WO1999041333A1 - Process for making a lube basestock - Google Patents

Process for making a lube basestock Download PDF

Info

Publication number
WO1999041333A1
WO1999041333A1 PCT/US1999/002986 US9902986W WO9941333A1 WO 1999041333 A1 WO1999041333 A1 WO 1999041333A1 US 9902986 W US9902986 W US 9902986W WO 9941333 A1 WO9941333 A1 WO 9941333A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
dimethylcyclopentane
trans
catalyst
metd
Prior art date
Application number
PCT/US1999/002986
Other languages
French (fr)
Inventor
William John Murphy
Gary Brice Mcvicker
Sylvain Hantzer
Ian Alfred Cody
Stuart Leon Soled
Sandra Jean Linek
Joseph Ernest Baumgartner
Original Assignee
Exxon Research And Engineering Company
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 Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to EP99908125A priority Critical patent/EP1054941A4/en
Priority to JP2000531517A priority patent/JP2002503753A/en
Priority to CA002319385A priority patent/CA2319385A1/en
Priority to AU27631/99A priority patent/AU742605B2/en
Publication of WO1999041333A1 publication Critical patent/WO1999041333A1/en

Links

Classifications

    • 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining 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
    • C10G45/60Refining 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
    • C10G45/64Refining 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
    • 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

