EP0413795B1 - Synthetische schmierölzusammensetzung und verfahren - Google Patents

Synthetische schmierölzusammensetzung und verfahren Download PDF

Info

Publication number
EP0413795B1
EP0413795B1 EP90904065A EP90904065A EP0413795B1 EP 0413795 B1 EP0413795 B1 EP 0413795B1 EP 90904065 A EP90904065 A EP 90904065A EP 90904065 A EP90904065 A EP 90904065A EP 0413795 B1 EP0413795 B1 EP 0413795B1
Authority
EP
European Patent Office
Prior art keywords
composition
lubricant
oligomers
catalyst
oligomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90904065A
Other languages
English (en)
French (fr)
Other versions
EP0413795A1 (de
Inventor
Bruce Patrick Pelrine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Priority to AT90904065T priority Critical patent/ATE88493T1/de
Publication of EP0413795A1 publication Critical patent/EP0413795A1/de
Application granted granted Critical
Publication of EP0413795B1 publication Critical patent/EP0413795B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties

Definitions

  • This invention relates to novel compositions prepared from synthetic lubricants by reaction with olefins and to the process for their production.
  • the invention particularly pertains to the modification of a high viscosity index synthetic lubricant oligomer fraction employing low molecular weight by-product oligomer fractions as reactant.
  • the modified synthetic lubricants are themselves useful, inter alia, as lubricants with improved thermal stability.
  • One characteristic of the molecular structure of 1-alkene oligomers that has been found to correlate very well with improved lubricant properties in commercial synthetic lubricants is the ratio of methyl to methylene groups in the oligomer.
  • the ratio is called the branch ratio and is calculated from infra red data as discussed in "Standard Hydrocarbons of High Molecular Weight", Analytical Chemistry , Vol.25, no.10, p.1466 (1953). Viscosity index has been found to increase with lower branch ratio.
  • branch ratio is calculated from infra red data as discussed in "Standard Hydrocarbons of High Molecular Weight", Analytical Chemistry , Vol.25, no.10, p.1466 (1953). Viscosity index has been found to increase with lower branch ratio.
  • oligomeric liquid lubricants exhibiting very low branch ratios have not been synthesized from 1-alkenes.
  • oligomers prepared from 1-decene by either cationic polymerization or Ziegler catalyst polymerization have branch ratios of greater than 0.20.
  • Shubkin, Ind. Eng.Chem. Prod. Res. Dev. 1980, 19, 15-19, provides an explanation for the apparently limiting value for branch ratio based on a cationic polymerization reaction mechanism involving rearrangement to produce branching.
  • Other explanations suggest isomerization of the olefinic group in the one position to produce an internal olefin as the cause for branching.
  • U.S.Patent 4,282,392 to Cupples et al. discloses an alpha-olefin oligomer synthetic lubricant having an improved viscosity-volatility relationship and containing a high proportion of tetramer and pentamer via a hydrogenation process that effects skeletal rearrangement and isomeric composition.
  • the composition claimed is a trimer to tetramer ratio no higher than one to one. The branch ratio is not disclosed.
  • HVI-PAO novel lubricant compositions
  • novel lubricant compositions comprising polyalpha-olefins and methods for their preparation employing as catalyst reduced chromium on a silica support
  • the HVI-PAO lubricants are made by a process which comprises contacting C6-C20 1-alkene feedstock with reduced valence state chromium oxide catalyst on porous silica support under oligomerizing conditions in an oligomerization zone whereby high viscosity, high VI liquid hydrocarbon lubricant is produced having branch ratios less than 0.19 and pour point below -15°C.
  • the process is distinctive in that little isomerization of the olefinic bond occurs compared to known oligomerization methods to produce polyalpha-olefins using Lewis acid catalyst.
  • Lubricants produced by the process cover the full range of lubricant viscosities and exhibit a remarkably high viscosity index (VI) and low pour point even at high viscosity.
  • the as-synthesized HVI-PAO oligomer has a preponderance of terminal olefinic unsaturation.
  • the HVI-PAO oligomer is hydrogenated to improve stability for lubricant applications. Those modifications to HVI-PAO oligomers that result in improved thermal stability are particularly preferred.
  • alpha-olefin dimer In the preparation of the novel HVI-PAO lubricant, alpha-olefin dimer,,containing olefinic unsaturation can be separated from the oligomerization reaction.
