EP1204723B1 - Procede de preparation d'huile minerale lubrifiante - Google Patents

Procede de preparation d'huile minerale lubrifiante Download PDF

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EP1204723B1
EP1204723B1 EP00948000A EP00948000A EP1204723B1 EP 1204723 B1 EP1204723 B1 EP 1204723B1 EP 00948000 A EP00948000 A EP 00948000A EP 00948000 A EP00948000 A EP 00948000A EP 1204723 B1 EP1204723 B1 EP 1204723B1
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fischer
tropsch
process according
base oil
product
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EP1204723A1 (fr
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Eric Duprey
Henri Francois Kessler
Jean-Louis Paillaud
Valentin Panov Valtchev
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/304—Pour point, cloud point, cold flow properties
    • 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 invention relates to a process for preparing a lubricating base oil from a hydrocarbon feed selected from a synthetic wax.
  • a catalyst e.g., a ruthenium, iron or cobalt catalyst
  • base oils can be obtained by catalytically converting the Fischer-Tropsch wax obtained from such process.
  • EP-A-776959 describes a process to prepare a base oil having a viscosity index (VI) of 151, a pour point of -27 °C and a Noack volatility of 8.8% by weight.
  • the base oil was prepared by first subjecting a synthetic wax, also referred to as a Fischer-Tropsch wax, to a hydroisomerisation step. Subsequently the fraction boiling above 390 °C of the effluent of the hydroisomerisation step is catalytically dewaxed using a silica-bound surface-dealuminated ZSM-23 catalyst.
  • US-A-5059299 describes a process to prepare a base oil having a pour point of -20 °C and a VI of 159 by first hydroisomerisation of the 390 °C+ fraction of a Fischer-Tropsch wax followed by solvent dewaxing.
  • US-A-5834522 describes a process in which a Fischer-Tropsch wax is first subjected to a hydrotreatment step in which unsaturated and/or oxygenated products present in the Fischer-Tropsch wax are removed.
  • the hydrotreated product having a T10vol% of 258 °C and a T90vol% of 493 °C is subsequently subjected to a hydroisomerisation step and finally solvent dewaxed.
  • the resulting base oil had a VI of 142 and a pour point of -21 °C.
  • EP-A-668342 describes the preparation of a base oil from a Fischer-Tropsch wax, in which first the Fischer-Tropsch wax is subjected to a hydrotreating step in which no isomerisation or cracking occurs. The hydrotreated effluent is subsequently subjected to a hydrocracking/hydroisomerisation step followed by a pour point reduction step.
  • the pour point reduction step can be performed by means of solvent dewaxing, catalytic dewaxing or isomerisation dewaxing, also referred to as isodewaxing.
  • US-A-5882505 describes converting a Fischer-Tropsch wax by first subjecting the wax to a hydroisomerisation step followed by catalytic dewaxing. According to the specification the hydroisomerisation step is to provide base oils with good cold flow properties.
  • a disadvantage of the above described processes is that a multiple of reaction steps are required to obtain the final base oil product.
  • the object of the present invention is a simple process which yields base oil products having a high viscosity index and a low pour point.
  • US-A-5362378 discloses a one step process to prepare a base oil starting from a Fischer-Tropsch derived feedstock.
  • Example 1 illustrates the conversion of Fischer-Tropsch wax using a Pt/zeolite beta catalyst.
  • the base oil yield calculated as the fraction boiling above 343 °C was 38 wt% on feed.
  • the viscosity index (VI) of the base oil was 151 and a pour point was -17.7 (0 °F).
  • the object of the present invention is achieved by the following process.
  • Process for preparing a lubricating base oil by contacting a synthetic waxes, which wax is obtained by a Fischer-Tropsch process and has not been subjected to a hydroisomerisation treatment, with a catalyst composition comprising at least a hydrogenation component, dealuminated aluminosilicate zeolite crystallites of the MTW type and a low acidity refractory oxide binder material which is essentially free of alumina.
  • the Fischer-Tropsch wax can be converted to a base oil product having excellent properties in one hydroconversion step instead of a hydroisomerisation step followed by a dewaxing step.
  • Excellent properties are for example a pour point below -27 °C and a VI of above 140.
  • the synthetic wax is the fraction boiling above 350 °C of a product obtained by a Fischer-Tropsch process.
