EP0583836B1 - Procédé de préparation de combustibles hydrocarbonés - Google Patents

Procédé de préparation de combustibles hydrocarbonés Download PDF

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Publication number
EP0583836B1
EP0583836B1 EP93202395A EP93202395A EP0583836B1 EP 0583836 B1 EP0583836 B1 EP 0583836B1 EP 93202395 A EP93202395 A EP 93202395A EP 93202395 A EP93202395 A EP 93202395A EP 0583836 B1 EP0583836 B1 EP 0583836B1
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Prior art keywords
process according
catalyst
hydrocarbon
hydroconversion
hydrogen
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German (de)
English (en)
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EP0583836A1 (fr
EP0583836B2 (fr
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Jacobus Eilers
Sytze Abel Posthuma
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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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps

Definitions

  • mishtha is a reference to hydrocarbons or hydrocarbon mixtures having a boiling point or boiling point range substantially corresponding to that of the naphtha (sometimes referred to as the gasoline) fractions obtained during the conventional atmospheric distillation of crude oil.
  • the following fractions are consecutively recovered from the crude oil: one or more naphtha fractions boiling in the range of from 30 to 220 °C, one or more kerosine fractions boiling in the range of from 120 to 300 °C and one or more gasoil fractions boiling in the range of from 170 to 370 °C.
  • hydrocarbon fuel is to be taken as a reference to either one of or a mixture of naphtha and middle distillates.
  • US-A-4,478,955 discloses a process scheme comprising contacting the effluent of a Fischer-Tropsch synthesis process with hydrogen in the presence of a suitable hydrogenation catalyst.
  • the effluent of the Fischer-Tropsch synthesis is described in US-A-4,478,955 as comprising predominantly olefins and carboxylic acids.
  • useful fuel components comprising alkanes, alcohols and esters are produced.
  • the present invention provides a process for the preparation of hydrocarbon fuels comprising the steps of:
  • the hydrocarbons prepared in the first stage, stage (a), of the process of the present invention are subjected to a hydroconversion in two separate and distinct stages.
  • the olefinic and oxygen-containing compounds are hydrogenated.
  • the operating conditions of the first hydroconversion stage are selected so as to substantially prevent hydrocracking and/or hydroisomerisation reactions from occurring.
  • stage (c) the desired hydrocarbon fuels are prepared by subjecting at least a part of the product of the first hydroconversion stage to a second hydroconversion treatment, in which the high molecular weight paraffinic hydrocarbons are hydroisomerised and hydrocracked.
  • water is formed as a product of the hydrogenation of the oxygen-containing hydrocarbons. It has been found that water produced during this reaction adversely affects certain hydroconversion catalysts, leading to a reduction in catalyst performance.
  • milder operating conditions are required in the second hydroconversion stage to achieve the desired degree of hydrocracking and hydroisomerisation than required in the single hydroconversion stage of the prior art process. This results in an improved lifetime of the hydroconversion catalyst and, most surprisingly, leads to a markedly improved product.
  • the process of the present invention most surprisingly exhibits an improved selectivity to valuable hydrocarbon fuels, in particular gasoil, compared with the processes of the prior art.
  • substantially paraffinic when used in connection with hydrocarbon products or hydrocarbon fuels refers to a hydrocarbon mixture comprising at least 70 %wt paraffins, preferably at least 80 %wt paraffins.
  • Hydrocarbon fuels produced by the process of this invention typically comprise at least 90 %wt paraffins, more typically at least 95 %wt paraffins.
  • a feed comprising a mixture of carbon monoxide and hydrogen is contacted at elevated temperature and pressure with a catalyst active in the synthesis of paraffinic hydrocarbons.
  • Suitable processes for the preparation of the mixture of carbon monoxide and hydrogen are well known in the art and include such processes as the partial oxidation of methane, typically in the form of natural gas, and the steam reforming of methane.
  • the relative amounts of carbon monoxide and hydrogen present in the feed may vary over a wide range and may be selected according to the precise catalyst and process operating conditions being employed.
  • the feed contacting the catalyst comprises carbon monoxide and hydrogen in a hydrogen/carbon monoxide molar ratio of below 2.5, preferably below 1.75. More preferably, the hydrogen/carbon monoxide ratio is in the range of from 0.4 to 1.5, especially from 0.9 to 1.3.
  • Unconverted carbon monoxide and hydrogen may be separated from the synthesis product and recycled to the inlet of the synthesis reactor.
  • the catalyst comprises, as the catalytically active component, a metal from Group VIII of the Periodic Table of Elements.
  • a metal from Group VIII include ruthenium, iron, cobalt and nickel.
  • a catalyst comprising cobalt as the catalytically active metal is preferred.
