EP1436360B1 - Verfahren zur kohlenwasserstoffsynthese in einem dreiphasenreaktor in gegenwart eines katalysators, der ein metall der gruppe viii auf zirconiumoxid oder zirconiumoxid-aluminiumoxid-mischoxid geträgert enthält - Google Patents

Verfahren zur kohlenwasserstoffsynthese in einem dreiphasenreaktor in gegenwart eines katalysators, der ein metall der gruppe viii auf zirconiumoxid oder zirconiumoxid-aluminiumoxid-mischoxid geträgert enthält Download PDF

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Publication number
EP1436360B1
EP1436360B1 EP02803430A EP02803430A EP1436360B1 EP 1436360 B1 EP1436360 B1 EP 1436360B1 EP 02803430 A EP02803430 A EP 02803430A EP 02803430 A EP02803430 A EP 02803430A EP 1436360 B1 EP1436360 B1 EP 1436360B1
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EP
European Patent Office
Prior art keywords
catalyst
zirconia
support
process according
weight
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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
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EP02803430A
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English (en)
French (fr)
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EP1436360A1 (de
Inventor
Magalie Roy-Auberger
Renaud Revel
Virginie Tissot
Dan Ion Enache
Roberto Zennaro
Giovanni Pederzani
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IFP Energies Nouvelles IFPEN
Eni SpA
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IFP Energies Nouvelles IFPEN
Eni SpA
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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
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • 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
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group