  • the synthetic wax will also be referred to as the Fischer-Tropsch wax.
  • the product directly obtained by the Fischer-Tropsch process will be referred to as the Fischer-Tropsch product.
  • the Fischer-Tropsch product When reference is made to boiling points and boiling point ranges the boiling point at atmospheric pressure is meant.
  • the Fischer-Tropsch wax has an initial boiling point of above 350 °C.
  • the congealing point of the Fischer-Tropsch wax is preferably at least 50 °C.
  • the Fischer-Tropsch process converts synthesis gas to a Fischer-Tropsch product comprising gaseous and liquid hydrocarbons and a Fischer-Tropsch wax.
  • Synthesis gas is suitably prepared by gasification of natural gas, a hydrocarbon fuel or coal under known conditions.
  • the Fischer-Tropsch product does not contain the sulphur, nitrogen or metal impurities normally found in crude oil, but is known to contain water, trace metals and a number of unsaturated compounds and oxygenate compounds such as alcohols, ketones, aldehydes, etc.
  • a method to prepare a Fischer-Tropsch product is for example described in the afore mentioned EP-A-668342.
  • the Fischer-Tropsch product including the wax, may have been subjected to a hydrotreatment process step in order to lower the content of these unsaturated or oxygenated products. These compounds may cause a deactivation of certain catalysts used in further downstream treatment of the Fischer-Tropsch product.
  • a hydrotreatment process step hydrogen is reacted with the feed in the presence of a hydrotreatment catalyst.
  • An examples of such a hydrotreating step is described in the afore mentioned US-A-5834522 and EP-A-668342. It must be understood that no or no substantial hydroisomerisation and/or cracking as illustrated in the above cited prior art takes place during such a hydrotreating step.
  • substantially no hydrocracking or hydroisomerisation is defined by that less than 10%, preferably less than 5%, of the fraction of the feed boiling above 370 °C in % by weight is converted to a fraction boiling below 370 °C.
  • the hydrotreating step will be typically performed prior to the fractionation of the Fischer-Tropsch product into a Fischer-Tropsch wax and lower boiling fractions.
  • These lower boiling fractions can be processed into valuable products by known processes as exemplified in some of the above referred to publications.
  • only the amount of the Fischer-Tropsch wax is removed from the Fischer-Tropsch product that is needed to prepare lubricating base oils.
  • the remaining part of the Fischer-Tropsch product including the remaining part of the Fischer-Tropsch wax is sent to a hydroisomerisation step as defined above.
  • the products thus obtained are fractionated and into valuable lower boiling fuel fractions, for example naphtha, kerosine and gas oil fractions.
  • Any lower boiling by-products and/or unconverted Fischer-Tropsch wax obtained in the catalytic dewaxing process according to the invention can suitable be routed to either the hydroisomerisation step or to the fractionator means here above described to further increase the overall yield to lower boiling fuel fractions.
  • the invention is also directed to a process to prepare a lubricating base oil as described above by performing at least the following steps:
  • lower boiling fuel products are prepared next to the lubricating base oil product.
  • the lower boiling fuels are prepared starting from the Fischer-Tropsch product from which all or part of the Fischer-Tropsch wax has been separated from in .step (c), which are subjected to an optional hydrotreating step (step (e)) followed by a hydroisomerisation step (step (f)) and a fractionation step (g).
  • the catalyst composition used in the present invention comprises a hydrogenation component, a surface dealuminated aluminosilicate zeolite crystallites of the MTW type and a low acidity refractory oxide binder material which is essentially free of alumina.
  • a good base oil product can be prepared when a catalyst is used containing ZSM-12, preferably ZSM-12 having a low cristobalite contamination, more preferably containing less than 5 wt% cristobalite.
  • ZSM-12 crystallites are used as obtainable by crystallising a synthesis mixture including a source of silicon, a source of aluminium, a source of a cations, and an organic directing agent having the following general formula (R 1 R 2 R 3 N + -X-N + R 4 R 5 R 6 )Y 2 , in which R 1 -R 6 are organic groups, X is a bivalent aryl group and Y is a anion.
  • the directing agent is preferably hexa-N-methyl-N,N'-p-xylylen-di-ammonium dihydroxide.
