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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/10—Lubricating oil

Definitions

• This invention relates to the hydrodewaxing 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 capable of promoting wax isomerization and naphthene destruction to form a lube basestock with minimum VI loss and having good 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 index (VI) which is undesirable.
• VI viscosity index
• This invention relates to a method for the hydrodewaxing of feeds to produce a lube basestock having improved low temperature properties which comprises: contacting the feed with a unitized mixed powder pellet catalyst under hydrodewaxing conditions, the catalyst comprising a metal hydrogenation component on a support having a first dewaxing component and a second isomerization component, wherein the first component is selected from 10 and 12 ring molecular sieves and mixtures thereof and the second component is an amorphous inorganic oxide and wherein the first and second components are present in a ratio such that when evaluated in the conversion of methyl cyclo- hexane 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-dimethylcyclopentane in the range of at least 1, and a selectivity to
• Figure 1 is a schematic drawing showing the conversion of methylcyclohexane to various cyclopentane compounds at 320°C.
• Figure 2 is a graph showing Brookfield viscosity vs. yield for various catalyst mixtures. 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 hydroisomerate, waxy raffmates and waxy distillates.
• waxy hydrocarbon oils such as slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer-Tropsch hydroisomerate, waxy raffmates and waxy distillates.
• waxy hydrocarbon oils such as slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer-Tropsch hydroisomerate, waxy raffmates and waxy distillates.
• waxy hydrocarbon oils such as slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer-Tropsch hydroisomerate, waxy raffmates and waxy distillates.
• waxy hydrocarbon oils such as slack wax, slack wax isomerate, Fischer-Tropsch wax, Fischer-
• any of the Group VEB to Group VIE and mixtures thereof (the metal 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 ppm or less nitrogen or 20 ppm 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 nitrogen. 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.
• 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 hydrodewaxing process of the present invention.
• the catalyst employed in the hydrodewaxing 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 catalytic component with a powdered second catalytic 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 catalysts, pulverizing and powdering such individual finished catalysts, mixing the powdered materials together to form a homogeneous mass, then compressing/extruding and pelleting thus producing the unitized pellet catalysts comprising a mixture of the individual, different, and distinct catalyst components. Pulverizing and powdering is to a consistency achievable using a mortar and pestle or other such conventional powdering means.
• the catalyst used in the process of the present invention comprises a metal hydrogenation component on a two component support.
• the metal hydrogenation component is at least one of a Group VIB or Group Vm metal, preferably a Group Vm metal, and more preferably Pt or Pd.
• the metal is dispersed on at least one of the first and second components of the support, and preferably on both components. Typically the metal will be present in an amount ranging from about 0.1 to about 30 wt%, and preferably about 0.1 to 10 wt%. If the metal is a Group VEI noble metal, then the preferred amount is 0.1 to 5 wt%.
• the catalyst may also include a substantially inert binder or matrix material.
• the first component is a catalytic dewaxing component including crystalline 10 and 12 ring molecular sieves.
• Crystalline molecular sieves include metallo-, e.g., alumino silicates, alumino phosphates and silicoalumino- phosphates.
• crystalline alumino silicates include zeolites, e.g., 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., alumina, silica-alumina, zirconia, titania, etc.) on which has been preferably deposited a catalytically active metal selected from Group VI B, Group VII B, Group Vi ⁇ metals and mixtures thereof, preferably Group Vi ⁇ , more preferably noble Group VHI, most preferably Pt or Pd and optionally - 6 -
• amorphous refractory metal oxide support base e.g., alumina, silica-alumina, zirconia, titania, etc.
• a catalytically active metal selected from Group VI B, Group VII B, Group Vi ⁇ metals and mixtures thereof, preferably Group Vi ⁇ , more preferably noble Group VHI, most preferably Pt or Pd and optionally - 6 -
• 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.
• the isomerization catalyst employs a base-material such as alumina
• acidity is imparted to the resultant catalyst by addition of a halogen, preferably fluorine.
• a halogen preferably fluorine
• it is present in an amount in the range 0.1 to 10 wt%, preferably 0.1 to 3 wt%, more preferably 0.1 to 2 wt%, most preferably 0.5 to 1.5 wt%.
• acidity can be controlled by adjusting the ratio of silica to alumina or by adding a dopant such as yttria, rare earth oxides, from, e.g., La, Ce, etc., boria or magnesia which reduces the acidity of the silica-alumina base material as taught on U.S. Patent 5,254,518 (Soled, McVicker, Gates, Miseo).
• a dopant such as yttria, rare earth oxides, from, e.g., La, Ce, etc., boria or magnesia which reduces the acidity of the silica-alumina base material as taught on U.S. Patent 5,254,518 (Soled, McVicker, Gates, Miseo).
