WO2014031030A1 - Procédé de production de catalyseur au cobalt - Google Patents

Procédé de production de catalyseur au cobalt Download PDF

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Publication number
WO2014031030A1
WO2014031030A1 PCT/RU2013/000524 RU2013000524W WO2014031030A1 WO 2014031030 A1 WO2014031030 A1 WO 2014031030A1 RU 2013000524 W RU2013000524 W RU 2013000524W WO 2014031030 A1 WO2014031030 A1 WO 2014031030A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
temperature
cobalt
carrier
hours
Prior art date
Application number
PCT/RU2013/000524
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English (en)
Russian (ru)
Inventor
Олег Николаевич ПРОТАСОВ
Сергей Анатольевич АЛХИМОВ
Дмитрий Александрович ГРИГОРЬЕВ
Михаил Николаевич МИХАЙЛОВ
Original Assignee
Общество с ограниченной ответственностью "Объединенный центр исследований и разработок"
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Publication of WO2014031030A1 publication Critical patent/WO2014031030A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • 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
    • C10G2/334—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 molecular sieve catalysts

Definitions

  • the invention relates to petrochemistry, gas chemistry, coal chemistry and relates to Fischer-Tropsch synthesis, in particular, technology for the preparation of cobalt catalyst for Fischer-Tropsch synthesis.
  • the disadvantage of this method is the use of a gas as an activating agent that is different in composition from the process gases used in the synthesis of hydrocarbons according to the Fischer-Tropsch method, which requires the creation of separate mixing units and separate lines for supplying these gases to the reactor.
  • the aim of this invention is to reduce energy consumption in the production of synthetic hydrocarbons in the presence of a catalyst due to its activation by synthesis gas or hydrogen-containing gas at temperatures not exceeding 250 ° C.
  • a granular carrier is prepared by calcining the feedstock at a temperature of from 400 to 800 ° C for 1 to 20 hours, which is then ground to particle sizes not exceeding 0.5 mm and before granulation are mixed with a modifier of transition metal compounds of groups III and IV of the Periodic Table D.
  • the feedstock for the carrier is selected from the group: aluminum, silicon, titanium, zirconium, cerium, or amorphous or crystalline aluminosilicates or mixtures thereof.
  • the carrier granules are calcined at temperatures of 400-800 ° C.
  • the active component is carried out in an amount of 10-30 wt.% On the finished catalyst in one or several stages, the number of which usually does not exceed three, by impregnating the support or catalyst precursor with an aqueous solution of cobalt salt, for example, cobalt hexahydrate, followed by calcination after each stage making the active component at temperatures of 270-500 ° C for 1-4 hours.
  • cobalt salt for example, cobalt hexahydrate
  • the introduction of promoters is carried out by a separate stage of impregnation, either by co-impregnation with the active component, for oxide promoters, preferably in the first stage of impregnation, or before the first stage of introducing the active component.
  • calcination is carried out at temperatures of 270-500 ° C for 1-4 hours.
  • the activation process is carried out at a temperature in the range from 180 to 250 ° C in the presence of hydrogen or synthesis gas.
  • the catalyst placed in a fixed-bed Fischer-Tropsch synthesis reactor, is heated in a stream of hydrogen or a mixture of carbon monoxide and hydrogen (synthesis gas) with a gas volumetric velocity selected for the process to an initial temperature, usually in the range of 240-250 ° C, to activate clean hydrogen or its mixture with an inert gas and 180-200 ° C for activation by synthesis gas. Then, in the case of using a mixture of carbon monoxide and hydrogen as an activation gas, the temperature rises stepwise to a final value of 250 ° C in increments of 8-12 ° C.
  • the rate of temperature rise to the initial value is 0.5-2 degrees / min, the rise rate between the steps of the temperature regime is 0.1-2 degrees / min.
  • the duration of aging at a temperature at each stage, for a catalyst activated by synthesis gas is determined by the stabilization of the values of CO conversion and selectivity for liquid hydrocarbons and methane at a given temperature.