Definitions

  • the present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising CO- (CO 2 ) -H 2 , that is to say a mixture comprising carbon monoxide, hydrogen and optionally carbon dioxide, called synthesis gas.
  • This process comprises the use of a catalyst comprising at least one Group VIII metal supported on a zirconia or a particular mixed zirconia-alumina oxide.
  • the synthesis gas can be converted to hydrocarbons in the presence of a transition metal-containing catalyst.
  • This conversion carried out at high temperature and under pressure is known in the literature as the Fischer-Tropsch synthesis.
  • metals of group VIII of the periodic table of elements such as iron, ruthenium, cobalt and nickel catalyze the conversion of mixtures CO- (CO 2 ) -H 2 , that is to say of mixtures comprising carbon monoxide, hydrogen and possibly carbon dioxide, in liquid and / or gaseous hydrocarbons.
  • the stabilizing element can be Si, Zr, Cu, Zn, Mn, Ba, Co, Ni and / or La. It makes it possible to substantially reduce the solubility of the support in acidic or neutral aqueous solutions. It is added to the preformed alumina support.
  • the patent application EP-A-0 716 883 describes catalytic catalysts and supports formed essentially of monoclinic zirconia prepared from zirconium nitrate or zirconium chloride in aqueous solution.
  • Such catalysts after addition of metals such as nickel, copper, cobalt or platinum, can be used for carrying out various reactions and in particular for Fischer-Tropsch synthesis.
  • the patent US 5,958,985 discloses a process for preparing hydrocarbons from a synthesis gas in the presence of a catalyst comprising a support selected from alumina, silica, titania, zirconia and mixtures thereof onto which cobalt and manganese in a proportion such that the molar ratio cobalt / manganese is between 13/1 and 9/1 so as to optimize the selectivity to C 5+ .
  • the patent US Patent 5,217,938 describes a process for the preparation of a zirconia-based catalyst optionally containing additional metals of groups IB-VIIB and VIII but preferably of group VIII.
  • the catalyst is in the form of extrudates and is used for Fischer-Tropsch synthesis.
  • EP-A-0 908 232 describes the preparation of an acid catalyst containing a substantial amount of mass or supported sulfated zirconia in crystalline form (monoclinic or quadratic) and a hydrogenating transition metal.
  • This catalyst is used in chemical conversion reactions of hydrocarbons requiring the use of an acid catalyst such as in the isomerization reactions of paraffins, olefins, cyclic compounds, aromatics, alkylation reactions, oligomerization or dehydration of light hydrocarbons.
  • the present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising carbon monoxide and hydrogen (CO-H 2 ), optionally carbon dioxide CO 2 , in the presence of a catalyst.
  • supported medium comprising at least one Group VIII metal, the support comprising zirconia or a mixed zirconia-alumina oxide and wherein the zirconia is in quadratic and / or amorphous form.
  • the catalyst is used in suspension in a liquid phase in a three-phase reactor, generally called slurry reactor. Most often, the triphasic reactor is of the bubble column type, also called slurry bubble column according to English terminology.
  • the Applicant has surprisingly discovered that the use of a support comprising zirconia in quadratic and / or amorphous form, optionally containing an alumina phase, allowed after impregnation of at least one metal of group VIII, preferably cobalt, to obtain a more active and selective catalyst than the previous catalysts in the process for the synthesis of hydrocarbons from a mixture comprising carbon monoxide and hydrogen.
  • Such catalysts have particularly stable performances and lead to the conversion of the synthesis gas into a mixture of linear and saturated hydrocarbons containing at least 50% by weight of C5 + hydrocarbons and less than 20% of methane with respect to all hydrocarbons formed.
  • this catalyst has an improved mechanical strength compared to a catalyst formed of a support of alumina alone or of titanium dioxide, the mechanical strength being determined by measuring the evolution of the particle size for a duration of test given in a bubble column implementation.
  • the quadratic crystalline structure of zirconia is characterized by X-ray diffraction.
  • Amorphous zirconia is characterized by the absence of significant diffraction line on the diffraction pattern. It is essential for the implementation of the hydrocarbon synthesis process according to the invention that the zirconia included in the catalytic support is entirely devoid of a monoclinic type crystalline structure. It should not be sulphated.
  • the support used in the process for the synthesis of hydrocarbons according to the present invention contains at least 10% by weight of zirconia in quadratic and / or amorphous form relative to the total mass of the support and contains from 0 to 90% by weight of Al 2 O 3 , preferably from 1 to 75%, even more preferably from 5% to 60% by weight of Al 2 O 3 relative to the total mass of the support.