Definitions

  • This invention relates to the hydroisomerization of waxy feeds including slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer- Tropsch hydroisomerate waxy raffinates, and waxy distillates to produce a lube oil basestock or blending stock. More specifically, this invention relates to the conversion of a waxy feed using a mixed catalyst having a preselected acidity capable of promoting the formation of a basestock having a predetermined (VI) within a range of VTs.
  • Waxy feeds can be converted to liquid products using well known catalytic dewaxing catalysts; however, in these instances the selective cracking of paraffins typically results in a loss of viscosity (VI) which is undesirable.
  • VI viscosity
  • This invention relates to a method for hydroisomerizing a waxy feed to produce improved yield of a lube basestock which comprises: contacting the waxy feed under hydroisomerization conditions with a catalyst comprising a unitized mixed powdered pellet catalyst having (1) a first dewaxing component selected from 8, 10 and 12 ring molecular sieves and mixtures thereof; (2) a second isomerization component which is an amorphous inorganic oxide; and (3) at least one of a Group VLB and a Group VHI metal hydrogenation component, wherein the first and second components are present in a ratio such that when evaluated in the conversion of methyl cyclohexane at 320°C to 1,1-dimethylcyclopentane, 1,2-dimethylcyclopentane, 1,3-dimethylcyclopentane and ethylcyclopentane, the catalyst will provide a trans-l,2-/trans-l,3-dimethyl- cyclopentane ratio of less than 1 and a
  • Figure 1 is a schematic drawing showing the conversion of methylcyclohexane to various cyclopentane compounds at 320°C. - 3 -
  • the feed suitable in the practice of the present invention includes waxy hydrocarbon oils such as slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer-Tropsch isomerate waxy raffinates and waxy distillates. Typically, such feeds will have wax contents of 15% or more.
  • the preferred feed will have a nitrogen and sulfur content each below about 20 wppm or more.
  • the preferred feed will have a nitrogen and sulfur content each below about 20 wppm. Indeed, if the feed contains higher amounts of sulfur and nitrogen, the feed can be first subjected to hydrotreating under typical hydrotreating conditions to reduce the sulfur and nitrogen contents.
  • any of the conventional hydrotreating catalysts can be employed like Ni/Mo on alumina, Ni/W on alumina Co/Mo on alumina.
  • any of the Group VTB to Group VDI (The groups referred to here and hereinafter are those metals of the Periodic Table of Elements; Sargent- Welch Scientific Co.) on metal oxide refractory supports may be employed. Commercial examples of such are identified as HDN-30 and KF-840.
  • Hydrotreating is conducted so as to lower the sulfur and nitrogen contents to levels of 20 wppm or less nitrogen or 20 wppm or less sulfur especially 10 ppm less nitrogen and 10 ppm or less sulfur and most preferably to levels below 5 ppm for nitrogen and 5 ppm or less for sulfur.
  • Waxy feeds secured from natural petroleum sources contain quantities of sulfur and nitrogen compounds which are known to deactivate wax hydroisomerization catalysts. To prevent this deactivation it is preferred that the feed contain no more than 10 ppm sulfur, preferably less than 2 ppm sulfur and no more than 2 ppm nitrogen, preferably less than 1 ppm mtrogen. - 4 -
  • the feed is preferably hydrotreated to reduce the sulfur and nitrogen content.
  • Hydrotreating can be conducted using any typical hydrotreating catalyst such as Ni/Mo on alumina, Co/Mo on alumina, Co/Ni/Mo on alumina, e.g., KF-840, KF-843, HDN-30, HDN-60, Criteria C-411, etc.
  • bulk catalysts comprising Ni/Mn/Mo or Cr/Ni/Mo sulfides as described in U.S. Patent 5,122,258 can be used.
  • Hydrotreating is performed at temperatures in the range 280°C to 400°C, preferably 340°C to 380°C at pressures in the range 500 to 3000 psi, hydrogen treat gas rate in the range of 500 to 5000 SCF/bbl and a flow velocity in the range 0.1 to 5 LHSV, preferably 1 to 2 LHSV.
  • the hydrotreated waxy oil is stripped to remove ammonia and H2S and then is subjected to the hydroisomerization process of the present invention.
  • the catalyst employed in the hydroisomerization of waxy feeds in accordance with the present invention is a unitized mixed powdered pellet catalyst.
  • unitized as used here and in the claims means that each pellet is one made by mixing together a powdered first component with a powdered second component and pelletizing the mixture to produce pellets each of which contain all of the powder components previously recited.
  • the unitized catalyst can be prepared by starting with individual finished powdered components pulverizing and powdering such individual finished components, mixing the powdered materials together to form a - 5 -
  • Pulverizing and powdering is to a consistency achievable using a ball mill or other such conventional powdering means to a particle size less than 100 microns.
  • the first component is a catalytic dewaxing component including crystalline 8, 10 and 12 ring molecular sieves.
  • Crystalline molecular sieves include metallo-, e.g., alumino silicates, alumino phosphates and sihco uminophosphates.
  • crystalline alumino silicates include zeolites such as erionite, chabazite, ZSM-5, ZSM-11, ZSM-12, Theta-1 (ZSM- 22), ZSM-23, ZSM-35, ZSM-48 natural and synthetic ferrierites, ZSM-57, beta mordenite and offretite.
  • Examples of crystalline alumino- and silicoalumino- phosphates include SAPO-11, SAPO-41, SAPO-31, MAPO-11 and MAPO-31. Preferred include ZSM-5, ZSM-22, ZSM-23, ferrierites, and SAPO-11.
  • the second isomerization component can be any of the typical isomerization catalyst such as those comprising amorphous refractory metal oxide support base (e.g., umina, silica, zirconia, titania, silica-magnesia, silica- alumina, etc.) on which has been preferably deposited a catalytically active metal selected from Group VI B, Group VII B, Group VU3 metals and mixtures thereof, preferably Group VUI, more preferably noble Group VIE, most preferably Pt or Pd and optionally including a promoter or dopant such as yttria, rare earth oxides, from, e.g., La, Ce, etc., boria, magnesia, etc.
  • amorphous refractory metal oxide support base e.g., umina, silica, zirconia, titania, silica-magnesia, silica- alumina, etc.
  • the catalytically active metals are present in the range 0.1 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.1 to 2 wt%, most preferably 0.1 to 1 wt%.
  • the promoters and dopants are used to control the acidity of the isomerization catalyst.
  • acidity of the resultant catalyst is reduced by addition of a basic material such as - 6 -
  • yttria rare earth oxides, from e.g., La, Ce, etc., boria or magnesia or by controlling the ratio of silica.alumina in the sihca- umina.
  • the metal hydrogenation component can be deposited on either the first dewaxing component, the second isomerization component or preferably on both the first and second components.
  • the metal is selected from at least one of Group VIB and Group VHI, preferably Group VIII, more preferably Pt or Pd.