  • the composition of the dimer mixture conforms to the unique specificity of the oligomerization reaction in that little double bond isomerization is found and shows a low branch ratio. Separation of the dimer, representing non-lube range molecular weight material, is necessitated to control product volatility and viscosity.
  • the non-lube range dimer fraction by-product yield increases in proportion to that lowering in average molecular weight of the oligomerization product.
  • the increase in dimer by-product yield represents a substantial economic burden on the overall process to produce useful lower viscosity lubricant.
  • non-lube range olefins produced in the oligomerization process can be effectively converted to lube range products by reaction with the lube range material. It has also been found that other olefins may also be used in a similar manner and that the reaction products possess unexpectedly better thermal stability than the original lube range material, regardless of the character of the olefin. The yield of lubricant material is also improved in this way.
  • a method for improving the thermal stability of synthetic lube produced by the oligomerization of a 1-alkene (alpha-olefin) comprises reacting the oligomer with an olefin.
  • the reaction which is believed to proceed mainly by alkylation with some side reactions such as cracking, isomerization and polymerization, is carried out in the presence of an alkylation catalyst under conditions appropriate for alkylation.
  • a preferred olefin for reaction with the lube oligomer is the lower molecular weight, non-lubricant olefin produced in the course of the oligomerization of the alpha-olefin starting arterial.
  • Using these lower molecular weight materials in this way not only improves the thermal stability of the final lube products but also increases the product yield and olefin utilization, thus avoiding the economic penalty attached to the production of the lower viscosity range lubricants.
  • the lower molecular weight non-lubricant range olefinic hydrocarbons produced in the course of the oligomerization of 1-alkenes are used to upgrade the lube range oligomer.
  • Effective acidic catalysts comprise alkylation catalysts, preferably the open-pore catalyst such as those derived from fluorided alumina.
  • composition of the present invention is polymeric residue of linear C6-C20 1-alkenes, which has at least one higher alkyl (C12-C40) branch per oligomer molecule.
  • the hydrocarbon oligomer contains from 30 to 1300 carbon atoms per molecule.
  • novel composition has a methyl to methylene branch ratio of less than 0.19 and pour point below -15°C.
  • the process for the conversion of the alpha-olefins to the desired thermally stable, high viscosity index lubricant product comprises: contacting C6 to C20 alpha-olefin feedstock, or mixtures thereof, under oligomerization conditions with a reduced valence state Group VIB metal catalyst on porous support whereby an oligomerization product mixture is produced containing oligomers comprising olefinic lubricant range hydrocarbons and olefinic non-lubricant range hydrocarbon by-product; separating the lubricant and non-lubricant hydrocarbons and hydrogenating the lubricant range hydrocarbons; contacting the hydrogenated hydrocarbons and the olefinic by-product hydrocarbons as alkylating agent in an alkylation zone under alkylating conditions with acidic catalyst whereby alkylated lubricant range hydrocarbons are produced.
  • Figure 1 shows the relationship between degree of alkylation and viscosity loss for modified HVI-PAO.
  • Figure 2 shows the relationship between viscosity and viscosity index for HVI-PAO oligomer and modified HVI-PAO oligomer.
  • synthetic hydrocarbon lubricants are modified by reaction with alkenes including the unique olefin dimers produced as by-product in the oligomerization reaction that produces the synthetic lubricant.
  • alkenes which can be used to react with HVI-PAO oligomers as described herein include C2-C40 linear or branched alkenes but, in particular, 1-alkenes and the olefinic dimer by-product of the HVI-PAO oligomerization reaction.
  • Preferred 1-alkenes for reaction with HVI-PAO oligomers include those olefins containing from 6 to 14 carbon atoms such as 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene and branched chain isomers such as 4-methyl-1-pentene.
  • Particularly preferred 1-alkenes are the C8 to C10 alpha-olefins, e.g., 1-octene, 1-decene and the olefin dimers produced in the oligomerization process for producing the initial lube range materials.
  • the oligomerization reaction is carried out by the oligomerization of 1-alkenes in contact with reduced metal catalysts, preferably reduced chromium oxide on a silica support.
