EP1354931A2 - Herstellung von schmieröl mit hohem viskositätsindex und niedrigem verzweigungsindex - Google Patents

Herstellung von schmieröl mit hohem viskositätsindex und niedrigem verzweigungsindex Download PDF

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EP1354931A2
EP1354931A2 EP03014566A EP03014566A EP1354931A2 EP 1354931 A2 EP1354931 A2 EP 1354931A2 EP 03014566 A EP03014566 A EP 03014566A EP 03014566 A EP03014566 A EP 03014566A EP 1354931 A2 EP1354931 A2 EP 1354931A2
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process according
pour point
oil
wax
molecular sieve
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English (en)
French (fr)
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EP1354931A3 (de
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Stephen J Miller
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Chevron USA Inc
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Chevron USA Inc
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Priority claimed from US09/107,835 external-priority patent/US6663768B1/en
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Publication of EP1354931A3 publication Critical patent/EP1354931A3/de
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    • 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

  • the present process is a dewaxing process for producing very high viscosity index, low pour point lubricating oil base stocks from a mineral oil feed.
  • viscosity index is generally increased to a target value during an upgrading step using hydrocracking, solvent refining, etc.
  • Pour point is generally reduced to a target value during a dewaxing step, using catalytic or solvent dewaxing.
  • the viscosity index generally decreases during dewaxing, since conventional dewaxing processes remove high viscosity index wax from the lubricating oil base stock. Improvements in automotive engine design is putting ever increasing pressure on the quality of motor oils. Demand for low volatility oils having superior low temperature properties is increasing, and refiners are constantly looking for new processes to aid them in meeting current demands.
  • High quality lubricants should be, and generally are, paraffinic in nature, since paraffins have a high viscosity index.
  • normal paraffins in particular, are waxy in character, and contribute to a high pour point in the oil.
  • Conventional processes for removing these normal paraffins reduce yield of the lubricant, and have a tendency to reduce the viscosity index of the dewaxed oil.
  • the viscosity index may be increased in the lubricating oil base stock by addition of viscosity index improvers.
  • viscosity index improvers are expensive, and tend to fragment at conditions of high temperature and high shear, both of which are commonly found in modem automotive engines.
  • Synthetic lubricants may be used when very low pour point and very high viscosity index lubricants are desired. But the starting materials used to make the synthetic lubricants, and the processes used in manufacturing these lubricants, are very expensive. The need remains for a lubricating oil base stock, having synthetic-like properties but prepared from a mineral oil feed using methods which are similar to those presently employed in refinery processes.
  • silicoaluminophosphate molecular sieves including SAPO-11, SAPO-31 and SAPO-41
  • Dewaxing processes using such molecular sieves are taught in U.S. Patent No. 4,859,311; U.S. Patent No. 4,867,862; U.S. Patent No. 4,921,594; U.S. Patent No. 5,082,986; U.S. Patent No. 5,135,638; U.S. Patent No. 5,149,421; U.S. Patent No. 5,246,566; U.S. Patent No. 5,413,695; and U.S. Patent No. 4,960,504.
  • SAPO molecular sieves belong to an important class of non-zeolitic molecular sieve dewaxing catalysts which are useful as isomerization catalysts for converting wax and wax-like components.
  • Non-zeolitic molecular sieves are microporous compositions that are formed from AlO 2 and PO 2 tetrahedra which form 3-dimensional crystalline structures, and are described broadly for this use in U.S. Patent No. 4,906,351 and U.S. Patent No. 4,880,760.
  • U.S. Patent No. 5,282,958 a feed including straight chain and slightly branched chain paraffins having 10 or more carbon atoms is isomerized with an intermediate pore size molecular sieve having a defined pore geometry, crystallite size, acidity and isomerization selectivity.
  • Feeds which may be processed by the method of U.S. Patent No. 5,282,958 include waxy feeds, which contain greater than about 50% wax. Such feeds are also taught as often containing greater then 70% paraffinic carbon.
  • U.S. Patent No. 5,376,260 is directed to pour point reduction of a heavy oil which contains naphthenic wax, using SSZ-32. Heavy oils comprising up to 100% wax are taught.