  • the amount of metal can range from 0.1 to 30 wt%, based on catalyst. If the metal is Pt or Pd, the preferred amount is from 0.1 to 5 wt%, based on catalyst. In order to maximize catalyst utilization, it is preferred that the metal dispersion be at least 0.3 (on a scale where 100% metal dispersion is 1.0) if the metal is only on one component. If the metal is on both components, then it is preferred that the metal dispersion (D) times the metal concentration (C) (i.e., D x C) on one of the components be at least 0.08.
  • the first and second components are combined in a ratio sufficient to promote wax isomerization and naphthene destruction without substantial decrease in VI.
  • the zeolite to amorphous inorganic oxide ratios for catalysts according to the invention range from about 1: 1 to 1:20 by weight, subject to the MCH test described below.
  • One technique for deteirnining the proper ratio of first and second components in the catalyst is based on an evaluation of the combined components containing about 0.5 wt% Pt in converting methylcyclohexane (MCH) to various cyclopentane compounds.
  • Catalyst that at 320°C provide a ratio of trans 1,2-dimethylcyclopentane to trans-l,3-dimethylcyclopentane (trans- 1,2/trans- 1,3 DMCP) in the range of less than 1 have been found to - 7 -
  • the second factor is when the catalyst, impregnated with about 0.5 wt% Pt and evaluated in converting methylcyclohexane to various cyclopentane compounds at 10% conversion, exhibits a selectivity for ethylcyclopentane (ECP) formation above at least 50%.
  • ECP ethylcyclopentane
  • the ratio of trans- 1,2-DCMP to trans-l,3-DCMP is adjusted to less than - 8 -
  • amorphous isomerization component about 1 predominantly by controlling both the number and strength of the amorphous isomerization component. It is preferred to use lower acid strength amorphous components such as alumina.
  • a catalyst that will maximize VI is produced by increasing the acid strength of the amorphous phase.
  • it is preferred to use higher acid strength amorphous components such as silica-aluminas or modified sihca-aluminas.
  • Another way of making such a catalyst is by changing the ratio of the microporous component to the amorphous component such that the unitized catalyst has a trans-l,2/trans-l,3 DMCP ratio of >1.
  • the hydroisomerization process utilizing the catalyst of the present invention is conducted at temperatures between about 200°C to 400°C, preferably 250°C to 380°C, and most preferably 300°C to 350°C at hydrogen partial pressures between about 350 to 5,000 psig (2.41 to 34.6 mPa), preferably 1,000 to 2500 psig (7.0 to 17.2 mPa), a hydrogen gas treat ratio of 500 to 10,000 SCF H 2 /bbl (89 to 1780 ⁇ /m 3 ), preferably 2,000 to 5,000 SCF H 2 /bbl (356 to 890 m 3 /m 3 ) and a LHSV of 0.1 to 10 v/v/hr, preferably 0.5 to 5 v/v/hr, and more preferably 1 to 2 v/v/hr.
  • the waxy feed is first subject to solvent dewaxing to a pour point of the order of +10°C or lower.
  • the dewaxing solvent used may include the C3-C6 ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK and MIBK, aromatic hydrocarbons like toluene, mixtures of ketones and aromatics like MEK/toluene, ethers such as methyl t-butyl ethers and mixtures of - 9 -
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • the solvent employed will be an equal volume mixture of methyl ethyl ketone and methyl isobutyl ketone.
  • the isomerate to solvent ratio will range between 1 to 10 and preferably will be about 1:3.
  • This example illustrates the yield- VI trade-off on a hydrocracker distillate (Feed A) for catalysts with different degrees of acidity in the amorphous component.
  • the physical properties of the hydrocracker distillate (Feed A) are shown in Table 1.
  • the catalyst in Table 2 (column B) was made by combining the zeolite theta-1 (TON) in the powder form with alumina (BET Surface Area 190 m ⁇ lm?) in the powder form followed by intimate mixing so as to form a - 10 -
  • the catalyst in Table 2 (column C) was made by combining the zeolite TON with silica-alumina (Si-Al) using the same technique as used in column A to produce a homogeneous powdered catalyst before forming into pellets.
  • the palladium was loaded (as palladium teu-aamine dinitrate) on to the finished unitized catalyst by incipient wetness.
  • Table 2 shows a comparison of activity and selectivity of these two catalysts for hydrodewaxing versus solvent dewaxing (column A).
  • the acidity differences of each catalyst component and the corresponding finished unitized catalysts is also shown using the reaction of methylcyclohexane at 320°C.
  • the table clearly shows the higher acidity (greater number and acid strength) silica- umina catalyst (column C) gives lower yield but much higher VI compared with the very low acidity associated with alumina (column B) which results in high yield but a debit in VI.
  • This example further illustrates the yield- VI trade off and shows a comparison of activity and selectivity of two catalysts for hydrodewaxing a hydrocraker distillate (Feed B) versus solvent dewaxing.
  • the physical properties of the hydrocracker distillate (Feed B) are shown in Table 3.
  • Wax Content wt% 22.4
  • This example further illustrates the yield- VI trade and shows a comparison of activity and selectivity of two catalysts for hydroisomerization a hydrocraker distillate (Feed B) versus solvent dewaxing.
  • This example illustrates that by changing the relative amounts of microporous component to amorphous component the overall acidity of the unitized catalyst an be tailored to maximize yield or VI.
  • Table 5 compares two unitized catalysts both of which have been made by combining the powdered ZSM-5 (Si Al ratio 110) with the powdered amorphous component in different ratios and then loading platinum by incipient wetness using platinum tetraamine dichloride.
  • Table 5 shows a comparison of activity and selectivity for these catalysts for dewaxing hydrocracker distillate B, the physical properties of which are shown in Table 3, with solvent dewaxing.
  • the catalyst in column B which has a trans-l,2/trans-l,3 DMCP ratio of less than 1 shows higher yield but lower VI than the catalyst in column C which has a trans-l,2/trans-l,3 DMCP ratio greater than 1.
  • the metal in a mixed powdered catalyst can be dispersed on the microporous component or on the amorphous component.
  • the catalysts in Table 6 were made by combining the zeolite theta- 1 (TON) in the powder form with alumina (BET Surface Area 190m 2 /m 3 ) in the powder form followed by intimate mixing so as to form a homogeneous powdered mixture and then forming into catalyst pellets by pressing in a die and sizing to the required mesh size.
  • TON zeolite theta- 1
  • BET Surface Area 190m 2 /m 3 alumina
  • the TON in the catalyst in column A had been loaded with platinum tetramine dinitrate before being mtermixed with alumina.
  • the catalyst in column D was made as described in Example 1.
  • Table 6 columns A and B, compares the activity of two TON zeoHte/ umina mixed powder catalysts in which the noble metal has been - 17 -
  • Loading additiond Pt or Pd on the dumina component improves the activity of the catdyst to the level of that observed in Column A.
  • Feed Hydrocracker Distillate, Feed B t >