  • the sources of silicon, aluminium and cations and the synthesis conditions can be those conventionally applied in the field of preparing aluminosilicate zeolite crystallites. Examples of possible cations are alkaline-earth ions like calcium, rubidium, sodium of which sodium is most preferred. Examples of silicon sources are fumed silica and silica sol. Examples of aluminium sources are aluminium hydroxide, aluminium isopropoxide (as obtainable from Aldrich) and sodium aluminate. R is preferably an C 1 -C 6 alkyl group of which methyl is most preferred.
  • zeolite having the MTW framework topology When referral is made to ZSM-12 a zeolite having the MTW framework topology is meant.
  • This class of zeolites includes CZH-5 as described in GB-A-2079735, Gallosilicate MTW as described in Y.X. Zhi, A. Tuel, Y. Bentaarit and C. Naccache, Zeolites 12, 138 (1992), Nu-13(5) as described in EP-A-59059, Theta-3 as described in EP-A-162719, TPZ-12 as described in US-A-4557919 and VS-12 as described in K. M. Reddy, I. Moudrakovski and A. Sayari, J. Chem. Soc., Chem. Commun. 1994, 1491 (1994)
  • the crystallite size of the aluminosilicate zeolite may be as high as 100 micron. Preferably small crystallites are used in order to achieve an optimum catalytic activity. Preferably crystallites smaller than 10 micron and more preferably smaller than 1 micron are used. The practical lower limit is suitably 0.1 micron.
  • the dewaxing catalyst composition used in the present process also comprises a low acidity refractory oxide binder material which is essentially free of alumina.
  • a low acidity refractory oxide binder material such as silica, zirconia, titanium dioxide, germanium dioxide, boria and mixtures of two or more of these.
  • the most preferred binder is silica.
  • the weight ratio of the molecular sieve and the binder can be anywhere between 5:95 and 95:5. Lower zeolite content may in some cases be advantageous for achieving a higher selectivity. A higher zeolite content is to be preferred when a higher activity is desired.
  • alumina moiety refers to an Al 2 O 3 -unit which is part of the framework of the aluminosilicate zeolite, i.e. which has been incorporated via covalent bindings with other oxide moieties, such as silica (SiO 2 ), in the framework of the aluminosilicate zeolite.
  • the mole percentage of alumina present in the aluminosilicate zeolite is defined as the percentage of moles Al 2 O 3 relative to the total number of moles of oxides constituting the aluminosilicate zeolite (prior to dealumination) or modified molecular sieve (after dealumination).
  • the surface of the zeolite crystallites are selectively dealuminated.
  • a selective surface dealumination results in a reduction of the number of surface acid sites of the zeolite crystallites, whilst not affecting the internal structure of the zeolite crystallites.
  • Dealumination can be attained by methods known in the art. Particularly useful methods are those, wherein the dealumination selectively occurs, or anyhow is claimed to occur selectively, at the surface of the crystallites of the molecular sieve. Examples of dealumination processes are described in the afore mentioned WO-A-9641849.
  • Preferably dealumination is performed by a process in which the zeolite is contacted with an aqueous solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula: (A) 2 /bSiF 6 wherein 'A' is a metallic or non-metallic cation other than H + having the valence 'b'.
  • Examples of cations 'b' are alkylammonium, NH 4 + , Mg ++ , Li + , Na + , K + , Ba ++ , Cd ++ , Cu + , Ca ++ , Cs+, Fe ++ , Co ++ , Pb ++ , Mn ++ , Rb + , Ag + , Sr ++ , Tl + , and Zn ++ .
  • Preferably 'A' is the ammonium cation.
  • the zeolite material may be contacted with the fluorosilicate salt at a pH of suitably between 3 and 7. Such a dealumination process is for example described in US-A-5157191.
  • the dealumination treatment is also referred to as the AHS-treatment.
  • the catalyst composition is preferably prepared by first extruding the aluminosilicate zeolite with the binder and subsequently subjecting the extrudate to a dealumination treatment, preferably the AHS treatment as described above. It has been found that an increased mechanical strength of the catalyst extrudate is obtained when prepared according to this sequence of steps.
  • the hydrogenation component suitably comprises at least one Group VIB metal component and/or at least one Group VIII metal component.