  • a characteristic of the novel oligomerization reaction from which the by-product dimers used as alkylating agent in the present invention are produced is the production of mixtures of dialkyl vinylidenic and 1,2 dialkyl or trialkyl mono-olefin oligomers, or HVI-PAO oligomers, as determined by infra-red and NMR analysis.
  • the HVI-PAO oligomers have the following regular head-to-tail structure where n is preferably 0 to 17, terminating in olefinic unsaturation: with some head-to-head connections.
  • the HVI-PAO process produces a surprisingly simpler and useful dimer compared to the dimer produced by 1-alkene oligomerization with BF3 or AlCl3 as commercially practiced.
  • the by-product dimer from 1-decene oligomerization according to the HVI-PAO process which can be used as alkylating olefin in the present invention, has been found to contain three major components, as determined by gas chromatography (GC). Based on C -13 NMR analysis, the unhydrogenated components were found to be 8-eicosene, 9-eicosene, 2-octyldodecene and 9-methyl-8 or 9-methyl-9-nonadecene.
  • Olefins suitable for use as starting material in the preparation of olefinic HVI-PAO oligomers and the by-product dimer used as starting material in the present invention include those olefins containing from 6 to 14 carbon atoms such as 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene and branched chain isomers such as 4-methyl-1-pentene.
  • a preferred 1-alkene is 1-decene.
  • olefin-containing refinery feedstocks or effluents are also suitable for use. However, the olefins used in this invention are preferably alpha olefinic as for example 1-octene to 1-dodecene and more preferably 1-decene, or mixtures of such olefins.
  • the lube range HVI-PAO oligomers of alpha-olefins used in this invention have a low branch ratio of less than 0.19 and superior lubricating properties compared to the alpha-olefin oligomers with a high branch ratio, as produced in all known commercial methods.
  • This class of unsaturated HVI-PAO alpha-olefin oligomers are prepared by oligomerization reactions in rich a major proportion of the double bonds of the alpha-olefins are not isomerized. These reactions include alpha-olefin oligomerization by supported metal oxide catalysts, such as Cr compounds on silica or other supported IUPAC Periodic Table Group VIB compounds.
  • the catalyst most preferred is a lower valence Group VIB metal oxide on an inert support.
  • Preferred supports include silica, alumina, titania, silica alumina, magnesia and the like.
  • the support arterial binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 angstroms are preferred.
  • the support arterial usually has high surface area and large pore volumes with average pore size of 40 x 10 ⁇ 7mm to 350 x 10 ⁇ 7mm.
  • the high surface area are beneficial for supporting large amount of highly dispersive, active chromium metal centers and to give maximum efficiency of metal usage, resulting in very high activity catalyst.
  • the support should have large average pore openings of at least 40 x 10 ⁇ 7mm, with an average pore opening of 60 x 10 ⁇ 7mm to 300 x 10 ⁇ 7mm preferred. This large pore opening will not impose any diffusional restriction of the reactant and product to and away from the active catalytic metal centers, thus further optimizing the catalyst productivity.
  • a silica support with good physical strength is preferred to prevent catalyst particle attrition or disintegration during handling or reaction.
  • the supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for example, ethanol,methanol, or acetic acid.
  • the solid catalyst precursor is then dried and calcined at 200 to 900°C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, CO, H2, NH3, H2S, CS2, CH3SCH3, CH3SSCH3,metal alkyl containing compounds such as R3Al, R3B,R2Mg, RLi, R2Zn, where R is alkyl, alkoxy, aryl and the like. Preferred are CO or H2 or metal alkyl containing compounds.
  • the Group VIB metal may be applied to the substrate in reduced form, such as CrII compounds.
  • the resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to 250°C at a pressure of 10.1 kPa (0.1 atmosphere) to 34580 kPa (5000 psi).
  • oligomerization temperature is preferably between 90-250°C at a feedstock to catalyst weight ratio between 10:1 and 30:1.
  • Contact time of both the olefin and the catalyst can vary from one second to 24 hours.
  • the catalyst can be used in a batch type reactor or in a fixed bed, continuous-flow reactor.
  • the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is then mixed and dried at room temperature.
  • the dry solid gel is purged at successively higher temperatures to 600°C for a period of 16 to 20 hours.
  • the catalyst is cooled down under an inert atmosphere to a temperature of 250 to 450°C and a stream of pure reducing agent is contacted therewith for a period when enough CO has passed through to reduce the catalyst as indicated by a distinct color change from bright orange to pale blue.