  • WO 96/13563 teaches an isomerization process for producing a high viscosity index lubricant using a low acidity large pore molecular sieve having a crystal size of less than 0.1 micron, an alpha value of not more than 30 and containing a noble metal hydrogenation component.
  • EP 225053 teaches isomerization dewaxing using a large pore, high silica zeolite dewaxing catalyst, followed by a subsequent dewaxing step which selectively removes the more waxy n-paraffin components.
  • the selective dewaxing step may be either a solvent or a catalyst dewaxing, preferably using highly shape selective zeolite such as ZSM-22 or ZSM-23.
  • An object of the present invention is to provide a process for producing an oil, having a very high viscosity index and a very low pour point, which is suitable for use as a lubricating oil base stock.
  • the feedstock to the present process is a waxy feed which may be derived from mineral oils and mineral oil crudes.
  • the oil which is produced has lubricating oil properties that approach, and may exceed, the lubricating oil properties of a synthetic lubricating oil base stock.
  • the present invention provides a process for preparing an oil suitable for use as a lubricating oil base stock and having a viscosity index of greater than 140 and a target pour point of less than or equal to -10°C comprising:
  • the target pour point may be less than about -20 °C, and may preferably be for preparing a lubricating oil base stock having a viscosity index of greater than 150.
  • the waxy feed contains more than about 50% wax, more preferably more than about 80% wax.
  • the waxy feed may contain more than about 70% paraffinic carbon.
  • the waxy feed may be selected from the group consisting of synthetic oils and waxes such as those by Fischer-Tropsch synthesis, high pour point polyalphaolefins, foots oils, normal alpha olefin waxes, slack waxes, deoiled waxes and microcrystalline waxes.
  • the isomerized oil resulting from the process may have a pour point of greater than about 0°C.
  • the between about 60% and about 99% by weight of the wax contained in the waxy feedstock may be removed in step a).
  • the hydrogenation component may be a Group VIII metal selected from the group consisting of platinum, palladium or mixtures thereof.
  • the catalyst may contain from about 0.2% to about 1% by weight of the hydrogenation component.
  • a particularly preferred molecular sieve useful in the isomerization step has sufficient isomerization selectivity such that, when contacting a n-C 24 feed at a total pressure of 1000 psig (6.99 MPa), hydrogen flow equivalent to 6.7 MSCF/bbl (1010 std liters H 2 /kg oil), and a feed rate equivalent to 0.6 ho -1 LHSV with a catalyst comprising the molecular sieve, to produce a 316°C+ dewaxed product having a pour point of about +20° and solvent dewaxing the dewaxed product to a pour point of-15°C or below, an isomerized product having a branching index of less than about 1.75 is formed.
  • a process for preparing an oil suitable for use as a lubricating oil base stock comprising: a) contacting a waxy feed over a catalyst comprising a molecular sieve having 1-D pores with a pore diameter of between about 5.0 ⁇ and about 7.0 ⁇ , and at least one Group VIII metal, at a pressure of from about 15 psig (103 kPa) to about 2500 psig (13.8 MPa) to produce an isomerized oil having a pour point of greater than about 0 °C; and b) solvent dewaxing the isomerized oil to produce a lubricating oil base stock having a pour point of less than or equal to -10°C, a viscosity index of greater than about 140 and a viscosity, measured at 100°C, of about 3 cSt or less.
  • the viscosity of the lubricating oil base stock measured at 100°C, may be less than about 3 cSt and the pour point less than or equal to -20°C. Further, the viscosity index of the lubricating oil base stock may be greater than 150 and the pour point may be less than -20°C. Further, the molecular sieve used in the process may be SSZ-32 or may be SM-3.
  • the present invention provides a unique lubricating oil base stock, which has a viscosity index of at least about 140, a pour point of less than or equal to about -10 °C, and a viscosity, measured at 100°C, of about 3 cSt or less.
  • the viscosity index is at least about 150, more preferably at least about 160.
  • the pour point is less than or equal to about -20 °C
  • Normal paraffins are a major contributor to wax and a high pour point in a lubricating oil base stock. It is desirable to isomerize the normal paraffins to low pour point branched paraffins which retain the boiling range of the normal paraffins from which there were converted.