  • Group VIB metal components include tungsten, molybdenum and/or chromium as sulphide, oxide and/or in elemental form. If present, a Group VIB metal component is suitably present in an amount of from 1 to 35% by weight, more suitably from 5 to 30% by weight, calculated as element and based on total weight of support, i.e. modified molecular sieve plus binder.
  • Group VIII metal components include those components based on both noble and non-noble metals. Particularly suitable Group VIII metal components, accordingly, are palladium, platinum, nickel and/or cobalt in sulphidic, oxidic and/or elemental form.
  • Nickel and/or cobalt may be present in an amount in the range of from 1 to 25% by weight, preferably 2 to 15% by weight, calculated as element and based on total weight of support.
  • the total amount platinum or palladium will suitably not exceed 10% by weight calculated as element and based on total weight of support, and preferably is in the range of from 0.1 to 5.0% by weight, more preferably from 0.2 to 3.0% by weight. If both platinum and palladium are present, the weight ratio of platinum to palladium may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5.
  • Catalysts comprising palladium and/or platinum as the hydrogenation component are preferred. Most preferred is when platinum is used as the sole hydrogenation component.
  • the hydrogenation component is suitably added to the catalyst extrudate comprising the dealuminated aluminosilicate zeolite crystallites by known techniques.
  • Catalytic dewaxing involve operating temperatures in the range of from 200 to 500 °C, preferably from 250 to 400 °C, hydrogen pressures in the range of from 10 to 200 bar, preferably from 15 to 100 bar, more preferably from 15 to 65 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/l/hr), preferably from 0.2 to 5 kg/l/hr, more preferably from 0.5 to 3 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil.
  • WHSV weight hourly space velocities
  • the synthesis was performed with a 250 ml autoclave, which was properly cleaned before the experiments.
  • a starting gel with a Si/Al ratio of 60.
  • the chemical composition of the system was: 1.0 NaOH : 1.0Q(OH) 2 : 0.166 Al(OH) 3 : 10 SiO 2 : 600 H 2 O where Q is hexa-N-methyl-N,N'-p-xylylen-di-ammonium (C 14 H 28 N 2 ).
  • the crystallisation was performed at 190 °C for 34 hours.
  • the XRD analysis showed that a pure well-crystallised product is synthesised. No other crystalline phases were observed.
  • the chemical analysis of the crystals showed a Si/Al of 62. SEM micrographs revealed that very large crystals (15-20 ⁇ m along the c-axis) were obtained.
  • the synthesis of smaller ZSM-12 crystals were also performed. To make the starting system more dense, the amount of template was decreased. In addition, 5 wt% as-synthesised ZSM-12 seeds, with respect to the silica content, were introduced into the starting gel.
  • the chemical composition of the gel was : 1.0 NaOH : 0.75 R : 0.166 Al(OH) 3 : 10 SiO 2 : 420 H 2 O where R is hexa-N-methyl-N,N'-p-xylylen-di-ammonium dihydroxide.
  • the crystallisation was performed at 190 °C for 34 hours.
  • the XRD analysis showed that a pure well-crystallised product is synthesised.
  • a dealuminated, silica bound ZSM-12 catalyst (10 wt% dealuminated ZSM-12, 90 wt% silica binder) was prepared according to the following procedure.
  • ZSM-12 crystallites as obtained in Example 1 were extruded with a silica binder (10% by weight of ZSM-12, 90% by weight of silica binder).
  • the extrudates were dried at 120 °C.
  • a solution of (NH 4 ) 2 SiF 6 (45 ml of 0.019 N solution per gram of ZSM-12 crystallites) was poured onto the extrudates. The mixture was then heated at 100 °C under reflux for 17 h with gentle stirring above the extrudates. After filtration, the extrudates were washed twice with deionised water, dried for 2 hours at 120 °C and then calcined for 2 hours at 480 °C.
  • the thus obtained extrudate was impregnated with an aqueous solution of platinum tetramine hydroxide followed by drying (2 hours at 120 °C) and calcining (2 hours at 300 °C).
  • the catalyst was activated by reduction of the platinum under a hydrogen rate of 100 1/hr at a temperature of 350 °C for 2 hours.
  • the resulting catalyst comprised 0.7% by weight Pt supported on the dealuminated, silica-bound ZSM-12.