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

A method for hydroisomerizing a waxy feed to favor one of VI or yield is described. The method uses a unitized pellet powder catalyst comprising a metal hydrogeneration component, a first catalytic component selected from 8, 10 and 12 ring molecular sieves and mixtures thereof, and a second amorphous isomerization component which is an amorphous inorganic oxide. Importantly, the ratio of feed and second components are present in a predetermined ratio to provide a preselected acidity favoring one of VI or yield resulting from the hydroisomerization.

Description

- 1 -
PROCESS FOR MAKING A LUBE BASESTOCK
FIELD OF THE INVENTION
This invention relates to the hydroisomerization of waxy feeds including slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer- Tropsch hydroisomerate waxy raffinates, and waxy distillates to produce a lube oil basestock or blending stock. More specifically, this invention relates to the conversion of a waxy feed using a mixed catalyst having a preselected acidity capable of promoting the formation of a basestock having a predetermined (VI) within a range of VTs.
BACKGROUND OF THE INVENTION
The performance criteria for lubricants such as those used in automatic transmission fluids and passenger car engine oils has become increasingly more severe with users requiring basestock that provide better wear protection, improved volatility and low temperature properties.
Waxy feeds can be converted to liquid products using well known catalytic dewaxing catalysts; however, in these instances the selective cracking of paraffins typically results in a loss of viscosity (VI) which is undesirable.
In contrast, isomerization of waxy feeds using molecular sieve based catalyst that have linear ID pore structures produces lube basestocks without loss in VI. While these catalysts offer benefits over those used in catalytic dewaxing, there nonetheless remains a need for improved catalysts for - 2 -
converting waxy feeds to lube basestocks that can be tailored to produce basestocks having a predetermined quality and yield.
SUMMARY OF THE INVENTION
This invention relates to a method for hydroisomerizing a waxy feed to produce improved yield of a lube basestock which comprises: contacting the waxy feed under hydroisomerization conditions with a catalyst comprising a unitized mixed powdered pellet catalyst having (1) a first dewaxing component selected from 8, 10 and 12 ring molecular sieves and mixtures thereof; (2) a second isomerization component which is an amorphous inorganic oxide; and (3) at least one of a Group VLB and a Group VHI metal hydrogenation component, wherein the first and second components are present in a ratio such that when evaluated in the conversion of methyl cyclohexane at 320°C to 1,1-dimethylcyclopentane, 1,2-dimethylcyclopentane, 1,3-dimethylcyclopentane and ethylcyclopentane, the catalyst will provide a trans-l,2-/trans-l,3-dimethyl- cyclopentane ratio of less than 1 and a selectivity to ethylcyclopentane, at 10% conversion, of at least about 50%. The invention also relates to a method for hydroisomerizing a waxy feed to produce improved viscosity index (VI) of a lube basestock by the foregoing method wherein the ratio is at least 1.
This and other embodiments of the invention will be discussed below.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a schematic drawing showing the conversion of methylcyclohexane to various cyclopentane compounds at 320°C. - 3 -
DESCRIPTION OF THE INVENTION
The feed suitable in the practice of the present invention includes waxy hydrocarbon oils such as slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer-Tropsch isomerate waxy raffinates and waxy distillates. Typically, such feeds will have wax contents of 15% or more. The preferred feed will have a nitrogen and sulfur content each below about 20 wppm or more. The preferred feed will have a nitrogen and sulfur content each below about 20 wppm. Indeed, if the feed contains higher amounts of sulfur and nitrogen, the feed can be first subjected to hydrotreating under typical hydrotreating conditions to reduce the sulfur and nitrogen contents. Any of the conventional hydrotreating catalysts can be employed like Ni/Mo on alumina, Ni/W on alumina Co/Mo on alumina. In other words any of the Group VTB to Group VDI (The groups referred to here and hereinafter are those metals of the Periodic Table of Elements; Sargent- Welch Scientific Co.) on metal oxide refractory supports may be employed. Commercial examples of such are identified as HDN-30 and KF-840.
Hydrotreating is conducted so as to lower the sulfur and nitrogen contents to levels of 20 wppm or less nitrogen or 20 wppm or less sulfur especially 10 ppm less nitrogen and 10 ppm or less sulfur and most preferably to levels below 5 ppm for nitrogen and 5 ppm or less for sulfur.
Waxy feeds secured from natural petroleum sources contain quantities of sulfur and nitrogen compounds which are known to deactivate wax hydroisomerization catalysts. To prevent this deactivation it is preferred that the feed contain no more than 10 ppm sulfur, preferably less than 2 ppm sulfur and no more than 2 ppm nitrogen, preferably less than 1 ppm mtrogen. - 4 -
To achieve these limits the feed is preferably hydrotreated to reduce the sulfur and nitrogen content.
Hydrotreating can be conducted using any typical hydrotreating catalyst such as Ni/Mo on alumina, Co/Mo on alumina, Co/Ni/Mo on alumina, e.g., KF-840, KF-843, HDN-30, HDN-60, Criteria C-411, etc. Similarly, bulk catalysts comprising Ni/Mn/Mo or Cr/Ni/Mo sulfides as described in U.S. Patent 5,122,258 can be used.
Hydrotreating is performed at temperatures in the range 280°C to 400°C, preferably 340°C to 380°C at pressures in the range 500 to 3000 psi, hydrogen treat gas rate in the range of 500 to 5000 SCF/bbl and a flow velocity in the range 0.1 to 5 LHSV, preferably 1 to 2 LHSV.
The hydrotreated waxy oil is stripped to remove ammonia and H2S and then is subjected to the hydroisomerization process of the present invention.
The catalyst employed in the hydroisomerization of waxy feeds in accordance with the present invention is a unitized mixed powdered pellet catalyst. The term "unitized" as used here and in the claims means that each pellet is one made by mixing together a powdered first component with a powdered second component and pelletizing the mixture to produce pellets each of which contain all of the powder components previously recited.
The unitized catalyst can be prepared by starting with individual finished powdered components pulverizing and powdering such individual finished components, mixing the powdered materials together to form a - 5 -
homogeneous mass, then compressing/extruding and pelleting thus producing the unitized pellet catalysts. Pulverizing and powdering is to a consistency achievable using a ball mill or other such conventional powdering means to a particle size less than 100 microns.
The first component is a catalytic dewaxing component including crystalline 8, 10 and 12 ring molecular sieves. Crystalline molecular sieves include metallo-, e.g., alumino silicates, alumino phosphates and sihco uminophosphates. Examples of crystalline alumino silicates include zeolites such as erionite, chabazite, ZSM-5, ZSM-11, ZSM-12, Theta-1 (ZSM- 22), ZSM-23, ZSM-35, ZSM-48 natural and synthetic ferrierites, ZSM-57, beta mordenite and offretite. Examples of crystalline alumino- and silicoalumino- phosphates include SAPO-11, SAPO-41, SAPO-31, MAPO-11 and MAPO-31. Preferred include ZSM-5, ZSM-22, ZSM-23, ferrierites, and SAPO-11.
