 1983-10-26 Mobil Oil Corporation Katalytisches Verfahren zur Herstellung von Schmierölen mit niedrigem Stockpunkt
EP0140468A1 (de) * 1983-08-31 1985-05-08 Mobil Oil Corporation Kombinationsprozess zur Herstellung Schmieröle aus Grenzbereich-Rohölen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755138A (en) * 1969-10-10 1973-08-28 Mobil Oil Corp Lube oils by solvent dewaxing and hydrodewaxing with a zsm-5 catalyst
US4104151A (en) * 1976-11-08 1978-08-01 Mobil Oil Corporation Organic compound conversion over ZSM-23
EP0016554A1 (de) * 1979-03-26 1980-10-01 Mobil Oil Corporation Herstellung eines Schmierölvorrates mit hohem Viskositätsindex
EP0092376A2 (de) * 1982-04-19 1983-10-26 Mobil Oil Corporation Katalytisches Verfahren zur Herstellung von Schmierölen mit niedrigem Stockpunkt
EP0140468A1 (de) * 1983-08-31 1985-05-08 Mobil Oil Corporation Kombinationsprozess zur Herstellung Schmieröle aus Grenzbereich-Rohölen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005436A1 (en) * 1993-08-12 1995-02-23 Aktsionernoe Obschestvo Otkrytogo Tipa 'yaroslavnefteorgsintez' Process for obtaining distillation oils
RU2220186C2 (ru) * 2001-06-15 2003-12-27 Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" Способ гидрооблагораживания и каталитической депарафинизации компонентов минеральных масел и система катализаторов для его осуществления

Also Published As

Publication number Publication date
JPS63154794A (ja) 1988-06-28
BR8706594A (pt) 1988-07-19
AU8205187A (en) 1988-06-09
ZA879145B (en) 1989-07-26

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Inventor name: GARWOOD, WILLIAM EVERETT