  • the support comprising zirconia or a mixed zirconia-alumina oxide and in which the zirconia is in quadratic and / or amorphous form has a specific surface area greater than 50 m 2 / g, preferably greater than 80 m 2 / g and still more preferably greater than 100 m 2 / g.
  • any zirconia synthesis process known to those skilled in the art leading to a quadratic and / or amorphous zirconia advantageously having a surface area greater than 50 m 2 / g is suitable for preparing the catalyst supports used in the synthesis process of hydrocarbons according to the invention.
  • the catalyst support used in the hydrocarbon synthesis process according to the invention can be prepared by true precipitation or coprecipitation in aqueous solution under controlled stationary operating conditions (pH, concentration, temperature, reaction time). average residence time) by reaction of an acid solution containing zirconium, for example zirconium nitrate or zirconium chloride, optionally aluminum, for example aluminum sulphate, aluminum nitrate, with a basic solution such as ammonia or hydrazine.
  • aqueous solution under controlled stationary operating conditions (pH, concentration, temperature, reaction time). average residence time) by reaction of an acid solution containing zirconium, for example zirconium nitrate or zirconium chloride, optionally aluminum, for example aluminum sulphate, aluminum nitrate, with a basic solution such as ammonia or hydrazine.
  • a particular method of preparing such media and resulting from the teaching of the patent application EP-A-0 908 232 consists in coprecipitating ZrO (NO 3 ) 2 and Al (NO 3 ) 3 at pH equal to 9.
  • Another preferred method is the precipitation of ZrO (NO 3 ) 2 by hydrazine, in the presence or absence of Al (NO 3 ) 3, for example, the method mentioned by Ciuparu (J. Mater Sci Lett 19 (2000) 931 ).
  • the support is then obtained by filtration and washing, drying with shaping and calcination.
  • the unitary step of drying with shaping is preferably carried out by atomization, which makes it possible to obtain substantially spherical microbeads less than 500 microns in size.
  • the product is calcined preferably in air and in a rotary oven at a temperature of between 400 ° C. and 1200 ° C., preferably between 400 ° C. and 800 ° C. and for a sufficient time so that the surface
  • the specific BET of the support advantageously has a value greater than 50 m 2 / g, preferably greater than 80 m 2 / g and even more preferably greater than 100 m 2 / g .
  • the support is generally in the form of a finely graded powder having a grain size of less than 500 microns, preferably of between 10 and 150 microns and even more preferably of between 20 and 120 microns, for optimum use in the presence of a liquid phase. in a bubble column.
  • the support has the following textural properties: a pore volume greater than 0.1 cm 3 / g and an average pore diameter greater than 6 nm, preferably greater than 8 nm.
  • the catalyst used in the hydrocarbon synthesis process according to the invention comprises at least one metal of group VIII of the periodic table of elements, supported on a quadratic and / or amorphous zirconia, optionally containing an alumina phase and / or optionally minus one stabilizing.
  • the element of group VIII of the Periodic Table of Elements is selected from the group consisting of iron, cobalt and ruthenium.
  • the Group VIII metal is cobalt.
  • the content by weight relative to the total weight of Group VIII metal catalyst is between 0.1 and 50%, preferably between 1 and 30%.
  • a particularly suitable catalyst preparation technique is the impregnation on the support comprising zirconia or zirconia-alumina mixed oxide of an aqueous solution of a Group VIII metal precursor of the Periodic Table of Elements, preferably cobalt, for example an aqueous solution of salts such as cobalt nitrates.
  • the catalyst may also contain other additional elements, in particular promoters of activity, such as for example at least one element chosen from ruthenium, molybdenum and tantalum or reducibility promoters such as, for example, platinum, palladium or ruthenium.
  • additional elements in particular promoters of activity, such as for example at least one element chosen from ruthenium, molybdenum and tantalum or reducibility promoters such as, for example, platinum, palladium or ruthenium.
  • the content, by weight, of an additional element relative to the total weight of catalyst is generally between 0.01 and 5%. These additional elements can be introduced at the same time as the Group VIII metal or in at least one subsequent step.
  • the catalyst contains cobalt and ruthenium.
  • the catalyst contains cobalt and tantalum.
  • the catalyst comprising at least one Group VIII metal impregnated on the support comprising quadratic and / or amorphous zirconia and optionally containing an alumina phase is subjected to at stages of drying and calcination, and then is pre-reduced by at least one reducing compound, for example chosen from the group formed by hydrogen, carbon monoxide and formic acid, possibly brought into contact with a gas inert form such as nitrogen, for example in a reducing compound / reducing compound (reducing compound + inert gas) molar ratio of between 0.001: 1 and 1: 1.
  • the reduction can be conducted in phase at a temperature of between 100 ° C.