• the first and second components are combined in a ratio sufficient to promote wax isomerization and napthene 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 determining 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- 1,3-dimethylcyclopentane (trans- 1,2/trans- 1,3 DMCP) in the range of at least one have been found to - 7 -
• the second factor is when the catalyst, impregnated with about 0.5 wt% Pt and evaluated in converting methylcyclohexane (MCH) to various cyclopentane compounds at 10% conversion, exhibits a selectivity for ethylcyclopentane (ECP) formation above at least 50%.
• MCH methylcyclohexane
• ECP ethylcyclopentane
• the ratio of trans- 1,2-DCMP to trans- 1,3- DCMP is adjusted to from 1:1 to 2:1 predominately by controlling the acid - 8 -
• amorphous isomerization component It is preferred to use higher acid strength amorphous components such as silica-alumina.
• a catalyst that will give high yield is produced by decreasing the acid strength of the amorphous phase.
• 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-1,2 trans-1,3 DMCP ratio of less than 1.
• the hydrodewaxing 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 pressures between about 500 to 5,000 psig (3.55 to 34.6 mPa), preferably 1,000 to 2000 psig (7.0 to 13.9 mPa), a hydrogen gas treat ratio of 500 to 10000 SCF H 2 /B (89 to 1780 m 3 /m 3 ), preferably 2,000 to 5,000 SCF H 2 /B (356 to 890 m 3 /m 3 ) and a LHSV of 0.5 to 5 v/v hr, preferably 1 to 2 v/v/hr.
• the feed is first subject to solvent dewaxing to a pour point on 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 same with ketones or aromatics.
• liquefied, normally gaseous hydrocarbons like propane, propylene, butane, butylene, and combinations thereof may be used as the solvent.
• the solvent employed will be an equal - 9 -
• the dewaxed feed is then subjected to hydrodewaxing as described hereinabove.
• a catalyst (B) comprising 0.5 wt% Pt ZSM-5 (silica/alumina ratio 220: 1) and alumina in the weight ratio of 25:75, was used in two runs to dewax a hydrocrackate distillate having the following properties:
• this catalyst When screened for activity and selectivity with methylcyclo- hexane, this catalyst had an ECP selectivity of 40 and a trans- 1, 2/trans-l,3 dimethylcylopentane ratio of 0.02 as shown in the Table.
• a comparison of columns A and B of the Table shows that the VI of the resulting liquid product (350°C+) was lower than that obtained by solvent dewaxing.
• the product low temperature properties as shown by the Brookfield Viscosity at -40°C (additized with a standard Ford type ATF adpack), are also shown in the Table.
• Brookfield Viscosity is reduced by catalytic dewaxing over that of a solvent dewaxed product.
• Brookfield Viscosities of both solvent and cat dewaxed products are very poor.
• a catalyst (C) comprising 0.5 wt% Pt ZSM-5 (silica alumina ratio 220:1) and silica-alumina in the weight ratio of 50:50, was used to dewax a hydrocrackate distillate having the properties noted in Comparative Example 1.
• This catalyst was made by combining the powdered ZSM-5 (Si/Al ratio 110) with the powdered amorphous component in the weight ratio of 50:50 and then loading platinum by incipient wetness using platinum tetraamine dichloride.
• this catalyst When screened for activity and selectivity with methylcyclo- hexane, this catalyst had an ECP selectivity of 47 and a trans- 1, 2/trans-l,3 dimethylcylopentane ratio of 0.82 as shown in the Table following Example 2.
• a comparison of columns A and C, in the Table shows that the VI of the resulting liquid product (350°C+) was lower than that obtained by solvent dewaxing.
• the product low temperature properties as shown by the Brookfield Viscosity -40°C (additized with a standard Ford type ATF adpack), are also shown in the Table. The Brookfield Viscosity is reduced by catalytic dewaxing over that of a solvent dewaxed product but not significantly over that obtained using the alumina bound catalyst in Example 1.
• a catalyst (D) comprising 0.5 wt% Pt ZSM-5 (silica/alumina ratio 220: 1) and silica alumina in the weight ratio of 10:90, was used to dewax a hydrocrackate distillate having the properties noted in Comparative Example 1.
• This catalyst was made by combining the powdered ZSM-5 (Si/Al ratio 110) - 11 -
• this catalyst When screened for activity and selectivity with methylcyclo- hexane, this catalyst had an ECP selectivity of 50 and a trans- 1,2/trans- 1,3 dimethylcylopentane ratio of 1.80 as shown in the Table following Example 2. Both of these values are within the criteria for catalysts of this invention.
• a comparison of columns A and D, in Table 1 shows that the VI of the resulting liquid product (350°C+) was higher than that obtained by solvent dewaxing.
• the product low temperature properties as shown by the Brookfield Viscosity at - 40°C (addized in a standard ECA/ATF adpack), are also shown in the Table. The Brookfield Viscosity is significantly reduced by catalytic dewaxing with this catalyst over that of a solvent dewaxed product in the Table 1.
• Example 1 The procedure of Example 1 was followed using 0.5 wt% on Pt on theta-1 (TON) on silica-alumina (Catalyst E)and 0.5 wt% Pt on AI2O3 in the weight ratio of 25:75 (Catalyst F-Comparative).
• Theta-1 is a 10 ring zeolite and is described in EP 057049.
• This catalyst was made by combining the powdered TON zeolite (Si/Al ratio 30) with the powdered amorphous component in different ratios and then loading platinum by incipient wetness using platinum tetraamine dichloride. The condition and results are set out in columns E and F of Table 1. TABLE 1 v?

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• 1999
  • 1999-02-12 AU AU26734/99A patent/AU743235B2/en not_active Ceased
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