  • the catalytically active metal is preferably supported on a porous carrier.
  • the porous carrier may be selected from any suitable refractory metal oxide or silicate or mixture thereof. Particular examples of preferred carriers include silica, alumina, titania, zirconia and mixtures thereof. Carriers comprising silica and/or alumina are especially preferred.
  • the catalytically active metal may be applied to the carrier by any of the techniques known in the art, for example comulling, impregnation or precipitation. Impregnation is a particularly preferred technique, in which the carrier is contacted with a compound of the catalytically active metal in the presence of a liquid, most conveniently in the form of a solution of the metal compound.
  • the compound of the active metal may be inorganic or organic, with inorganic compounds being preferred, in particular nitrates.
  • the liquid employed may also be either organic or inorganic. Water is a most convenient liquid.
  • the amount of catalytically active metal present on the carrier is typically in the range of from 1 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of carrier material.
  • the catalytically active metal may be present in the catalyst together with one or more metal promoters or co-catalysts.
  • the promoters may be present as metals or as the metal oxide, depending upon the particular promoter concerned. Suitable metal oxide promoters include oxides of metals from Groups IIA, IIIB, IVB, VB or VIB of the Periodic Table, oxides of the lanthanides and/or the actinides.
  • the catalyst comprises an oxide of an element in Group IVB of the Periodic Table, in particular titanium or zirconium. Catalysts comprising zirconium are especially preferred.
  • the promoter if present in the catalyst, is typically present in an amount of from 1 to 60 parts by weight, preferably from 2 to 40 parts by weight, per 100 parts by weight of carrier material.
  • the hydrocarbon synthesis is conducted under conditions of elevated temperature and pressure. Typically, the synthesis is effected at a temperature in the range of from 125 to 300 °C, preferably from 175 to 250 °C.
  • the reaction pressure is typically in the range of from 5 to 100 bar, preferably from 12 to 50 bar.
  • the synthesis may be conducted using a variety of reactor types and reaction regimes, for example in a fixed bed regime, a slurry phase regime or an ebullating bed regime.
  • the hydrocarbon product of the synthesis stage is subjected to a two-stage hydroconversion treatment in stages (b) and (c) of the process of the present invention.
  • the entire effluent of the synthesis stage may be led directly to the first hydroconversion stage.
  • the low molecular weight products of the synthesis stage in particular the C 4 - fraction, for example methane, ethane and propane, may also be removed prior to the hydroconversion treatment.
  • the separation is conveniently effected using distillation techniques well known in the art.
  • the hydrocarbon product is contacted with hydrogen in the presence of a hydrogenation catalyst.
  • a hydrogenation catalyst Suitable catalysts for use in this stage are known in the art.
  • the catalyst comprises as catalytically active component one or more metals selected from Groups VIB and VIII of the Periodic Table of Elements, in particular one or more metals selected from molybdenum, tungsten, cobalt, nickel, ruthenium, iridium, osmium, platinum and palladium.
  • the catalyst comprises on or more metals selected from nickel, platinum and palladium as the catalytically active component.
  • a particularly suitable catalyst comprises nickel as a catalytically active component.
  • Catalysts for use in the first hydroconversion stage typically comprise a refractory metal oxide or silicate as a carrier.
  • Suitable carrier materials include silica, alumina, silica-alumina, zirconia, titania and mixtures thereof.
  • Preferred carrier materials for inclusion in the catalyst for use in the process of this invention are silica, alumina and silica-alumina.
  • Suitable catalysts for use in the first hydroconversion stage of the process of this invention are available commercially, or may be prepared by methods well known in the art, for example the methods discussed hereinbefore with reference to the preparation of the hydrocarbon synthesis catalyst.
  • the hydrocarbon product leaving the first hydroconversion stage substantially consists of high molecular weight, paraffinic hydrocarbons having a boiling point range above that of the middle distillates. At least a part of this hydrocarbon product is subjected to a second hydroconversion in stage (c) of the process of this invention, to yield the desired hydrocarbon fuel product. If desired, the entire effluent of the first hydroconversion stage may be led directly to the second hydroconversion stage. However, it is preferred to separate the low molecular weight hydrocarbons, especially the C 4 -fraction, from the higher molecular weight hydrocarbons prior to the second hydroconversion stage. The separation may be conveniently achieved using distillation techniques well known in the art. At least a part of the remaining C 5 + fraction of the hydrocarbon product is then used as feed for the second hydroconversion stage.