  • the present invention is based on the discovery that the number of branches produced while isomerizing a normal paraffin molecule significantly impacts the quality of the dewaxed oil product.
  • isomerizing a normal C 24 paraffin, tetracosane, using a large pore zeolite catalyst conventionally taught for wax isomerization generally produces a significant quantity of triply branched paraffin isomers.
  • Even medium pore catalysts taught for wax isomerization when isomerizing a waxy feed to a low pour point, produces significant quantities of the triply branched isomers.
  • normal paraffins are isomerized at high selectivity to singly and doubly branched paraffins using a process which produces few triply branched paraffins.
  • the shape selective catalyst of the present invention comprising a 1-D intermediate pore size molecular sieve, restricts the amount of triply branched paraffins which are formed in the isomerization of a waxy feed, while producing a product having an intermediate pour point.
  • the remaining wax is removed in a solvent dewaxing step to produce a lubricating oil base stock with a very low pour point and a viscosity index which approaches, and can exceed, the viscosity index of synthetic lubricants having the same viscosity.
  • a normal paraffin, or alkane is a saturated aliphatic hydrocarbon containing only --CH 3 and --CH 2 -- groups.
  • a branched paraffin is a saturated aliphatic hydrocarbon containing one or more or groups.
  • each R represents a branch, where R is an alkyl independently selected from --CH 3 , --C 2 H 5 , --C 3 H 7 , or --C 4 H 9 , and preferably from --CH 3 or --C 2 H 5 .
  • R 1 and R 2 represent portions of the paraffin chain or backbone.
  • a singly branched paraffin has one R group per paraffin molecule, a doubly branched paraffin two R groups, a triply branched paraffin three R groups, etc.
  • the feedstock to the present process is a "waxy feed".
  • the feedstock will normally be a C 20 + feedstock, generally boiling above about 316°C and containing paraffins, olefins, naphthenes, aromatics and heterocyclic compounds and a substantial proportion of higher molecular weight.
  • n-paraffins and slightly branched paraffins which contribute to the waxy nature of the feedstock.
  • Hydroprocessed stocks are a convenient source of stocks of this kind and also of other distillate fractions since they normally contain significant amounts of waxy n-paraffins.
  • waxy feed includes petroleum waxes.
  • exemplary suitable feeds for use in the process of the invention also include waxy distillate stocks such as gas oils, lubricating oil stocks, synthetic oils and waxes such as those by Fischer-Tropsch synthesis, high pour point polyalphaolefins, foots oils, normal alpha olefin waxes, slack waxes, deoiled waxes and microcrystalline waxes.
  • Slack wax is wax recovered from a conventional solvent dewaxing process. Slack wax can be obtained from either a straight run gas oil, a hydrocracked lube oil or a solvent refined lube oil. Hydrocracking is preferred because that process can also reduce the nitrogen content to low values.
  • slack wax derived from solvent refined oils deoiling can be used to reduce the nitrogen content.
  • hydrotreating of the slack wax can be carried out to lower the nitrogen content thereof.
  • Slack waxes possess a very high viscosity index, normally in the range of from 120 to 200, depending on the oil content and the starting material from which the wax has been prepared. Slack waxes are therefore eminently suitable for the preparation of lubricating oils having very high viscosity indices, i.e., from about 140 to about 180.
  • Foots oil is prepared by separating oil from the wax. The isolated oil is referred to as foots oil.
  • the feedstock employed in the process of the invention preferably contains greater than about 50% wax, more preferably greater than about 80% wax, most preferably greater than about 90% wax.
  • a highly paraffinic feed having a high pour point, generally above about 0°C, more usually above about 10°C, but containing less than 50% wax is also suitable for use in the process of the invention.
  • Such a feed should preferably contain greater than about 70% paraffinic carbon, more preferably greater than about 80% paraffinic carbon, most preferably greater than about 90% paraffinic carbon.
  • a catalyst useful in the present process comprises an intermediate pore size molecular size and a hydrogenation component.
  • Catalysts of this type are taught in U.S. Patent No. 5,135,638, the entire disclosure of which is incorporated herein by reference for all purposes.