  • the catalyst is treated with an amount of CO equivalent to a two-fold stoichiometric excess to reduce the catalyst to a lower valence CrII state.Finally the catalyst is cooled to room temperature and is ready for use.
  • the product oligomers have a very wide range of viscosities with high viscosity indices suitable for high performance lubrication use.
  • the product oligomers also have atactic molecular structure of mostly uniform head-to-tail connections with some head-to-head type connections in the structure.
  • These low branch ratio oligomers have high viscosity indices at least 15 to 20 units and typically 30-40 units higher than equivalent viscosity prior art oligomers, which regularly have higher branch ratios and correspondingly lower viscosity indices. These low branch oligomers maintain better or comparable pour points.
  • Branch ratio wt fraction of methyl group 1-(wt fraction of methyl group)
  • the unique olefinic dimers used as alkylating agent in the present invention are produced as by-product of the HVI-PAO oligomerization reaction.
  • the oligomerization reaction mixture is separated from the catalyst and separated by vacuum distillation to remove unreacted alpha-olefin and lower boiling by-products of the oligomerization reaction, such as alpha-olefin dimer.
  • This provides a lubricant basestock of suitably high volatility and viscosity. While other methods known to those skilled in the art, such as solvent extraction, may be used to separate the alpha-olefin dimer by-product, distillation is preferred.
  • the reaction provides as a by-product the olefinic dimer used as alkylating agent or reactant in the present invention.
  • the dimer is separated by distillation from the oligomerization reaction mixture.
  • the temperature is then set at 600°C with dry air purging for 16 hours. At this time the catalyst is cooled under N2 to a temperature of 300°C. Then a stream of pure CO (99.99% from Matheson) is introduced for one hour. Finally, the catalyst is cooled to room temperature under N2 and ready for use.
  • Example 1 The catalyst prepared in Example 1 (3.2 g ) is packed in a 9.5 mm (3/8 ⁇ ) stainless steel tubular reactor inside an N2 blanketed dry box. The reactor under N2 atmosphere is then heated to 150°C by a single-zone Lindberg furnace. Pre-purified 1-hexene is pumped into the reactor at 1069 kPa (140 psi) and 20 ml/hr. The liquid effluent is collected and stripped of the unreacted starting material and the low boiling material at 6.7 kPa (0.05 mm Hg). The residual clear, colorless liquid has viscosities and VI's suitable as a lubricant base stock.
  • a commercial chrome/silica catalyst which contains 1% Cr on a large-pore volume synthetic silica gel is used.
  • the catalyst is first calcined with air at 800°C for 16 hours and reduced with CO at 300°C for 1.5 hours. Then 3.5 g of the catalyst is packed into a tubular reactor and heated to 100°C under the N2 atmosphere. 1-Hexene is pumped through at 28 ml per hour at 101 kPa (1 atmosphere). The products are collected and analyzed as follows:
  • lubricants prepared by the methods described above contain olefinic unsaturation they are typically hydrogenated to stabilize them for lubricant use.
  • very high molecular weight oligomers may not need to be hydrogenated since the number of olefin bonds in such oligomers is comparatively small.
  • Lower molecular weight oligomers of particular interest in the present invention to provide low viscosity lubricants are hydrogenated by means well known to those skilled in the lubricant arts.
  • the thermal stability of the hydrogenated lubricant range oligomers is improved by reaction with an olefin, preferably the non-lube range olefins produced as a by-product in the oligomerization reaction.
  • an olefin preferably the non-lube range olefins produced as a by-product in the oligomerization reaction.
  • the reaction employed herein to modify HVI-PAO oligomer is described as an alkylation reaction and the reactant alkene as an alkylating agent.
  • alkylation is a significant reaction occurring in the instant invention carried out under alkylation conditions, other reactions are occurring as well, e.g., cracking, isomerization and polymerization. Accordingly, the term alkylation as used herein includes all those reactions occurring that result in the beneficial modification of HVI-PAO oligomers as herein described.
  • the catalyst used in the alkylation reaction of the present invention is preferably a porous, solid acidic catalyst containing large pore openings.
  • a preferred catalyst is a fluorided alumina, prepared as described hereinafter.
  • Other useful solid catalysts include acidic zeolites.