  • the catalyst comprises as catalytically active component one or more metals selected from Groups VIB and VIII of the Periodic Table of Elements, in particular one or more metals selected from molybdenum, tungsten, cobalt, nickel, ruthenium, iridium, osmium, platinum and palladium.
  • the catalyst comprises one or more metals selected from nickel, platinum and palladium as the catalytically active component. Catalysts comprising platinum as the catalytically active component have been found to be particularly suitable for use in the second hydroconversion stage.
  • Catalysts for use in the second hydroconversion stage typically comprise a refractory metal oxide or silicate as a carrier.
  • the carrier material may be amorphous or crystalline. Suitable carrier materials include silica, alumina, silica-alumina, zirconia, titania and mixtures thereof.
  • the carrier may comprise one or more zeolites, either alone or in combination with one or more of the aforementioned carrier materials.
  • Preferred carrier materials for inclusion in the catalyst for use in the process of this invention are silica, alumina and silica-alumina.
  • a particularly preferred catalyst comprises platinum supported on a silica-alumina carrier.
  • the catalyst may comprise the catalytically active component in an amount of from 0.05 to 80 parts by weight, preferably from 0.1 to 70 parts by weight, per 100 parts by weight of carrier material.
  • the amount of catalytically active metal present in the catalyst will vary according to the specific metal concerned.
  • a particularly preferred catalyst for use in the second hydroconversion stage comprises platinum in an amount in the range of from 0.05 to 2 parts by weight, more preferably from 0.1 to 1 parts by weight, per 100 parts by weight of carrier material.
  • Suitable catalysts for use in the second hydroconversion stage of the process of this invention are available commercially, or may be prepared by methods well known in the art, for example the methods discussed hereinbefore with reference to the preparation of the hydrocarbon synthesis catalyst.
  • the hydrocarbon product of the first hydroconversion stage is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure.
  • the temperatures necessary to yield the hydrocarbon fuels will lie in the range of from 175 to 400 °C, preferably from 250 to 375 °C.
  • the pressure typically applied ranges from 10 to 250 bars, more preferably from 25 to 250 bars.
  • Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10000 Nl/l/hr, preferably from 500 to 5000 Nl/l/hr.
  • the hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/l/hr, preferably from 0.25 to 2 kg/l/hr.
  • the ratio of hydrogen to hydrocarbon feed may range from 100 to 5000 Nl/kg and is preferably from 250 to 2500 Nl/kg.
  • the degree of hydrocracking and isomerisation occurring in the second hydroconversion stage may be measured by determining the degree of conversion of the fraction boiling above 370 °C, as hereinbefore defined.
  • the second hydroconversion stage is operated at a conversion of at least 40%.
  • the hydrogen required for the operation of both the first and the second hydroconversion stages may be generated by processes well known in the art, for example by the steam reforming of a refinery fuel gas.
  • the hydrocarbon fuel produced in the second hydroconversion stage will typically comprise hydrocarbons having boiling points lying in a number of different fuel fractions, for example the naphtha, kerosine and gasoil fractions discussed hereinbefore. Separation of the hydrocarbon fuel into the appropriate fractions may be conveniently achieved using distillation techniques well known in the art.
  • Example 1(C)(i) hereabove A sample of the catalyst prepared as described in Example 1(C)(i) hereabove was loaded into a reaction vessel.
  • the C 5 + hydrocarbon product of the hydrocarbon synthesis stage was fed to the reaction vessel at a weight hourly space velocity of 1.103 kg/l/hr and a pressure of 31 bars.
  • Hydrogen was supplied to the reaction vessel at a gas hourly space velocity of 660 Nl/l/hr (that is a hydrogen to hydrocarbon ratio of 596 Nl/kg).
  • a liquid recycle rate of 0.23 kg/l/hr was applied.
  • a conversion of 55% (as defined in Example 1(B) (ii) hereabove) was achieved at an operating temperature of 338 °C.
  • the effluent of the reaction vessel was collected and separated by means of distillation into a number of fractions.
  • the properties of a gasoil fraction boiling in the temperature range of from 170 to 340 °C recovered from the effluent are given in Table 1.
  • Example 1(C)(i) hereabove A sample of the catalyst prepared as described in Example 1(C)(i) hereabove was loaded into a reaction vessel.
  • the C 5 + hydrocarbon product of the hydrocarbon synthesis stage was fed to the reaction vessel at a weight hourly space velocity of 1.01 kg/l/hr and a pressure of 31.4 bars.
  • Hydrogen was supplied to the reaction vessel at a gas hourly space velocity of 660 Nl/l/hr (that is a hydrogen to hydrocarbon ratio of 655 Nl/kg).
  • a liquid recycle rate of 0.13 kg/l/hr was applied.
  • a conversion of 39% (as defined in Example 1(B) (ii) hereabove) was achieved at an operating temperature of 334 °C.
  • the effluent of the reaction vessel was collected and separated by means of distillation into a number of fractions.
  • the selectivity of the second hydroconversion stage to a gasoil fraction boiling in the temperature range of from 220 to 370 °C was 40%.