The second isomerization component can be any of the typical isomerization catalyst such as those comprising amorphous refractory metal oxide support base (e.g., umina, silica, zirconia, titania, silica-magnesia, silica- alumina, etc.) on which has been preferably deposited a catalytically active metal selected from Group VI B, Group VII B, Group VU3 metals and mixtures thereof, preferably Group VUI, more preferably noble Group VIE, most preferably Pt or Pd and optionally including a promoter or dopant such as yttria, rare earth oxides, from, e.g., La, Ce, etc., boria, magnesia, etc. The catalytically active metals are present in the range 0.1 to 5 wt%, preferably 0.1 to 3 wt%, more preferably 0.1 to 2 wt%, most preferably 0.1 to 1 wt%. The promoters and dopants are used to control the acidity of the isomerization catalyst. Thus, when the isomerization catalyst employs an acidic material such as silica-alumina, acidity of the resultant catalyst is reduced by addition of a basic material such as - 6 -
yttria, rare earth oxides, from e.g., La, Ce, etc., boria or magnesia or by controlling the ratio of silica.alumina in the sihca- umina.
The metal hydrogenation component can be deposited on either the first dewaxing component, the second isomerization component or preferably on both the first and second components. The metal is selected from at least one of Group VIB and Group VHI, preferably Group VIII, more preferably Pt or Pd. The amount of metal can range from 0.1 to 30 wt%, based on catalyst. If the metal is Pt or Pd, the preferred amount is from 0.1 to 5 wt%, based on catalyst. In order to maximize catalyst utilization, it is preferred that the metal dispersion be at least 0.3 (on a scale where 100% metal dispersion is 1.0) if the metal is only on one component. If the metal is on both components, then it is preferred that the metal dispersion (D) times the metal concentration (C) (i.e., D x C) on one of the components be at least 0.08.
The first and second components are combined in a ratio sufficient to promote wax isomerization and naphthene destruction without substantial decrease in VI. The zeolite to amorphous inorganic oxide ratios for catalysts according to the invention range from about 1: 1 to 1:20 by weight, subject to the MCH test described below.
One technique for deteirnining the proper ratio of first and second components in the catalyst is based on an evaluation of the combined components containing about 0.5 wt% Pt in converting methylcyclohexane (MCH) to various cyclopentane compounds. Catalyst that at 320°C provide a ratio of trans 1,2-dimethylcyclopentane to trans-l,3-dimethylcyclopentane (trans- 1,2/trans- 1,3 DMCP) in the range of less than 1 have been found to - 7 -
promote maximum yields of basestocks whereas ratios in the range of greater than about 1 promote maximum VI.
The second factor is when the catalyst, impregnated with about 0.5 wt% Pt and evaluated in converting methylcyclohexane to various cyclopentane compounds at 10% conversion, exhibits a selectivity for ethylcyclopentane (ECP) formation above at least 50%.
This technique is further explained as follows. The reaction of MCH over the catalyst to various cyclopentane products is shown in Figure 1. As indicated in Figure 1, the products of MCH decomposition include ethylcyclopentane, cis- and trans- 1,2-dimethylcyclopentane, cis- and trans- 1,3- dimethylcyclopentane and 1,1-dimethylcyclopentane. This technique, also known as the MCH test is used to define relative acid site concentration, strengths and active site constraint for the catalysts according to the invention.
The key factors are summarized as follows: (1) total conversion of MCH for a given catalyst weight at 320°C is an indication of the relative number of acid sites; (2) selectivity to ECP, at 10% conversion, is a measure of the relative acid strength wherein high ECP selectivity values indicates low acid strength and low ECP selectivity values indicates high acid strength; and (3) the ratio of trans- 1,2-DCMP to trans- 1,3-DCMP correlates with the constraint at the catalyst active site wherein a high ratio (>1) indicates little or no physical constraint at the active site and a low ratio (<1) indicates a physical constraint at the active site.
In the present process, to produce a catalyst that will give high yield, the ratio of trans- 1,2-DCMP to trans-l,3-DCMP is adjusted to less than - 8 -
about 1 predominantly by controlling both the number and strength of the amorphous isomerization component. It is preferred to use lower acid strength amorphous components such as alumina.
Conversely, a catalyst that will maximize VI is produced by increasing the acid strength of the amorphous phase. In this case it is preferred to use higher acid strength amorphous components such as silica-aluminas or modified sihca-aluminas. Another way of making such a catalyst is by changing the ratio of the microporous component to the amorphous component such that the unitized catalyst has a trans-l,2/trans-l,3 DMCP ratio of >1.
The hydroisomerization process utilizing the catalyst of the present invention is conducted at temperatures between about 200°C to 400°C, preferably 250°C to 380°C, and most preferably 300°C to 350°C at hydrogen partial pressures between about 350 to 5,000 psig (2.41 to 34.6 mPa), preferably 1,000 to 2500 psig (7.0 to 17.2 mPa), a hydrogen gas treat ratio of 500 to 10,000 SCF H2/bbl (89 to 1780 π /m3), preferably 2,000 to 5,000 SCF H2/bbl (356 to 890 m3/m3) and a LHSV of 0.1 to 10 v/v/hr, preferably 0.5 to 5 v/v/hr, and more preferably 1 to 2 v/v/hr.
In an alternate embodiment of the present invention the waxy feed is first subject to solvent dewaxing to a pour point of the order of +10°C or lower.
The dewaxing solvent used may include the C3-C6 ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK and MIBK, aromatic hydrocarbons like toluene, mixtures of ketones and aromatics like MEK/toluene, ethers such as methyl t-butyl ethers and mixtures of - 9 -
same with ketones or aromatics. Similarly, liquefied, normally gaseous hydrocarbons like propane, propylene, butane, butylene, and combinations thereof may be used as the solvent. Preferably the solvent employed will be an equal volume mixture of methyl ethyl ketone and methyl isobutyl ketone. Typically the isomerate to solvent ratio will range between 1 to 10 and preferably will be about 1:3. The dewaxed feed is then subjected to hydroisomerizing as described hereinabove.
The present invention is demonstrated below in the non-limiting examples.
EXAMPLES
Example 1
This example illustrates the yield- VI trade-off on a hydrocracker distillate (Feed A) for catalysts with different degrees of acidity in the amorphous component. The physical properties of the hydrocracker distillate (Feed A) are shown in Table 1.
Table 1: Properties of Hydrocracker Distillate Feed A
Viscosity, cSt at 100°C, 5.19
Viscosity, cSt at 135°C, 2.994
VI 150
Wax Content, wt% 33.5
Boiling Range, (5/95%) °C 235-533
The catalyst in Table 2 (column B) was made by combining the zeolite theta-1 (TON) in the powder form with alumina (BET Surface Area 190 m^lm?) in the powder form followed by intimate mixing so as to form a - 10 -
homogeneous powdered mixture and then forming into catalyst pellets by pressing in a die and sizing to the required mesh size. Both the TON and the alumina had been loaded with palladium in the powdered form using aqueous palladium tetraamine dinitrate (at pH = 10) and palladium dichloride respectively before being intermixed.
The catalyst in Table 2 (column C) was made by combining the zeolite TON with silica-alumina (Si-Al) using the same technique as used in column A to produce a homogeneous powdered catalyst before forming into pellets. In this case, the palladium was loaded (as palladium teu-aamine dinitrate) on to the finished unitized catalyst by incipient wetness.