  • the conversion of the synthesis gas into hydrocarbons is then carried out under a total pressure usually of between 0.1 and 15 MPa and preferably between 1 and 10 MPa, the temperature generally being between 150 and 350 ° C. and preferably between 170 and 300 ° C.
  • the hourly volumetric rate is usually between 100 and 20 000 volumes of synthesis gas per volume of catalyst per hour and preferably between 400 and 5000 volumes of synthesis gas per volume of catalyst per hour, and the ratio H 2 /
  • the CO in the synthesis gas is usually between 1: 2 and 5: 1, preferably between 1.2: 1 and 2.5: 1.
  • the catalyst is preferably used in the form of fine calibrated powder having a grain size of less than 500 microns, preferably between 10 and 150 microns, more desirably between 20 and 120 microns, in the presence of a liquid phase which may be constituted by at least one hydrocarbon having at least 5, preferably at least 10, carbon atoms per molecule.
  • a liquid phase which may be constituted by at least one hydrocarbon having at least 5, preferably at least 10, carbon atoms per molecule.
  • the use of the catalyst in suspension in a liquid phase in a three-phase reactor of bubble column type is advantageous because this type of implementation allows optimal use of the catalyst performance (activity and selectivity), by limiting the diffusional phenomena within the granular, as well as a very significant limitation of thermal effects in the catalyst grain, which is surrounded by a liquid phase.
  • This type of implementation requires a separation of the catalyst from the reaction products. Under these conditions, the catalyst has improved mechanical properties allowing optimal catalyst and product separation and increased catalyst life.
  • Example 1 (according to the invention) : Catalyst A
  • a catalyst, Co / ZrO 2 is prepared by impregnating cobalt nitrate on a zirconia powder.
  • the cobalt metal content is 13%.
  • the zirconia is prepared beforehand by precipitation of zirconium nitrate with hydrazine: it is amorphous and has a specific surface area of 250 m 2 / g after calcination at 550 ° C.
  • the suspension obtained is atomized and the support thus obtained is in the form of a powder with a particle size of between 20 and 150 microns.
  • the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • Example 2 (according to the invention) : Catalyst B
  • a catalyst B Co / ZrO 2 -Al 2 O 3 , is prepared by impregnation of cobalt nitrate on a zirconia-alumina.
  • the cobalt metal content is equal to 12.5%.
  • the zirconia-alumina is prepared beforehand by coprecipitation of a mixture ZrOCl 2 and Al (NO 3 ) 3 to which NH 4 OH is added. After drying and calcining at 700 ° C., the support is amorphous, its specific surface area is 158 m 2 / g. The support contains 15% alumina.
  • the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • a C, Co / ZrO 2 catalyst is prepared by impregnating cobalt nitrate with a zirconia.
  • the cobalt metal content is 13%.
  • the zirconia is previously prepared by precipitation of ZrOCl 2 with NH 4 OH followed by ripening at constant pH. After drying and calcination at 500 ° C., the zirconia is quadratic and has a specific surface area of 135 m 2 / g.
  • the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • a catalyst D is prepared by impregnation of cobalt nitrate on a support containing 70% of alumina, 25% of zirconia and 5% of silica. The content of cobalt metal is equal to 12%.
  • the support is prepared as in Example 2 by coprecipitation of a mixture ZrOCl 2 and Al (NO 3 ) 3 to which NH 4 OH is added. Simultaneously with the addition of NH 4 OH, a small amount of ammonium silicate is added so as to obtain the composition of the catalyst support described above. After drying and calcination at 550 ° C., the support obtained is amorphous and has an area of 90 m 2 / g. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • An E, Co / Al 2 O 3 catalyst is prepared by impregnating cobalt nitrate on a support consisting of a Puralox Scca 5-170 alumina powder with a specific surface area equal to 180 m 2 / g. The final cobalt content is 12.5%.
  • the alumina support employed is in the form of a powder having a particle size of between 20 and 150 microns.
  • the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • Catalyst F is prepared by impregnating cobalt nitrate on a support containing 90% alumina, 10% zirconia. The cobalt metal content is 13%.
  • the support is prepared by impregnating zirconium isopropoxide with Puralox Scca 5-170 alumina powder having a specific surface area of 180 m 2 / g. After drying and calcination at 550 ° C., the support obtained has zirconia in monoclinic form. The catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • a catalyst G Co / ZrO 2 , is prepared by impregnation of cobalt nitrate on a zirconia.
  • the cobalt metal content is 13%.
  • the zirconia is prepared by precipitation of ZrOCl 2 with NH 4 OH.
  • the freshly prepared gel is washed with ethanol. After drying and calcining at 500.degree.
  • Zirconia is monoclinic and has an area of 112 m 2 / g.
  • the catalyst resulting from the impregnation is dried and calcined at 400 ° C.
  • the catalysts used in the process according to the invention (A to D) have a significantly higher mechanical strength compared to catalysts E, F and G.