  • Zeolites useful as catalysts in the present invention include all natural or synthetic acidic large pore size zeolites, typically with a pore size of 6.4 x 10 ⁇ 7mm to 7.5 x 10 ⁇ 7mm.
  • particularly useful catalysts include the acidic form of ZSM-4, ZSM-12, ZSM-20, Faujasite X & Y with pore size of 7.4 x 10 ⁇ 7mm (7,4 Angstroms), Cancrinite, Gmelinite, Mazzite, Mordenite and Offretite.
  • Other alkylation catalysts which are also useful in the process of the present invention include conventional alkylation catalysts known to those skilled in the art including HF, AlCl3, BF3 and BF3 complexes, SbCl5, SnCl4, TiCl4, P2O5, H2SO4, ZnCl2 and acidic clays.
  • the alkylation reaction of the present invention produces alkylated synthetic lube containing large alkyl branches.
  • the alkyl branches contain between 12 and 40 carbon atoms, or mixtures thereof, depending on the olefin used in the alkylation reaction, e.g. the dimer of the C6-C20 alpha-olefin.
  • Branches containing between 2 and 40 carbon atoms can be produced when monomeric olefins, e.g. ethylene, propylene, 1-decene, are used as alkylating agent.
  • branching introduced by the olefin can be controlled by the mole ratio of alkene such as dimer olefin to synthetic lube in the alkylation reaction.
  • the molar ratio of olefin to the lube range material will be between 40 to 1 and 1 to 1, preferably between 5 to 1 and 1 to 1 molar ratio.
  • the product characteristics can range from synthetic lube containing at least one large alkyl group per mole to a reaction product containing a mixture of alkylated synthetic lube and synthetic lube.
  • alkylation with alkene dimer according to the present invention produces an alkylated product that maintains the high VI and low pour point of the unalkylated HVI-PAO oligomer and shows an increase in thermal stability.
  • alumina Harshaw Catapal-S, 0.8 mm (1/32 inch) extrudate
  • 25 grams of alumina Harshaw Catapal-S, 0.8 mm (1/32 inch) extrudate
  • aluminum nitrate nona hydrate in 30ml water for 1 hour.
  • excess water is removed under reduced pressure at 80°C.
  • the aluminum nitrate impregnated alumina is then contacted with 8.17 grams ammonium fluoride in 50ml water to form aluminum fluoride in the alumina.
  • the aluminum fluoride/alumina catalyst is dried under vacuum at 115°C for 18 hours and then calcined at 538°C for 12 hours.
  • Synthetic lube is prepared according to the process for HVI-PAO reacting 1-decene over chromium supported silica as previously described herein.
  • the unsaturated decene dimer is separated by distillation as a by-product to remove unreacted decene and lubricant product hydrogenated.
  • the lube product viscosity was 9.2 mm2/s (9.2cS), measured at 100°C.
  • Alkylation reactions are performed in a fixed-bed reactor.
  • the unit is maintained at 2861 kPa (400 psig) and the liquid hourly space velocity (LHSV) is 0.5.
  • the feed is a mixture of 315 grams of 1-decene HVI-PAO lube and 140 grams of 1-decene dimer representing 30.8 weight percent.
  • Alkylation reactions are carried out at reaction temperatures of 167, 204 and 250°C, Examples 7-1, 7-2 & 7-3. The results of these alkylation reactions are presented in Table 1
  • HVI-PAO fed Based upon the initial percent of HVI-PAO present in the feed, the amount of HVI-PAO fed can be calculated and is found in Table 1 for each example. After alkylation, a weight increase is expected and is noted in the table. Weight increases vary between 8.4 and 15.9 percent and appear to be a function of reaction temperature.
  • the overall yield of final product is increased by the addition by alkylation of dimer by-product to the synthetic HVI-PAO lubricant.
  • the alkylated product has an increased viscosity compared to the starting HVI-PAO lubricant and maintains the high VI characteristic of these oligomers.
  • alumina 25 grams is contacted with a solution comprised of 5.3 grams of alumina nitrate (nona-hydrate) in 30ml of water for one hour. Excess water is removed by vacuum. The dried alumina nitrate impregnated alumina is then contacted with another solution containing 2.7 grams of ammonium fluoride in 50ml of water. After five minutes the excess water is decanted and the resulting fluorided alumina is dried in vacuum at 95°C for three days. This catalyst contains 5% aluminum fluoride.
  • HVI-PAO is alkylated as described above using the same fluorided alumina catalyst, except 1-decene alone was mixed with the HVI-PAO for reaction instead of HVI-PAO dimer.
  • Table 4 presents the thermal stability test results on the product of Example 9.
  • Figure 2 shows a comparison of viscosity and VI for unreacted vs reacted HVI-PAO illustrating that VI remains unchanged for the reacted product of the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (20)