Table 2 shows a comparison of activity and selectivity of these two catalysts for hydrodewaxing versus solvent dewaxing (column A). The acidity differences of each catalyst component and the corresponding finished unitized catalysts is also shown using the reaction of methylcyclohexane at 320°C. The table clearly shows the higher acidity (greater number and acid strength) silica- umina catalyst (column C) gives lower yield but much higher VI compared with the very low acidity associated with alumina (column B) which results in high yield but a debit in VI.
TABLE 2 Feed: Hydrocracker Distillate A O
A B C t*>
Solvent 0.25 wt% Pd TON / 0.3 wt% Pd TON /
CATALYST Dewaxing 0.25 wt% Pd Alumina 0.3 wt% Silica-Alumina
CONDITIONS
Temperature, °C 340 329
Pressure, psig 1000 1000 v/v hour 1.0 1.0
T G Rate, scf bbl 2500 2500
PRODUCT PROPERTIES
Yield, 370°C 50 65 40
VI 117 119 122
Viscosity at 100°C, cSt 5.45 5.45 4.81
Viscosity at 40°C, cSt 30.23 29.97 24.09
Pour Point, °C - 33 - 37 - 38
MCH (microporous) Conversion at 320°C 19.2 19.2 (0.5 wt% Pt on TON) ECP 61 61 trans- 1,2/trans- 1,3 DMCP 0.16 0.16
MCH (amoφhous support) Conversion at 320°C 0.1 > 8
ECP n/a 50 trans- 1,2/trans- 1,3 DMCP < 1 > 1 o
MCH (unitized catalyst) Conversion at 320°C 7.1 14.4
ECP 57 59 © t
Figure imgf000013_0001
trans- 1,2/trans- 1,3 DMCP 0.15 1.48 00 o
- 12 -
Example 2
This example further illustrates the yield- VI trade off and shows a comparison of activity and selectivity of two catalysts for hydrodewaxing a hydrocraker distillate (Feed B) versus solvent dewaxing. The physical properties of the hydrocracker distillate (Feed B) are shown in Table 3.
Table 3 : Properties of Hydrocracker Distillate Feed B
Viscosity, cSt at 100°C, 3.99
Viscosity, cSt at 135°C, 2.366
VI 127
Wax Content, wt% 22.4
Boiling Range, (5/95%), °C 325-475
TABLE 4 Feed: Hydrocracker Distillate B SO SO
A B C
Solvent Pd TON (25) / Pd TON (25) /
CATALYST Dewaxing Pt AI2O3 (75) Si-Al (75)
Average Reactor Temperature, °C 314 329
Pressure, psig 1000 1000 v/v/hr 1.0 1.0
TG Rate, scf/bbl 2500 2500
PRODUCT PROPERTIES
Yield, 350°C+ 75 80 74
VI 110 113 117
Viscosity at 100°C, cSt 3.94 3.93 3.75
Viscosity at 40°c, cSt 1
Pour Point, °C - 21 - 23 - 18
MCH (microporous) Conversion at 320°C 19.2 19.2 (0.5 wt% Pt on TON) ECP 61 61 trans- 1,2/trans- 1,3 DMCP 0.16 0.16
MCH (amoφhous support) Conversion at 320°C n/a 0.1 < 8
ECP n/a n/a 50 trans-l,2/trans-l,3 DMCP n a < 1 > 1 o
MCH (unitized catalyst) Conversion at 320°C n/a 7.1 14.4
SO
ECP n/a 57 59 so
©
Figure imgf000015_0001
trans-l,2/trans-l,3 DMCP n/a 0.15 1.48 SO 00 OS
- 14 -
The methods of making two of these catalysts (columns B and C) were described in Example 1.
Columns B and C in Table 4 allow a comparison of the yields and VTs obtained by both catalysts. Again the least acidic catalyst (column B) exhibits higher yields with lower VTs compared with the higher acidic catalyst (column C).
Example 3
This example further illustrates the yield- VI trade and shows a comparison of activity and selectivity of two catalysts for hydroisomerization a hydrocraker distillate (Feed B) versus solvent dewaxing. This example illustrates that by changing the relative amounts of microporous component to amorphous component the overall acidity of the unitized catalyst an be tailored to maximize yield or VI.
Table 5 compares two unitized catalysts both of which have been made by combining the powdered ZSM-5 (Si Al ratio 110) with the powdered amorphous component in different ratios and then loading platinum by incipient wetness using platinum tetraamine dichloride. Table 5 shows a comparison of activity and selectivity for these catalysts for dewaxing hydrocracker distillate B, the physical properties of which are shown in Table 3, with solvent dewaxing. The catalyst in column B which has a trans-l,2/trans-l,3 DMCP ratio of less than 1 shows higher yield but lower VI than the catalyst in column C which has a trans-l,2/trans-l,3 DMCP ratio greater than 1. TABLE 5 Feed: Hydrocracker Distillate B
SO SO
A B C
Solvent Pt ZSM-5 (50) / Pt ZSM-5 (10) /
CATALYST (WT%) Dewaxing Silica- Alumina (50) Silica-Alumina (90)
CONDITIONS
Average Reactor Temperature, °C 314 329 329 339
Pressure, psig 1000 1000 v/v/hr 1.0 1.0
TG Rate, scf/bbl 2500 2500
PRODUCT PROPERTIES
Yield, 350°C+ 75 65 50 55 45
VI 110 106 102 112 109
Viscosity at 100°C, cSt 3.94 4.1 4.05 3.83 3.81
Viscosity at 40°c, cSt 18.56 19.528 19.84 17.33 17.306 I
Pour Point, °C - 21 - 23 -43 - 20 - 36
MCH (microporous) Conversion at 320°C 21.1 21.1 (0.5 wt% Pt on ZSM-5) ECP 52 52 trans-l,2/trans-l,3 DMCP 0.02 0.02
MCH (amoφhous support) Conversion at 320°C 12.1 12.1
ECP 48 48 O H trans-l,2/trans-l,3 DMCP 2.11 2.1 1 so SO
©
MCH (unitized catalyst) Conversion at 320°C n/a 10.6 12 SO 00
ECP n/a 47 50 OS
Figure imgf000017_0001
trans- 1,2/trans- 1,3 DMCP n/a 0.82 1.8
- 16 -
Example 4
This example illustrates that good hydrogenation metal dispersion is required for maximum catalyst conversion. However, the metal in a mixed powdered catalyst can be dispersed on the microporous component or on the amorphous component.
The catalysts in Table 6 were made by combining the zeolite theta- 1 (TON) in the powder form with alumina (BET Surface Area 190m2/m3) in the powder form followed by intimate mixing so as to form a homogeneous powdered mixture and then forming into catalyst pellets by pressing in a die and sizing to the required mesh size.
The TON in the catalyst in column A had been loaded with platinum tetramine dinitrate before being mtermixed with alumina.
The TON in the catalyst in column B had been loaded with palladium in the powdered form using aqueous palladium tetraamine dinitrate (at pH=10) before being mtermixed with alumina.
The TON in the catalyst in column C had been loaded with palladium in the powdered form using aqueous tetiamine dinitrate (at pH=10) before being intermixed with platinum loaded (as platinum dichloride) alumina.
The catalyst in column D was made as described in Example 1.
Table 6, columns A and B, compares the activity of two TON zeoHte/ umina mixed powder catalysts in which the noble metal has been - 17 -
loaded only on the TON zeolite component. The Pd TON/dumina catdyst (column B), which has 12% metd dispersion, is shown to have much lower activity for pour point reduction than the Pt TON/dumina catdyst (column A) which has 65% metd dispersion.
Loading additiond Pt or Pd on the dumina component (Column C, and Column D, respectively) improves the activity of the catdyst to the level of that observed in Column A.
TABLE 6 so
Feed: Hydrocracker Distillate, Feed B t >
A B C D
Catalyst 0.46 wt% Pt TON (25) / 0.25 wt% Pd TON (25) / 0.25 wt% Pt TON / 0.25 wt% Pd TON / Components A1203 (75) A1203 (75) 0.46 wt% Pt AI2O3 0.25 wt% Pd Al2O3
Metal Dispersion 0.65 / -- 0.12 / - 0.12 / 0.94 0.12 / 0.41 on Components
Average Reactor Pour Yield on Pour Yield on Pour Yield on Pour Yield on I
Temperature, Point, Feed, Point, Feed, Point, Feed, Point, Feed,
°C °C VI wt% °C VI wt% °C VI wt% °C VI wt%
315 - 4 117 89 11 118 85 - 16 116 79 - 7 117 86
329 - 38 107 75 - 17 108 75 - 40 107 73 - 38 108 74
Figure imgf000020_0001
38 - 43 105 71 - 21 106 69 - 44 107 69 - 44 105 69
Comments: Good metal dispersion on zeolite - excellent catalyst activity. Poor metal dispersion on zeolite - poor catalyst activity. o
Poor metal dispersion on zeolite, good metal dispersion on support - good catalyst activity H Dispersion of metal on support can be less than 50% and still give good initial catalyst activity. so so o-- bJ