  • the phrase "intermediate pore size", as used herein means an effective pore aperture in the range of from about 5.0 to about 7.0 ⁇ , preferably from about 5.3 to about 6.5 ⁇ , when the porous inorganic oxide is in the calcined form.
  • the effective pore size of the molecular sieves can be measured using standard adsorption techniques and hydrocarbonaceous compounds of known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves. 1974 (especially Chapter 8); Anderson et al., J. Catalysis 58, 114 (1979); and U.S. Pat. No. 4,440,871, the pertinent portions of which are incorporated herein by reference.
  • Intermediate pore size molecular sieves will typically admit molecules having kinetic diameters of 5.3 to 6.5 ⁇ with little hindrance.
  • Examples of such compounds (and their kinetic diameters in ⁇ ) are: n-hexane (4.3), 3-methylpentane (5.5), benzene (5.85), and toluene (5.8).
  • Compounds having kinetic diameters of about 6 to 6.5 ⁇ can be admitted into the pores, depending on the particular sieve, but do not penetrate as quickly and in some cases are effectively excluded.
  • Compounds having kinetic diameters in the range of 6 to 6.5 ⁇ include: cyclohexane (6.0), 2,3-dimethylbutane (6.1), and m-xylene (6.1).
  • intracrystalline channels must be parallel and must not be interconnected. Such channels are conventionally referred to as 1-D diffusion types or more shortly as 1-D pores.
  • 1-D diffusion types or more shortly as 1-D pores.
  • the classification of intrazeolite channels as 1-D, 2-D and 3-D is set forth by R. M. Barrer in Zeolites, Science and Technology, edited by F. R. Rodrigues, L. D. Rollman and C. Naccache, NATO ASI Series, 1984 which classification is incorporated in its entirety by reference (see particularly page 75).
  • Known 1-D zeolites include cancrinite hydrate, laumontite, mazzite, mordenite and zeolite L.
  • the pores of the molecular sieve have a major axis between about 5.0 ⁇ and about 7.0 ⁇ , i.e. the pore diameter of the molecular sieve is between about 5.0 ⁇ and about 7.0 ⁇ .
  • the preferred molecular sieves useful in the practice of the present invention have pores which are oval in shape, by which is meant the pores exhibit two unequal axes referred to herein as a minor axis and a major axis.
  • oval as used herein is not meant to require a specific oval or elliptical shape but rather to refer to the pores exhibiting two unequal axes.
  • the present invention makes use of molecular sieve catalysts with selected shape selectivity properties. These shape selectivity properties are defined by carrying out standard isomerization selectivity tests for isomerizing tetracosane (n-C 24 ).
  • the test conditions include a total pressure of 1000 psig (6.89 MPa), hydrogen flow equivalent to 6.7 MSCF/bbl (1010 std liters H 2 /kg oil), a feed rate equivalent to 0.6 hr -1 ⁇ LHSV and the use of 0.5g of catalyst (impregnated with 0.5 wt% Pt and sized to 24-42 mesh [0.35 mm-0.70 mm]) loaded in the center of a 3 feet long (0.91 m) by 3/16 inch (0.48 cm) inner diameter stainless steel reactor tube (the catalyst is located centrally of the tube and extends about 1 to 2 inches [2.54-5.08 cm] in length) with alundum loaded upstream of the catalyst for preheating the feed.
  • the reactor temperature is adjusted to achieve a pour point of about +20°C in the 600°F+ (316°C) distillation bottoms of the reactor effluent.
  • the 600°F+ (316°C) distillation bottoms are then solvent dewaxed to a pour point of about -15°C.
  • the branching index is determined by analyzing a sample of the product from the standard isomerization selectivity test using carbon-13 NMR according to the following four-step process. References cited in the description detail the process steps.
  • a catalyst if it is to qualify as a catalyst of this invention, when tested in this manner, must convert sufficient normal C 24 paraffin to form an isomerized product having a pour point of about -15°C or less and a branching index of less than about 1.75.
  • Non-zeolitic molecular sieves having the characteristics of an intermediate pore size molecular sieve as described herein are useful in the present process.