  1. Verfahren zur Umwandlung von α-Olefinen in Oligomere im Schmiermittelbereich mit hohem Viskositätsindex und mit erhöhter Ausbeute, wobei dieses Verfahren umfaßt:
    i. Kontakt des α-Olefin-Ausgangsmaterials mit C₆ bis C₂₀ oder Mischungen davon bei Oligomerisierungsbedingungen mit einem Metallkatalysator der Gruppe VIB mit reduziertem Wertigkeitszustand auf einem porösen Träger, um eine Produktmischung zu erzeugen, die Oligomere mit hohem Viskositätsindex, geringersiedende olefinische Kohlenwasserstoff-Nebenprodukte und ein unreagiertes α-Olefin-Ausgangsmaterial umfaßt;
    ii. Trennung der Oligomere, der olefinischen Kohlenwasserstoff-Nebenprodukte und des unreagierten Ausgangsmaterials und Hydrierung der Oligomere; und
    iii. Kontakt der hydrierten Oligomere mit einem Alkylierungsmittel, das die olefinischen Kohlenwasserstoff-Nebenprodukte vom Schritt ii. umfaßt, in einer Alkylierungszone bei Alkylierungsbedingungen mit einem festen sauren Katalysator, um alkylierte Oligomere im Schmiermittelbereich mit hohem Viskositätsindex zu erzeugen.
  2. Verfahren nach Anspruch 1, worin das Alkylierungsmittel die olefinische C₁₂-C₄₀-Dimerfraktion des Oligomerisierungsprozesses umfaßt.
  3. Verfahren nach Anspruch 1, worin der feste saure Katalysator aus der Gruppe genommen wird, die einen großporigen Zeolith und fluoridisiertes Aluminiumoxid umfaßt.
  4. Verfahren nach Anspruch 1, worin die alkylierten Kohlenwasserstoffe im Schmiermittelbereich einen Viskositätsindex von mehr als 130, einen Pourpoint von weniger als -15°C und eine Viskosität zwischen 3 und 750 mm²/s aufweisen.
  5. Verfahren nach Anspruch 1, worin der Metallkatalysator der Gruppe VIB mit Kohlenmonoxid reduziertes Chromoxid auf Siliciumdioxid umfaßt.
  6. Verfahren nach Anspruch 1, worin das Alkylierungsmittel C₂-C₄₀ -Alken umfaßt.
  7. Verfahren nach Anspruch 1, worin der saure Katalysator aus HF, AlCl₃, BF₃ und BF₃-Komplexen, SbCl₅, SnCl₄, TiCl₄, P₂O₅, H₂SO₄, ZnCl₄ und sauren Tonen ausgewählt wird.
  8. Verfahren nach Anspruch 1, worin der saure Katalysator großporige Zeolithe umfaßt.
  9. Verfahren nach Anspruch 1, worin der saure Katalysator fluoridisiertes Aluminiumoxid umfaßt.
  10. Verfahren nach Anspruch 1, worin der Metallkatalysator der Gruppe VIB mit reduziertem Wertigkeitszustand auf dem porösen Träger reduziertes Chromoxid auf Siliciumdioxid umfaßt.
  11. Verfahren nach Anspruch 10, worin der Metallkatalysator mit Kohlenmonoxid reduziert wird.
  12. Verfahren nach Anspruch 2, worin das Alkylierungsmittel eine olefinische C₁₂-C₄₀-Kohlenwasserstofffraktion außerhalb des Schmiermittelbereichs des Oligomerisierungsproduktes umfaßt.
  13. Flüssige Oligomer-Schmiermittelzusammensetzung, die nach dem Verfahren nach einem der Ansprüche 1 bis 12 hergestellt wurde und C₃₀-C₁₃₀₀-Kohlenwasserstoffe umfaßt, die mindestens eine höhere Alkylverzweigung pro Oligomermolekül umfassen, wobei diese Alkylverzweigung 12 bis 40 Kohlenstoffatome umfaßt.
  14. Zusammensetzung nach Anspruch 13, worin diese ein Methyl/Methylen-Verzweigungsverhältnis von weniger als 0,19 und einen Pourpoint unterhalb -15°C aufweist.
  15. Zusammensetzung nach Anspruch 13, die einen Viskositätsindex von mehr als 130 und eine Viskosität bei 100°C von 3 bis 750 mm²/s aufweist.
  16. Zusammensetzung nach Anspruch 13, worin die Alkylverzweigung 20 Kohlenstoffatome enthält.
  17. Zusammensetzung nach Anspruch 13, worin das flüssige Oligomer-Schmiermittel ein im wesentliches lineares flüssiges Oligomer-Schmiermittel umfaßt.
  18. Zusammensetzung nach Anspruch 13, worin die Oligomerzusammensetzung den hydrierten polymeren Rückstand von 1-Alkenen umfaßt, der von linearen 1-Alkenen mit C₆-C₂₀ entnommen wurde.
  19. Zusammensetzung nach Anspruch 18, worin die 1-Alkene 1-Decen umfassen und die höhere Alkylverzweigung 20 Kohlenstoffatome enthält.
  20. Zusammensetzung nach Anspruch 18 mit einem Viskositätsindex von mehr als 130 und einer Viskosität bei 100°C zwischen 3 mm²/s und 750 mm²/s.
EP90904065A 1989-02-21 1990-02-15 Synthetische schmierölzusammensetzung und verfahren Expired - Lifetime EP0413795B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90904065T ATE88493T1 (de) 1989-02-21 1990-02-15 Synthetische schmieroelzusammensetzung und verfahren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31357689A 1989-02-21 1989-02-21
US313576 1989-02-21