Claims

- 19 -CLA S:
1. A method for hydroisomerizing a waxy feed to produce improved yield of a lube basestock which comprises: contacting the waxy feed under hydroisomerization conditions with a catdyst comprising a unitized mixed powdered pellet catdyst having (1) a first dewaxing component selected from 8, 10 and 12 ring molecular sieves and mixtures thereof; (2) a second isomerization component which is an amorphous inorganic oxide; and (3) at least one of a Group VTB and a Group V I metd hydrogenation component, wherein the first and second components are present in a ratio such that when evduated in the conversion of methyl cyclohexane at 320┬░C to 1,1-dimethylcyclopentane, 1,2- dimethylcyclopentane, 1,3-dimethylcyclopentane and ethylcyclopentane, the catdyst will provide a trans-l,2-/trans-l,3-dimethylcyclopentane ratio in the range of less than 1 and a selectivity to ethylcyclopentane, at 10% conversion, of at least about 50%.
2. The method of claim 1 wherein the dewaxing component is at least one of a 10 ring and 12 ring molecular sieve.
3. The method of claim 1 wherein the isomerization component is at least one of silica, dumina, titania, zirconia, silica-dumina and silica- magnesia.
4. The method of claim 1 wherein the isomerization component is at least one of silica, dumina, titania and zirconia.
5. The method of claim 1 wherein the isomerization component is dumina. - 20 -
6. The method of claim 1 wherein the hydrogenation component is a Group Vm metd.
7. The method of claim 6 wherein the metd is Pt or Pd.
8. The method of claim 6 or 7 wherein the metd is dispersed on both the first dewaxing and second isomerization components.
9. The method of claim 8 wherein the metd dispersion on at least one of the components be at least about 0.3.
10. The method of claim 1 wherein the Group VIB and Group Viπ metd hydrogenation component is promoted or doped.
11. The method of claim 1 wherein the waxy feed is solvent dewaxed to a pour point of up to +10┬░C before hydroisomerization.
12. The method of claim 10 wherein the promoter or dopant is selected from yttria, rare earth oxides, boria and magnesia.
13. A method for hydroisomerizing a waxy feed to produce improved yield of a lube basestock which comprises: contacting the waxy feed under hydroisomerization conditions with a catdyst comprising a unitized mixed powdered pellet catdyst having (1) a first dewaxing component selected from 8, 10 and 12 ring molecular sieves and mixtures thereof; (2) a second isomerization component which is an amoφhous inorganic oxide; and (3) at least one of a Group VIB and a Group VUi metd hydrogenation component, wherein the first - 21 -
and second components are present in a ratio such that when evduated in the conversion of methyl cyclohexane at 320┬░C to 1, 1-dimethylcyclopentane, 1,2- dimethylcyclopentane, 1,3-dimethylcyclopentane and ethylcyclopentane, the catdyst will provide a trans-l,2-/trans-l,3-dimethylcyclopentane ratio in the range of at least 1 and a selectivity to ethylcyclopentane, at 10% conversion, of at least about 50%.
PCT/US1999/002986 1998-02-13 1999-02-12 Process for making a lube basestock WO1999041333A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP99908125A EP1054941A4 (en) 1998-02-13 1999-02-12 Process for making a lube basestock
JP2000531517A JP2002503753A (en) 1998-02-13 1999-02-12 Manufacturing method of base oil for lubrication
CA002319385A CA2319385A1 (en) 1998-02-13 1999-02-12 Process for making a lube basestock
AU27631/99A AU742605B2 (en) 1998-02-13 1999-02-12 Process for making a lube basestock

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7457998P 1998-02-13 1998-02-13
US60/074,579 1998-02-13

Publications (1)

Publication Number Publication Date
WO1999041333A1 true WO1999041333A1 (en) 1999-08-19

Family

ID=22120330

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/002986 WO1999041333A1 (en) 1998-02-13 1999-02-12 Process for making a lube basestock

Country Status (5)

Country Link
EP (1) EP1054941A4 (en)
JP (1) JP2002503753A (en)
AU (1) AU742605B2 (en)
CA (1) CA2319385A1 (en)
WO (1) WO1999041333A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2805762A1 (en) * 2000-03-02 2001-09-07 Inst Francais Du Petrole Extruded catalyst contains at least one matrix, at least one noble metal and at least one zeolite
WO2004044097A1 (en) * 2000-10-02 2004-05-27 Exxonmobil Research And Engineering Company Process for making a lube basestock
WO2004043594A1 (en) * 2000-11-16 2004-05-27 Exxonmobil Research And Engineering Company Process for improving basestock low temeperature performance using a combination catalyst system
WO2018167081A1 (en) * 2017-03-14 2018-09-20 Haldor Topsøe A/S Hydroisomerization catalyst
CN114196070A (en) * 2021-12-07 2022-03-18 武汉楚域现代客车内饰件有限公司 Composite nano material and method for manufacturing PVC hollow section bar with knurled surface

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101942320B (en) * 2009-07-09 2014-12-10 中国石油化工股份有限公司 Method for producing base oil by isodewaxing