  • Non-zeolitic molecular sieves are microporous compositions that are formed from AlO 2 and PO 2 tetrahedra.
  • the process of the invention may be carried out using a catalyst comprising an intermediate pore size non-zeolitic molecular sieve and at least one Group VIII metal.
  • Non-zeolitic molecular sieves are described, for example, in U.S. Patent No. 4,861,743, the disclosure of which is completely incorporated herein by reference for all purposes.
  • Non-zeolitic molecular sieves include aluminophosphates (AlPO 4 ) as described in U.S. Patent No. 4,310,440, silicoaluminophosphates (SAPO), metalloaluminophosphates (MeAPO), and nonmetal substituted aluminophosphates (EIAPO).
  • SAPO silicoaluminophosphates
  • MeAPO metalloaluminophosphates
  • EIAPO nonmetal substituted aluminophosphates
  • Metalloaluminophosphate molecular sieves are described in U.S. Patent Nos. 4,500,651; 4,567,029; 4,544,143; 4,686,093 and 4,861,743.
  • Non-zeolitic molecular sieves are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of aluminum, phosphorus, optionally one or more elements, other than aluminum and phosphorous, which are capable of forming oxides in tetrahedral coordination with AlO 2 and PO 2 units, and one or more organic templating agents.
  • the reaction mixture is placed in a sealed pressure vessel and heated, preferably under autogenous pressure at a temperature of at least about 100°C., and preferably between 100°C. and 250°C., until crystals of the molecular sieve product are obtained, usually for a period of from 2 hours to 2 weeks.
  • a silicoaluminophosphate molecular sieve is suitable as an intermediate pore size molecular sieve for the present process.
  • the silicoaluminophosphate molecular sieves belong to a class of non-zeolitic molecular sieves characterized by a three-dimensional microporous framework structure of AlO 2 , and PO 2 tetrahedral oxide units with a unit empirical formula on an anhydrous basis of: (Si x Al y P z )O 2 wherein "x”, "y”, and “z” represent the mole fractions, respectively, of silicon, aluminum, and phosphorus, wherein "x” has a value equal to or greater than zero (0), and "y” and “z” each have a value of at least 0.01.
  • Catalytic particulates containing at least one of the intermediate pore molecular sieves SAPO-11, SAPO-31 and SAPO-41 are particularly useful in the present process.
  • U.S. Patent No. 4,440,871 describes SAPO's generally and SAPO-11, SAPO-31, and SAPO-41 specifically.
  • the most preferred intermediate pore size silicoaluminophosphate molecular sieve for use in the process of the invention is SAPO-11.
  • the SAPO-11 converts the waxy components to produce a lubricating oil having excellent yield, very low pour point, low viscosity and high viscosity index.
  • SAPO-11 comprises a silicoaluminophosphate material having a three-dimensional microporous crystal framework structure of PO 2 , AlO 2 and SiO 2 tetrahedral units whose unit empirical formula on an anhydrous basis is: mR: (Si x Al y P z )O 2 wherein "R” represents at least one organic templating agent present in the intracrystalline pore system; “m” represents the moles of “R” present per mole of (Si x Al y P z )O 2 and has a value of from zero to about 0.3, “x", “y” and “z” represent respectively, the mole fractions of silicon, aluminum and phosphorous, wherein "x” has a value greater than zero (0), and "y” and “z” each have a value of at least 0.01.
  • SM-3 The most particularly preferred intermediate pore SAPO prepared by the present process is SM-3, which has a crystalline structure falling within that of the SAPO-11 molecular sieves.
  • SM-3 The preparation of SM-3 and its unique characteristics are described in U.S. Patent Nos. 4,943,424 and 5,158,665. The entire disclosure of each of these patents is incorporated herein by reference for all purposes.
  • SAPO-41 has characteristic X-ray powder diffraction pattern (as-synthesized and calcined) which contains at least the d-spacings set forth below in Table III.
  • "m" preferably has a value of from 0.02 to 0.03.
  • the original cations of the as-synthesized ZSM-22 can be replaced at least in part by other ions using conventional ion exchange techniques. It may be necessary to pre-calcine the ZSM-22 zeolite crystals prior to ion exchange.