  • a Fischer-Tropsch wax which has been subjected to a hydrotreatment in order to reduce the oxygen content to below 500 ppmw as molecular oxygen, but which has not been subjected to a hydroisomerisation treatment having the properties as listed in Table I:
  • Final Boiling Point 575 °C was contacted in the presence of hydrogen with the catalyst as obtained in Example 3 at an outlet pressure of 40 bar, a temperature of 388 °C, a WHSV of 1.0 kg/l.hr and a hydrogen gas rate of 700 Nl/kg. Gaseous components were separated from the effluent by vacuum flashing at a cutting temperature of 300 °C.
  • Table 2 The properties of the obtained lubricating base oil product and the yield of the catalytic dewaxing are given Table 2.
  • Example 4 was repeated except that the dewaxing temperature was 390 °C and the hydrogen gas rate of 700 Nl/kg was used.
  • the properties of the obtained lubricating base oil product and the yield of the catalytic dewaxing are given Table 2.
  • product properties Example 4 Example 5 yield calculated on feed (wt%) 45 36 viscosity at 40 °C (cSt) 21.52 21.14 viscosity at 100 °C (cSt) 4.832 4.724 VI 154 149 Pour Point (+/-1 °C) -20 -32
  • Example 5 was repeated at 345 °C with a dealuminated silica bound ZSM-12 catalyst (10 wt% dealuminated ZSM-12, 90 wt% silica binder), wherein the ZSM-12 crystallites were prepared as described in "Verified synthesis of zeolitic materials", volume 22 (1998), pages 644-645. The crystallite size range was between 10-100 nm.
  • the catalyst was further prepared as described in Example 3. The yield as calculated on feed was 45 wt%.
  • the viscosity at 40 °C was 20.67 cSt.
  • the viscosity at 100 °C was 4,593 cSt.
  • the VI was 143 and the Pour Point ( ⁇ 1 °C) was -32 °C.

Claims (10)

  1. Procédé de préparation d'une huile de base lubrifiante par mise en contact d'une cire de synthèse, ladite cire étant obtenue par un procédé de Fischer-Tropsch et n'ayant pas été soumise à un traitement d'hydroisomérisation, avec une composition catalytique comprenant au moins un composant d'hydrogénation, des cristallites de zéolite aluminosilicatée désaluminée du type MTW et un matériau liant d'oxyde réfractaire de faible acidité qui est essentiellement dépourvu d'alumine.
  2. Procédé selon la revendication 1, dans lequel le composant d'hydrogénation est le platine.
  3. Procédé selon l'une quelconque des revendications 1 et 2, dans lequel le liant de faible acidité est la silice.
  4. Procédé selon l'une quelconque des revendications 1 à 2, dans lequel les cristallites de zéolite aluminosilicatée du type MTW contiennent moins de 5% en poids d'une impureté de cristobalite.
  5. Procédé selon la revendication 4, dans lequel les cristallites de zéolite aluminosilicatée du type MTW peuvent être obtenues par cristallisation d'un mélange de synthèse comprenant une source de silicium, une source d'aluminium, une source d'un cation et un agent directeur organique ayant la formule générale suivante (R1R2R3N+-X-N+R4R5R6)Y2, dans lequel R1-R6 sont des groupes organiques, X est un groupe aryle bivalent et Y est un anion.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel les cristallites de zéolite aluminosilicatée désaluminée du type MTW sont obtenues par mise en contact des cristallites de zéolite avec une solution aqueuse d'un sel de fluorosilicate, ledit sel de fluorosilicate étant représenté par la formule : (A)2/bSiF6 dans laquelle "A" est un cation métallique ou non métallique autre que H+ ayant la valence "b", de préférence l'ammonium.
  7. Procédé selon la revendication 6, dans lequel un extrudat de cristallites de zéolite du type TW et du liant de faible acidité est mis en contact avec la solution aqueuse du sel de fluorosilicate.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'huile de base lubrifiante a un point d'écoulement en dessous de -27°C et un VI supérieur à 140.
  9. Procédé de préparation d'une huile de base lubrifiante en effectuant les étapes suivantes :
    (a) préparation d'un produit de Fischer-Tropsch au moyen d'un procédé de Fischer-Tropsch en partant d'un gaz de synthèse,
    (b) hydrotraitement éventuel du produit de Fischer-Tropsch afin de réduire la quantité de produits insaturés et oxygénés,
    (c) séparation d'une cire de Fischer-Tropsch du produit de Fischer-Tropsch obtenu à l'étape (b) ou (a),
    (d) déparaffinage catalytique de la cire de Fischer-Tropsch selon le procédé tel que revendiqué dans l'une quelconque des revendications 1 à 8 pour obtenir ainsi l'huile de base lubrifiante.