Publications (2)

Publication Number Publication Date
EP0413795A1 EP0413795A1 (de) 1991-02-27
EP0413795B1 true EP0413795B1 (de) 1993-04-21

Family

ID=23216279

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90904065A Expired - Lifetime EP0413795B1 (de) 1989-02-21 1990-02-15 Synthetische schmierölzusammensetzung und verfahren

Country Status (5)

Country Link
EP (1) EP0413795B1 (de)
JP (1) JP2945134B2 (de)
AU (1) AU629618B2 (de)
CA (1) CA2027547C (de)
WO (1) WO1990010050A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990709A (en) * 1989-04-28 1991-02-05 Mobil Oil Corporation C2-C5 olefin oligomerization by reduced chromium catalysis
US4967032A (en) * 1989-09-05 1990-10-30 Mobil Oil Corporation Process for improving thermal stability of synthetic lubes
DE4136617C2 (de) * 1991-11-07 1997-08-14 Henkel Kgaa Füllmasse und deren Verwendung
US5902849A (en) * 1991-11-07 1999-05-11 Henkel Kommanditgesellschaft Auf Aktien Filling compound
US7572943B2 (en) * 2005-12-20 2009-08-11 Chevron U.S.A. Inc. Alkylation of oligomers to make superior lubricant or fuel blendstock
US8168838B2 (en) 2009-01-21 2012-05-01 Shell Oil Company Hydrocarbon compositions useful as lubricants