  • the replacement ions are those taken from Group VIII of the Periodic Table, especially platinum, palladium, iridium, osmium, rhodium and ruthenium.
  • the average crystal size is no greater than about 10 microns (i.e. micrometers), preferably no more than about 5 microns, more preferably no more than about 1 micron and still more preferably no more than about 0.5 micron.
  • the physical form of the catalyst depends on the type of catalytic reactor being employed and may be in the form of a granule or powder, and is desirably compacted into a more readily usable form (e.g., larger agglomerates), usually with a silica or alumina binder for fluidized bed reaction, or pills, prills, spheres, extrudates, or other shapes of controlled size to accord adequate catalyst-reactant contact.
  • the preferred catalyst is in the form of extrudates with a cross-sectional diameter between about 1 ⁇ 4 inch and about 1 / 32 inch.
  • the molecular sieve can be composited with other material resistant to the temperatures and other conditions employed in organic conversion processes.
  • the catalyst may also contain metals which reduce the number of strong acid sites on the catalyst and thereby lower the selectivity for cracking versus isomerization.
  • the Group IIA metals such as magnesium and calcium.
  • the Group VIII metal utilized in the process of this invention can mean one or more of the metals in its elemental state or in some form such as the sulfide or oxide and mixtures thereof.
  • the active metal or metals it is intended to encompass the existence of such metal in the elementary state or in some form such as the oxide or sulfide as mentioned above, and regardless of the state in which the metallic component actually exists, the concentrations are computed as if they existed in the elemental state.
  • the catalytic isomerization step of the invention may be conducted by contacting the feed with a fixed stationary bed of catalyst, with a fixed fluidized bed, or with a transport bed.
  • a simple and therefore preferred configuration is a trickle-bed operation in which the feed is allowed to trickle through a stationary fixed bed, preferably in the presence of hydrogen.
  • the catalytic isomerization conditions employed depend on the feed used and the desired pour point. Generally, the temperature is from about 200°C to about 475°C, preferably from about 250°C and to about 450°C.
  • the pressure is typically from about 15 psig (103 kPa) to about 2500 psig (27.2 MPa), preferably from about 50 psig (345 kPa) to about 2000 psig (13.8 MPa), more preferably from about 100 psig to about 1500 psig (10.3 MPa).
  • the liquid hourly space velocity is preferably from about 0.1hr -1 to about 20 hr -1 , more preferably from about 0.1hr -1 to about 5hr -1 , and most preferably from about 0.1 hr -1 to about 1.0 hr -1 .
  • Low pressure and low liquid hourly space velocity provide enhanced isomerization selectivity which results in more isomerization and less cracking of the feed thus producing an increased yield.
  • Hydrogen is preferably present in the reaction zone during the catalytic isomerization process.
  • the hydrogen to feed ratio is typically from about 500 to about 30,000 SCF/bbl (standard cubic feet per barrel) (76-4540 std liters H 2 /kg oil), preferably from about 1,000 to about 10,000 SCF/bbl (151-1510 std liters H 2 /kg oil).
  • SCF/bbl standard cubic feet per barrel
  • the pour point of the isomerized product is lower than the pour point of the waxy feed to the dewaxing process.
  • the pour point of the oil is generally below about 10°C, and often below 0°C. While a low pour point is desired in the product from the isomerization step, excessive isomerization has a detrimental effect on product viscosity index, as described hereinbefore.
  • the wax content of the isomerized oil is between about 1% and about 40%, preferably between about 3% and about 20%, of the wax content of the waxy feed. The isomerization step, then preferentially removes between about 60% and about 99% by weight of the wax contained in the waxy feedstock.
  • the pour point of the isomerized product while being substantially lower than the pour point of the feed to the isomerization process, will be at least about 6°C, and more usually at least about 12°C above the target pour point set for the finished lubricating oil base stock.
  • the viscosity index of the isomerized product will be generally above about 140 and preferably above about 150. With some products, a viscosity index of 160 or above is possible.
  • the wax content of the oil set forth herein is determined from a conventional solvent dewaxing method.