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419220A (en) * 1982-05-18 1983-12-06 Mobil Oil Corporation Catalytic dewaxing process
US4428819A (en) * 1982-07-22 1984-01-31 Mobil Oil Corporation Hydroisomerization of catalytically dewaxed lubricating oils
US4601993A (en) * 1984-05-25 1986-07-22 Mobil Oil Corporation Catalyst composition dewaxing of lubricating oils
US4743355A (en) * 1979-10-15 1988-05-10 Union Oil Company Of California Process for producing a high quality lube oil stock
US4767522A (en) * 1984-11-28 1988-08-30 Mobil Oil Corporation Distillate dewaxing process with mixed zeolites
US5135638A (en) * 1989-02-17 1992-08-04 Chevron Research And Technology Company Wax isomerization using catalyst of specific pore geometry
US5264116A (en) * 1991-07-24 1993-11-23 Mobil Oil Corporation Production of lubricants by hydrocracking and hydroisomerization
US5378351A (en) * 1992-10-28 1995-01-03 Shell Oil Company Process for the preparation of lubricating base oils
US5413695A (en) * 1993-01-06 1995-05-09 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Process for producing lube oil from solvent refined oils by isomerization over a silicoaluminophosphate catalyst
US5723716A (en) * 1994-11-22 1998-03-03 Exxon Research And Engineering Company Method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle (LAW082)
US5725755A (en) * 1995-09-28 1998-03-10 Mobil Oil Corporation Catalytic dewaxing process for the production of high VI lubricants in enhanced yield
US5885438A (en) * 1993-02-12 1999-03-23 Mobil Oil Corporation Wax hydroisomerization process

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743355A (en) * 1979-10-15 1988-05-10 Union Oil Company Of California Process for producing a high quality lube oil stock
US4419220A (en) * 1982-05-18 1983-12-06 Mobil Oil Corporation Catalytic dewaxing process
US4428819A (en) * 1982-07-22 1984-01-31 Mobil Oil Corporation Hydroisomerization of catalytically dewaxed lubricating oils
US4601993A (en) * 1984-05-25 1986-07-22 Mobil Oil Corporation Catalyst composition dewaxing of lubricating oils
US4767522A (en) * 1984-11-28 1988-08-30 Mobil Oil Corporation Distillate dewaxing process with mixed zeolites
US5135638A (en) * 1989-02-17 1992-08-04 Chevron Research And Technology Company Wax isomerization using catalyst of specific pore geometry
US5264116A (en) * 1991-07-24 1993-11-23 Mobil Oil Corporation Production of lubricants by hydrocracking and hydroisomerization
US5378351A (en) * 1992-10-28 1995-01-03 Shell Oil Company Process for the preparation of lubricating base oils
US5413695A (en) * 1993-01-06 1995-05-09 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Process for producing lube oil from solvent refined oils by isomerization over a silicoaluminophosphate catalyst
US5885438A (en) * 1993-02-12 1999-03-23 Mobil Oil Corporation Wax hydroisomerization process
US5723716A (en) * 1994-11-22 1998-03-03 Exxon Research And Engineering Company Method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle (LAW082)
US5770542A (en) * 1994-11-22 1998-06-23 Exxon Research & Engineering Company Method for upgrading waxy feeds using a catalyst comprising mixed powered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle
US5725755A (en) * 1995-09-28 1998-03-10 Mobil Oil Corporation Catalytic dewaxing process for the production of high VI lubricants in enhanced yield

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1054941A4 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2805762A1 (en) * 2000-03-02 2001-09-07 Inst Francais Du Petrole Extruded catalyst contains at least one matrix, at least one noble metal and at least one zeolite
WO2001064339A1 (en) * 2000-03-02 2001-09-07 Institut Francais Du Petrole Zeolite zsm-48 catalyst and method for improving paraffinic feedstock flow point
JP2003525118A (en) * 2000-03-02 2003-08-26 アンスティテュ フランセ デュ ペトロール Zeolite ZSM-48 based catalyst and method for improving pour point of paraffin charge
US6984309B2 (en) 2000-03-02 2006-01-10 Institut Francais Du Petrole Zeolite ZSM-48 catalyst and method for improving paraffinic feedstock flow point
WO2004044097A1 (en) * 2000-10-02 2004-05-27 Exxonmobil Research And Engineering Company Process for making a lube basestock
WO2004043594A1 (en) * 2000-11-16 2004-05-27 Exxonmobil Research And Engineering Company Process for improving basestock low temeperature performance using a combination catalyst system
WO2018167081A1 (en) * 2017-03-14 2018-09-20 Haldor Topsøe A/S Hydroisomerization catalyst
US11384296B2 (en) 2017-03-14 2022-07-12 Haldor Topsøe A/S Hydroisomerization catalyst
CN114196070A (en) * 2021-12-07 2022-03-18 武汉楚域现代客车内饰件有限公司 Composite nano material and method for manufacturing PVC hollow section bar with knurled surface
CN114196070B (en) * 2021-12-07 2023-09-19 武汉楚域现代客车内饰件有限公司 Method for manufacturing PVC hollow profile with composite nano material and knurled surface

Also Published As

Publication number Publication date
EP1054941A1 (en) 2000-11-29
JP2002503753A (en) 2002-02-05
AU2763199A (en) 1999-08-30
EP1054941A4 (en) 2004-12-22
AU742605B2 (en) 2002-01-10
CA2319385A1 (en) 1999-08-19

Similar Documents

Publication Publication Date Title
AU743235B2 (en) Process for improving basestock low temperature performance using a combination catalyst system
US5723716A (en) Method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle (LAW082)
EP1244762B1 (en) A diesel fuel having a very high iso-paraffin to normal paraffin mole ratio
US6620312B1 (en) Process for making a lube basestock with excellent low temperature properties
AU717101B2 (en) Process for highly shape selective dewaxing which retards catalyst aging
US5977425A (en) Method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle
JPH10503542A (en) Production of lubricating oils with VI-selective catalysts
SG193576A1 (en) Novel process and catalyst system for improving dewaxing catalyst stability and lubricant oil yield
AU742605B2 (en) Process for making a lube basestock
US20060138023A1 (en) Process for making a lube basestock
WO2004043594A1 (en) Process for improving basestock low temeperature performance using a combination catalyst system
US20060142142A1 (en) Process for improving basestock low temeperature performance using a combination catalyst system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2319385

Country of ref document: CA

Ref country code: CA

Ref document number: 2319385

Kind code of ref document: A

Format of ref document f/p: F

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 531517

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 27631/99

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1999908125

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09601867

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1999908125

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 27631/99

Country of ref document: AU

WWW Wipo information: withdrawn in national office

Ref document number: 1999908125

Country of ref document: EP