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

Claims (11)

  1. Verfahren zur Synthese von Kohlenwasserstoffen aus einem Gemisch, das Kohlenmonoxid und Wasserstoff, gegebenenfalls Kohlendioxid CO2, umfasst, in Gegenwart eines Katalysators, der mindestens ein Metall der Gruppe VIII umfasst, dessen Gehalt im Bereich zwischen 0,1 und 50 Gew.-% liegt, bezogen auf das Gesamtgewicht des Katalysators, und einen Träger, der mindestens 10 Gew.-% Zirkoniumdioxid in quadratischer und/oder amorpher Form enthält, bezogen auf die Gesamtmasse des Trägers, wobei der Träger Zirkoniumdioxid oder ein Zirkoniumdioxid-Aluminiumoxid-Mischoxid umfasst, wobei der Katalysator in Suspension in einer flüssigen Phase in einem Dreiphasenreaktor eingesetzt wird.
  2. Verfahren nach Anspruch 1, wobei der Träger mindestens 0 bis 90 Gew.-% Aluminiumoxid enthält, bezogen auf die Gesamtmasse des Trägers.
  3. Verfahren nach Anspruch 2, wobei der Träger mindestens 10 Gew.-% Zirkoniumdioxid in quadratischer und/oder amorpher Form, bezogen auf die Gesamtmasse des Trägers, und 1 bis 75 Gew.-% Aluminiumoxid, bezogen auf die Gesamtmasse des Trägers, enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der Träger eine spezifische Oberfläche größer als 50 m2/g aufweist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei der Träger eine spezifische Oberfläche größer als 80 m2/g aufweist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei der Träger mindestens ein stabilisierendes Element, ausgewählt aus der Gruppe gebildet aus Silicium, Niob, Lanthan, Praseodym, Neodym, enthält.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei das Metall der Gruppe VIII ausgewählt ist aus der Gruppe bestehend aus Eisen, Cobalt und Ruthenium.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei das Metall der Gruppe VIII Cobalt ist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei der Katalysator mindestens einen Aktivitätspromotor enthält.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei der Katalysator mindestens einen Reduzierbarkeitspromotor enthält.
  11. Verfahren nach einem der Ansprüche 1 bis 10, wobei der Katalysator in Form eines feinen Pulver vorliegt, der eine Korngröße von weniger als 500 µm aufweist.
EP02803430A 2001-10-11 2002-10-08 Verfahren zur kohlenwasserstoffsynthese in einem dreiphasenreaktor in gegenwart eines katalysators, der ein metall der gruppe viii auf zirconiumoxid oder zirconiumoxid-aluminiumoxid-mischoxid geträgert enthält Expired - Lifetime EP1436360B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0113138 2001-10-11
FR0113138A FR2830858B1 (fr) 2001-10-11 2001-10-11 Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumine
PCT/FR2002/003415 WO2003044126A1 (fr) 2001-10-11 2002-10-08 Procede de synthese d'hydrocarbures dans un reacteur triphasique en presence d'un catalyseur comprenant un metal du groupe viii supporte sur zircone ou sur oxyde mixte zircone-alumine

Publications (2)

Publication Number Publication Date
EP1436360A1 EP1436360A1 (de) 2004-07-14
EP1436360B1 true EP1436360B1 (de) 2010-04-07

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EP02803430A Expired - Lifetime EP1436360B1 (de) 2001-10-11 2002-10-08 Verfahren zur kohlenwasserstoffsynthese in einem dreiphasenreaktor in gegenwart eines katalysators, der ein metall der gruppe viii auf zirconiumoxid oder zirconiumoxid-aluminiumoxid-mischoxid geträgert enthält

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EP (1) EP1436360B1 (de)
CA (1) CA2462535C (de)
DE (1) DE60235903D1 (de)
FR (1) FR2830858B1 (de)
WO (1) WO2003044126A1 (de)
ZA (1) ZA200402139B (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005079979A1 (ja) * 2004-02-24 2005-09-01 Japan Oil, Gas And Metals National Corporation 炭化水素類製造用触媒、その製造方法、及びその触媒を用いた炭化水素類の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH670250A5 (de) * 1986-11-05 1989-05-31 Lonza Ag
DE4445142A1 (de) * 1994-12-17 1996-06-20 Basf Ag Katalysatoren oder Träger die im wesentlichen aus monoklinem Zirconiumdioxid bestehen
ZA9711090B (en) * 1996-12-13 1998-06-15 Shell Int Research Process for the preparation of hydrocarbons.
FR2769519B1 (fr) * 1997-10-13 1999-12-31 Total Raffinage Distribution Catalyseur acide a base de zircone sulfatee et ses utilisations

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EP1436360A1 (de) 2004-07-14
CA2462535A1 (fr) 2003-05-30
ZA200402139B (en) 2005-09-28
DE60235903D1 (de) 2010-05-20
CA2462535C (fr) 2010-06-29
FR2830858A1 (fr) 2003-04-18
FR2830858B1 (fr) 2003-12-12
WO2003044126A1 (fr) 2003-05-30

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