  10. Procédé selon la revendication 9, dans lequel la partie restante du produit de Fischer-Tropsch et la partie de cire de Fischer-Tropsch du produit de Fischer-Tropsch qui n'est pas utilisée à l'étape (d) obtenus toutes deux à l'étape (c) et la cire de Fischer-Tropsch non convertie obtenue à l'étape (d) est soumise à une étape d'hydroisomérisation et le produit d'hydroisomérisation ainsi obtenu est fractionné en fractions de carburant à points d'ébullition plus bas.
EP00948000A 1999-07-26 2000-07-25 Procede de preparation d'huile minerale lubrifiante Expired - Lifetime EP1204723B1 (fr)

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EP99401906 1999-07-26
EP99401906 1999-07-26
PCT/EP2000/007178 WO2001007538A1 (fr) 1999-07-26 2000-07-25 Procede de preparation d'huile minerale lubrifiante
EP00948000A EP1204723B1 (fr) 1999-07-26 2000-07-25 Procede de preparation d'huile minerale lubrifiante

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Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6695965B1 (en) * 2000-04-04 2004-02-24 Exxonmobil Research And Engineering Company Process for adjusting the hardness of Fischer-Tropsch wax by blending
MXPA03007088A (es) 2001-02-13 2003-11-18 Shell Int Research Composicion lubricante.
AR032941A1 (es) 2001-03-05 2003-12-03 Shell Int Research Un procedimiento para preparar un aceite base lubricante y aceite base obtenido, con sus diversas utilizaciones
MY139353A (en) 2001-03-05 2009-09-30 Shell Int Research Process to prepare a lubricating base oil and a gas oil
AR032932A1 (es) 2001-03-05 2003-12-03 Shell Int Research Procedimiento para preparar un aceite de base lubricante y un gas oil
ES2254973T3 (es) 2002-07-18 2006-06-16 Shell Internationale Research Maatschappij B.V. Procedimiento de preparacion de una cera microcristalina y de un combustible de destilado medio.
CN1266257C (zh) * 2002-07-19 2006-07-26 国际壳牌研究有限公司 含有增量油的硅橡胶组合物和制备所述增量油的方法
US7077947B2 (en) * 2002-10-08 2006-07-18 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI using oxygenated dewaxing catalyst
US7282137B2 (en) * 2002-10-08 2007-10-16 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI
US7087152B2 (en) * 2002-10-08 2006-08-08 Exxonmobil Research And Engineering Company Wax isomerate yield enhancement by oxygenate pretreatment of feed
US7344631B2 (en) * 2002-10-08 2008-03-18 Exxonmobil Research And Engineering Company Oxygenate treatment of dewaxing catalyst for greater yield of dewaxed product
CN100428994C (zh) * 2002-10-08 2008-10-29 埃克森美孚研究工程公司 含氧化合物处理的脱蜡催化剂及使用该催化剂对蜡质费－托烃进行加氢脱蜡
US7704379B2 (en) 2002-10-08 2010-04-27 Exxonmobil Research And Engineering Company Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate
US7201838B2 (en) * 2002-10-08 2007-04-10 Exxonmobil Research And Engineering Company Oxygenate treatment of dewaxing catalyst for greater yield of dewaxed product
US7220350B2 (en) * 2002-10-08 2007-05-22 Exxonmobil Research And Engineering Company Wax isomerate yield enhancement by oxygenate pretreatment of catalyst
US7125818B2 (en) * 2002-10-08 2006-10-24 Exxonmobil Research & Engineering Co. Catalyst for wax isomerate yield enhancement by oxygenate pretreatment
US6951605B2 (en) 2002-10-08 2005-10-04 Exxonmobil Research And Engineering Company Method for making lube basestocks
CA2509369A1 (fr) * 2002-12-09 2004-06-24 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un lubrifiant