  • An example method is as follows:
  • 300 g of oil is diluted 50/50 with a 4:1 mixture of methyl ethyl ketone and toluene which is cooled to -20°C in a refrigerator.
  • the mixture is filtered through a Coors funnel at -15 °C. using Whatman No. 3 filter paper.
  • the wax is removed from the filter and placed in a tared 2 liter flask. The solvent is removed on a hot plate and the wax weighed.
  • the present integrated two-step process comprises a catalytic isomerization step and a solvent dewaxing step.
  • the pour point of the isomerized oil will generally be at least about 6°C and preferably at least about 12°C above a target pour point of the finished oil.
  • the isomerized oil is solvent dewaxed to a desired target pour point, which is determined by the particular grade of oil which is being produced.
  • the target pour point will generally be less than or equal to about -10°C.
  • Lubricating oil stocks will generally boil above 230°C (450°F), more usually above 315°C (600°F).
  • solvent dewaxing processes which are commonly used in the preparation of a lubricating oil base stock are suitable for the present integrated process. Such processes include crystallization of the wax from a chilled mixture of waxy oil and a solvent such as a blended methyl ethyl ketone/toluene solvent.
  • the slack wax and/or the foots oil recovered as the residual oil remaining in the slack wax may be recovered or recycled to the isomerization reaction zone.
  • the isomerized oil which is the feed to the solvent dewaxing step of the present process will generally have a pour point of less than about 40°C, and a viscosity index of greater than about 125 and preferably greater than about 140, and more preferably greater than about 150.
  • Feed to the isomerization process may require pretreatment before it can be satisfactorily processed in the isomerization step.
  • the pretreatment steps remove heteroatoms such as nitrogen and sulfur which might poison the isomerization catalyst, or low viscosity index components such as aromatics and polycyclic naphthenes.
  • a typical hydrocracking process is described, for example, in U.S. Patent No. 5,158,665, the entire disclosure of which is already incorporated by reference.
  • hydrofinishing it may further be desired to hydrofinish the dewaxed oil in a mild hydrogenation process to produce more stable lubrication oils.
  • the hydrofinishing can be conventionally carried out in the presence of a metallic hydrogenation catalyst, for example, platinum on alumina.
  • the hydrofinishing can be carried out at a temperature of from about 190°C to about 340°C and a pressure of from about 400 psig to about 3000 psig (2.76-20.7 MPa).
  • a description of a typical hydrofinishing process and catalyst which is useful in the present process is taught in U.S. Patent No. 5,158,665. Hydrofinishing in this manner is also described in U.S. Pat. 3,852,207, both of which are incorporated herein by reference for all purposes.
  • the present process is suitable for preparing very high viscosity index lubricating oil base stocks having a wide range of viscosities, including base stocks having a viscosity, measured at 100°C, of 10 cSt or higher.
  • These base oils have a viscosity index of at least about 140 (preferably at least about 150 and more preferably at least about 160), and a pour point of less than or equal to about -10°C (preferably less than or equal to about -20°C, and more preferably less than or equal to about -30°C).
  • a particularly important base oil prepared in the present process has a viscosity, measured at 100°C, of about 3 cSt or less, preferably less than about 3 cSt, and a viscosity index of at least about 140, preferably at least about 150, and more preferably at least about 160.
  • This relatively light oil prepared in the present process has a viscosity index higher than that produced even in synthetic oils having a viscosity, measured at 100°C, of about 3 cSt or less.
  • Tetracosane (n-C 24 , purchased from Aldrich), which had a pour point of +50 C and a viscosity at 100 C of about 2.5 cSt, was isomerized over SM-3 impregnated with 0.5 wt% Pt. The catalyst was pelleted, then crushed to 24-42 mesh for testing. The catalyst was sulfided in situ prior to testing by injecting H 2 S through a septum into the hydrogen line ahead of the reactor. Isomerization was carried out in a continuous feed high pressure pilot plant with once-through hydrogen gas.
  • Tetracosane was isomerized over the same PVSM-3 catalyst as in Comparative Example A, but to a pour point of +20 °C.
  • the 316 °C+ distillation bottoms were then solvent dewaxed (SDW) to a pour point of -29 °C.