Claims (20)

  1. Procédé de préparation de carburants hydrocarbonés, caractérisé en ce qu'il comprend les étapes consistant à :
    a) mettre en contact un mélange de monoxyde de carbone et d'hydrogène avec un catalyseur de synthèse d'hydrocarbures, à température et pression élevées, de manière à préparer un produit hydrocarboné sensiblement paraffinique, contenant au moins 70% en poids de paraffines;
    b) mettre en contact le produit hydrocarboné ainsi obtenu avec de l'hydrogène en présence d'un catalyseur d'hydroconversion dans des conditions telles que la conversion, définie comme le pourcentage pondéral de la fraction de la charge de produit hydrocarboné bouillant au-delà de 370°C et qui est convertie au cours de l'hydroconversion en une fraction bouillant en dessous de 370°C, demeure inférieure à 20%; et
    c) mettre en contact au moins une partie du produit hydrocarboné de l'étape b) avec de l'hydrogène en présence d'un catalyseur d'hydroconversion, dans des conditions telles que l'hydrocraquage et l'isomérisation du produit s'opèrent pour donner un carburant hydrocarboné sensiblement paraffinique, contenant au moins 70% en poids de paraffines.
  2. Procédé suivant la revendication 1, caractérisé en ce que le mélange de monoxyde de carbone et d'hydrogène entrant en contact avec le catalyseur dans l'étape (a) possède un rapport hydrogène/monoxyde de carbone inférieur à 2,5, de préférence, inférieur à 1,75, plus avantageusement, de 0,4 à 1,5.
  3. Procédé suivant l'une quelconque des revendications 1 ou 2, caractérisé en ce que le catalyseur de synthèse d'hydrocarbures de l'étape (a) comprend du ruthénium, du fer, du nickel, ou du cobalt, à titre de métal catalytiquement actif, de préférence, du cobalt.
  4. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le catalyseur de synthèse d'hydrocarbures dans l'étape (a) comprend un support, de préférence, choisi parmi la silice, l'alumine, l'oxyde de titane, la zircone et leurs mélanges, plus avantageusement, la silice ou l'alumine.
  5. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le catalyseur de synthèse d'hydrocarbures dans l'étape (a) comprend, à titre de promoteur, un oxyde d'un métal choisi parmi les éléments du groupe IVB du tableau périodique, de préférence, le titane ou le zirconium.
  6. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que l'on met le mélange de monoxyde de carbone et d'hydrogène en contact avec le catalyseur dans l'étape (a), à une température qui varie de 125 à 300°C, de préférence, de 175 à 250°C.
  7. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que l'on met le mélange de monoxyde de carbone et d'hydrogène en contact avec le catalyseur dans l'étape (a), sous une pression de 5 à 100 bars, de préférence, de 12 à 50 bars.
  8. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le catalyseur d'hydroconversion de l'étape (b) comprend du molybdène, du tungstène, du cobalt, du nickel, du ruthénium, de l'iridium, de l'osmium, du platine ou du palladium, à titre de métal catalytiquement actif, de préférence, un ou plusieurs éléments choisis parmi le nickel, le platine et le palladium.
  9. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le catalyseur d'hydroconversion de l'étape (b) comprend un support, de préférence, choisi parmi la silice, l'alumine, la silice-alumine, l'oxyde de titane, la zircone et leurs mélanges, plus avantageusement, la silice, l'alumine et la silice-alumine.
  10. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (b), on met le produit hydrocarboné en contact avec le catalyseur d'hydroconversion, à une température qui varie de 100 à 300°C, de préférence, de 150 à 275°C.
  11. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (b), on met le produit hydrocarboné en contact avec le catalyseur d'hydroconversion, sous une pression de 5 à 150 bars, de préférence, de 10 à 50 bars.
  12. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (b), on fournit l'hydrogène à la vitesse spatiale horaire gazeuse de 100 à 1000 litres normaux/litre/ heure, de préférence, 250 à 5000 litres normaux/litre/heure.
  13. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (b), la conversion est inférieure à 10%, plus avantageusement encore, inférieure à 5%.
  14. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le catalyseur d'hydroconversion de l'étape (c) comprend du molybdène, du tungstène, du cobalt, du nickel, du ruthénium, de l'iridium, de l'osmium, du platine ou du palladium, à titre de métal catalytiquement actif, de préférence un ou plusieurs éléments choisis parmi le nickel, le platine et le palladium.
  15. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le catalyseur d'hydroconversion de l'étape (c) comprend un support, choisi, de préférence, parmi la silice, l'alumine, la silice-alumine, l'oxyde de titane, la zircone et leurs mélanges, de préférence, la silice, l'alumine et la silice-alumine.
  16. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (c), on met le produit hydrocarboné en contact avec le catalyseur d'hydroconversion, à une température qui varie de 175 à 400°C, de préférence, de 250 à 375°C.
  17. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (c), on met le produit hydrocarboné en contact avec le catalyseur d'hydroconversion, sous une pression de 10 à 250 bars, de préférence, de 25 à 250 bars.
  18. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que dans l'étape (c), on fournit l'hydrogène à une vitesse spatiale horaire gazeuse de 100 à 10000 litres normaux/litre/ heure, de préférence, de 500 à 5000 litres normaux/litre/heure.
  19. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que la conversion atteint au moins 40% dans l'étape (c).
  20. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que l'on élimine les composant légers, de préférence, les composants en C4-, du produit de la synthèse d'hydrocarbures de l'étape (a) ou de l'hydroconversion de l'étape (b), ou à la fois de la synthèse d'hydrocarbures de l'étape (a) et de l'hydroconversion de l'étape (b).
EP93202395A 1992-08-18 1993-08-16 Procédé de préparation de combustibles hydrocarbonés Expired - Lifetime EP0583836B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP93202395A EP0583836B2 (fr) 1992-08-18 1993-08-16 Procédé de préparation de combustibles hydrocarbonés