CN1774393A (zh) 2003-04-15 2006-05-17 国际壳牌研究有限公司 进行蒸汽重整反应的反应器和制备合成气的方法
US7815789B2 (en) 2003-06-23 2010-10-19 Shell Oil Company Process to prepare a lubricating base oil
EP1641898B1 (fr) 2003-07-04 2007-09-19 Shell Internationale Researchmaatschappij B.V. Procede de preparation d'huiles de base a partir d'un produit de synthese fisher-tropsch
US7727378B2 (en) 2003-07-04 2010-06-01 Shell Oil Company Process to prepare a Fischer-Tropsch product
US8137531B2 (en) * 2003-11-05 2012-03-20 Chevron U.S.A. Inc. Integrated process for the production of lubricating base oils and liquid fuels from Fischer-Tropsch materials using split feed hydroprocessing
US8372263B2 (en) 2007-06-27 2013-02-12 Nippon Oil Corporation Hydroisomerization catalyst, method of dewaxing hydrocarbon oil, process for producing base oil, and process for producing lube base oil
RU2465959C2 (ru) * 2008-02-08 2012-11-10 ДжейЭкс НИППОН ОЙЛ ЭНД ЭНЕРДЖИ КОРПОРЕЙШН Катализатор гидроизомеризации, способ его получения, способ депарафинизации углеводородного масла и способ получения базового смазочного масла
JP5221999B2 (ja) * 2008-03-31 2013-06-26 Ｊｘ日鉱日石エネルギー株式会社 潤滑油基油の製造方法
TWI473652B (zh) * 2008-12-26 2015-02-21 Nippon Oil Corp Hydrogenated isomerization catalyst, method for producing the same, dewaxing method for hydrocarbon oil and method for producing lubricating base oil
FR2952380B1 (fr) 2009-11-10 2012-05-18 Inst Francais Du Petrole Procede de production de distillat moyen a partir de cires fischer tropsch mettant en oeuvre un catalyseur a base de zeolithe modifiee par un traitement basique
KR101354235B1 (ko) * 2010-04-14 2014-02-13 에스케이이노베이션 주식회사 수소화 탈왁스 공정을 위한 촉매 및 이의 제조 방법
CN105728023B (zh) * 2014-12-08 2018-11-16 中国石油天然气股份有限公司 用于费-托蜡加氢异构反应的分子筛催化剂及制备方法
JP7249911B2 (ja) * 2019-08-27 2023-03-31 東ソー株式会社 ヘキサヒドロベンゾジピロリウム塩及びその用途
JP7412110B2 (ja) * 2019-08-27 2024-01-12 東ソー株式会社 ヘキサヒドロベンゾジピロール及びその製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU603344B2 (en) * 1985-11-01 1990-11-15 Mobil Oil Corporation Two stage lubricant dewaxing process
US5157191A (en) * 1986-01-03 1992-10-20 Mobil Oil Corp. Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index
US5362378A (en) * 1992-12-17 1994-11-08 Mobil Oil Corporation Conversion of Fischer-Tropsch heavy end products with platinum/boron-zeolite beta catalyst having a low alpha value
EP0668342B1 (fr) * 1994-02-08 1999-08-04 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'une huile lubrifiante de base
US5628978A (en) * 1994-12-23 1997-05-13 Intevep, S.A. MTW zeolite for cracking feedstock into olefins and isoparaffins
MY125670A (en) * 1995-06-13 2006-08-30 Shell Int Research Catalytic dewaxing process and catalyst composition
US5833837A (en) * 1995-09-29 1998-11-10 Chevron U.S.A. Inc. Process for dewaxing heavy and light fractions of lube base oil with zeolite and sapo containing catalysts
FR2765209B1 (fr) * 1997-06-25 1999-10-22 Inst Francais Du Petrole Zeolithe eu-1, catalyseur et procede pour l'amelioration du point d'ecoulement de charges contenant des paraffines

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AU755622B2 (en) 2002-12-19
JP2003505576A (ja) 2003-02-12
DE60019935D1 (de) 2005-06-09
AU6160100A (en) 2001-02-13
RU2228947C2 (ru) 2004-05-20
DE60019935T2 (de) 2006-02-16
CN1364188A (zh) 2002-08-14
CN1190473C (zh) 2005-02-23
EP1204723A1 (fr) 2002-05-15
WO2001007538A1 (fr) 2001-02-01
JP4860861B2 (ja) 2012-01-25

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