  • the viscosity index of the oil was 148 (Table VII), much higher (about 18 numbers) than obtained with isomerization only to the same pour point ( Figure I).
  • the isomerized and solvent dewaxed oil had a much lower average number of branches per molecule.
  • Comparative Example B was repeated, except in this case, the feed was isomerized over the SM-3 catalyst to a pour point of 0°C, followed by solvent dewaxing to -18°C.
  • the viscosity index (143, Table IX) was about the same as in the comparative example, but the pour point was lower. In addition, the cloud point was considerably lower.
  • Comparative Example C was repeated, except in this case, the feed was isomerized at 1100 psig (7.58 MPa) over the SM-3 catalyst to a pour point of-3°C, followed by solvent dewaxing to -14°C.
  • the viscosity index (144, Table XI) was higher than in the comparative example, and the pour point was lower.
  • Comparative Example D was repeated, except in this case; the feed was isomerized over the SSZ-32 catalyst to a pour point of +4°C, followed by solvent dewaxing to -21°C.
  • the viscosity index (156, Table XII) was higher than in the comparative example by an estimated 8-9 numbers at the same pour point.

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
EP03014566A 1998-03-06 1999-01-29 Herstellung von schmieröl mit hohem viskositätsindex und niedrigem verzweigungsindex Withdrawn EP1354931A3 (de)

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US7707098P 1998-03-06 1998-03-06
US77070P 1998-03-06
US107835 1998-06-30
US09/107,835 US6663768B1 (en) 1998-03-06 1998-06-30 Preparing a HGH viscosity index, low branch index dewaxed
EP99904511A EP1060231B1 (de) 1998-03-06 1999-01-29 Herstellung von schmieröl mit hohem viskositätsindex

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2407100A (en) * 2003-10-14 2005-04-20 Chevron Usa Inc Lubricant base oils with optimised branching and high viscosity index
GB2407326A (en) * 2003-10-14 2005-04-27 Chevron Usa Inc Lubricant base oils with optimised branching and high viscosity index
US20220154086A1 (en) * 2019-03-28 2022-05-19 Eneos Corporation Method for producing lubricant base oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919788A (en) * 1984-12-21 1990-04-24 Mobil Oil Corporation Lubricant production process
US5037528A (en) * 1985-11-01 1991-08-06 Mobil Oil Corporation Lubricant production process with product viscosity control
US5282958A (en) * 1990-07-20 1994-02-01 Chevron Research And Technology Company Use of modified 5-7 a pore molecular sieves for isomerization of hydrocarbons
US5643440A (en) * 1993-02-12 1997-07-01 Mobil Oil Corporation Production of high viscosity index lubricants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919788A (en) * 1984-12-21 1990-04-24 Mobil Oil Corporation Lubricant production process
US5037528A (en) * 1985-11-01 1991-08-06 Mobil Oil Corporation Lubricant production process with product viscosity control
US5282958A (en) * 1990-07-20 1994-02-01 Chevron Research And Technology Company Use of modified 5-7 a pore molecular sieves for isomerization of hydrocarbons
US5643440A (en) * 1993-02-12 1997-07-01 Mobil Oil Corporation Production of high viscosity index lubricants

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2407100A (en) * 2003-10-14 2005-04-20 Chevron Usa Inc Lubricant base oils with optimised branching and high viscosity index
GB2407326A (en) * 2003-10-14 2005-04-27 Chevron Usa Inc Lubricant base oils with optimised branching and high viscosity index
GB2407100B (en) * 2003-10-14 2005-12-14 Chevron Usa Inc Process for producing lubricant base oils with optimized branching
US7018525B2 (en) 2003-10-14 2006-03-28 Chevron U.S.A. Inc. Processes for producing lubricant base oils with optimized branching
GB2407326B (en) * 2003-10-14 2007-05-09 Chevron Usa Inc Lubricant base oils with optimized branching
AU2004281377B2 (en) * 2003-10-14 2010-06-03 Chevron U.S.A. Inc. Processes for producing lubricant base oils with optimized branching
US20220154086A1 (en) * 2019-03-28 2022-05-19 Eneos Corporation Method for producing lubricant base oil

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