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB636372A (en) * 1947-03-07 1950-04-26 Standard Oil Dev Co Production of synthetic lubricating oil
US4827064A (en) * 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
US4827073A (en) * 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties

Also Published As

Publication number Publication date
JPH03504141A (ja) 1991-09-12
JP2945134B2 (ja) 1999-09-06
CA2027547C (en) 1999-08-31
AU5171490A (en) 1990-09-26
WO1990010050A1 (en) 1990-09-07
EP0413795A1 (de) 1991-02-27
CA2027547A1 (en) 1990-08-22
AU629618B2 (en) 1992-10-08

Similar Documents

Publication Publication Date Title
US5264642A (en) Molecular weight control of olefin oligomers
US4827073A (en) Process for manufacturing olefinic oligomers having lubricating properties
US4967032A (en) Process for improving thermal stability of synthetic lubes
US4827064A (en) High viscosity index synthetic lubricant compositions
US4990709A (en) C2-C5 olefin oligomerization by reduced chromium catalysis
US5254274A (en) Alkylaromatic lubricant fluids
US5113030A (en) High viscosity index lubricant compositions
US4914254A (en) Fixed bed process for high viscosity index lubricant
EP0417273B1 (de) Verfahren zur alkylierung von aromaten mit dimer eines alpha-olefins
US4990711A (en) Synthetic polyolefin lubricant blends having high viscosity indices
US5132478A (en) Alkylaromatic lubricant fluids
EP0442656B1 (de) Schmiermittel mit hohem Viskositätsindex aus niedrigen Olefinoligomeren
US4906799A (en) Process for the production of reduced viscosity high VI hydrocarbon lubricant
EP0511756B1 (de) Verfahren zur Herstellung von alkylaromatischen Schmiermitteln
US5026948A (en) Disproportionation of alpha-olefin dimer to liquid lubricant basestock
EP0422019B1 (de) Olefinoligomere mit schmierungseigenschaften und verfahren zu ihrer herstellung
US4417082A (en) Thermal treatment of olefin oligomers via a boron trifluoride process to increase their molecular weight
EP0413795B1 (de) Synthetische schmierölzusammensetzung und verfahren
US5015795A (en) Novel synthetic lube composition and process
US4395578A (en) Oligomerization of olefins over boron trifluoride in the presence of a transition metal cation-containing promoter
US4967030A (en) Hydrocracking high viscosity synthetic lubricant
US4996384A (en) Regeneration of reduced metal oxide oligomerization catalyst
CA2042103A1 (en) Process for co-oligomerizing 1,3-di-isopropenyl benzene and alpha-olefins to prepare synthetic lubricant base stocks having improved properties
DE69001412T2 (de) Synthetische schmieroelzusammensetzung und verfahren.
CA2034687A1 (en) C2-c5 olefin oligomerization by reduced chromium catalysis

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901020

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE FR GB IT NL SE

17Q First examination report despatched

Effective date: 19910717

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE FR GB IT NL SE

REF Corresponds to:

Ref document number: 88493

Country of ref document: AT

Date of ref document: 19930515

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 69001412

Country of ref document: DE

Date of ref document: 19930527

ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 90904065.1

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990119

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19990121

Year of fee payment: 10

Ref country code: GB

Payment date: 19990121

Year of fee payment: 10

Ref country code: AT

Payment date: 19990121

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19990122

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19990126

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19990208

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000215

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000228

BERE Be: lapsed

Owner name: MOBIL OIL CORP.

Effective date: 20000228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000901

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20000215

EUG Se: european patent has lapsed

Ref document number: 90904065.1

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001031

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20000901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050215