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP92202537 1992-08-18
EP92202537 1992-08-18
EP93202395A EP0583836B2 (fr) 1992-08-18 1993-08-16 Procédé de préparation de combustibles hydrocarbonés

Publications (3)

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EP0583836A1 EP0583836A1 (fr) 1994-02-23
EP0583836B1 true EP0583836B1 (fr) 1997-10-29
EP0583836B2 EP0583836B2 (fr) 2002-02-13

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EP (1) EP0583836B2 (fr)
JP (1) JP3522797B2 (fr)
AU (1) AU666960B2 (fr)
CA (1) CA2104158C (fr)
DE (1) DE69314879T3 (fr)
DK (1) DK0583836T4 (fr)
DZ (1) DZ1708A1 (fr)
ES (1) ES2110051T5 (fr)
MY (1) MY108862A (fr)
NO (1) NO305288B1 (fr)
NZ (1) NZ248415A (fr)
RU (1) RU2101324C1 (fr)
ZA (1) ZA935964B (fr)

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WO2007133554A2 (fr) 2006-05-09 2007-11-22 Exxonmobil Research And Engineering Company Composition d'huile de graissage
WO2008002425A1 (fr) 2006-06-23 2008-01-03 Exxonmobil Research And Engineering Company Compositions lubrifiantes
EP2581436A1 (fr) 2011-10-14 2013-04-17 IFP Energies nouvelles Procédé de production de distillats moyens à partir d'un melange d'une charge issue de sources renouvelables et d'un effluent paraffinique
EP2586851A1 (fr) 2011-10-27 2013-05-01 IFP Energies nouvelles Procédé de production de distillats moyens dans lequel la charge issue du procédé fischer-tropsch et le flux d'hydrogéne contiennent une teneur limitée en oxygène
US8771385B2 (en) 2008-12-29 2014-07-08 Shell Oil Company Fuel compositions
US8968427B2 (en) 2010-12-24 2015-03-03 Shell Oil Company Blending fuels

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US5689031A (en) † 1995-10-17 1997-11-18 Exxon Research & Engineering Company Synthetic diesel fuel and process for its production
US6043288A (en) * 1998-02-13 2000-03-28 Exxon Research And Engineering Co. Gas conversion using synthesis gas produced hydrogen for catalyst rejuvenation and hydrocarbon conversion
IT1301801B1 (it) * 1998-06-25 2000-07-07 Agip Petroli Procedimento per la preparazione di idrocarburi da gas di sintesi
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DE69314879D1 (de) 1997-12-04
EP0583836B2 (fr) 2002-02-13
JPH06158058A (ja) 1994-06-07
DE69314879T3 (de) 2002-07-18
NO932905D0 (no) 1993-08-16
NO932905L (no) 1994-02-21
CA2104158C (fr) 2005-11-15
ZA935964B (en) 1994-03-15
RU2101324C1 (ru) 1998-01-10
AU4467693A (en) 1994-02-24

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