  • the activation procedure using pure hydrogen or its mixture with an inert gas continues continuously for 16-48 hours.
  • the calculation of CO conversion is carried out according to the following formula:
  • t, s s / SOv is the mass of carbon contained in carbon monoxide in 1 m of gas leaving the reactor.
  • V ⁇ y is the volume of synthesis gas passing through the catalyst bed, m 3 .
  • the activation process according to the present invention is carried out in one of two ways.
  • Freshly prepared catalyst is crushed to a fraction of 0.1-0.2 mm, loaded into a Fischer-Tropsch synthesis reactor, a mixture of hydrogen and inert gas (argon, nitrogen or helium) with a hydrogen content of at least 10 vol.% Or pure hydrogen at a space velocity of 1000-3000 h "1 and a pressure of 0.05 to 2.0 MPa. Then the catalyst is heated to an initial temperature in the range of 240-250 ° C with a heating rate of 0.5-2 degUmin and the catalyst is kept under these conditions for 16-48 hours.
  • argon, nitrogen or helium argon, nitrogen or helium
  • the reactor After activation, the reactor is cooled in a stream of hydrogen or hydrogen-containing gas to a temperature of less than 160 ° C and the flow of the activating agent is replaced by a stream of a mixture of carbon monoxide and hydrogen at a space velocity of 1000 h "1 and the working pressure in the reactor is set to 2.0 MPa. Then, the catalyst is heated to selected synthesis temperature of 210-230 ° C.
  • Example 1-A (comparison example)
  • the 10% Co / catalyst (90% Al 2 O 3 + 10% CeO 2 ) contains 10% cobalt by weight of the catalyst and 90% of the support.
  • the 10% Co / catalyst (88% ZrO2 + 12% La 2 O 3 ) contains 10% cobalt by weight of the catalyst and 90% of the support.
  • the active component is carried out in two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate in an amount of 20 wt.%, followeded by calcination of the catalyst precursor at a temperature of 380 ° C for 2.5 hours.
  • the precursor of the carrier Zr0 2 - two -water zirconyl nitrate ZrO (N0 3 ) 2 -2H 2 0 calcined at a temperature of 500 ° C for 12 hours.
  • the resulting powder is ground to a fraction of less than 0.15 mm.
  • the ground carrier is mixed with a modifier — aluminum oxide A1 2 0 3 in an amount of 20 wt.% By weight of the catalyst and cobalt hexahydrate nitrate, corresponding to 30 wt.% cobalt per finished catalyst.
  • the resulting mass is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 400 ° C for 12 hours.
  • the rate of temperature increase between steps is 1, 5 deg./min.
  • the precursor of the carrier Zr0 2 - two -water zirconyl nitrate ZrO (N0) 2 -2H 2 0 calcined at a temperature of 400 ° C for 6 hours.
  • the resulting powder is ground to a fraction of less than 0.35 mm.
  • the crushed support is mixed with a modifier — Ce oxide in an amount of 10% by weight of the support — and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 800 ° C.
  • the catalyst was activated at 249 ° C in a stream of hydrogen with a space velocity of 1200 h "1 for 20 hours at a pressure of 0.1 MPa.
  • the rate of temperature rise to the final value was 0.8 deg / min.
  • the catalyst 10% Co + l% Pd / (90% ZrO 2 -SO 4 + 10% Y-Al 2 O 3 ) contains 20% cobalt by weight of the catalyst, 1.0 wt.% Palladium and 79% of the support and is activated by the method 2 of the present invention.
  • Application of the active component is carried out in an amount of 10 wt.% By one stage of impregnation of an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 270 ° C for 2 hours. Palladium is introduced into the catalyst by co-impregnation with cobalt in the first stage of introducing the active component from an appropriate amount of an ammonia solution of palladium chloride (I) (PdCl 2 ).
  • I palladium chloride
  • the catalyst was activated at 250 ° C. in a stream of hydrogen with a space velocity of 3000 h 1 1 for 24 hours at a pressure of 0.1 MPa.
  • the rate of temperature rise to the final value was 1.5 deg / min.

Abstract

L'invention se rapporte au domaine de la pétrochimie, de la chimie du gaz, de la chimie du charbon, et concerne une synthèse de Fischer-Tropsch, et notamment un procédé de production puis d'activation d'un catalyseur au cobalt pour une synthèse de Fischer-Tropsch. Le procédé d'activation consiste à mettre le catalyseur en contact avec un gaz contenant de l'hydrogène ou avec un mélange de monoxyde de carbone et d'hydrogène dans un processus visant à les convertir en hydrocarbures à des températures de synthèse de Fischer-Tropsch. Le catalyseur produit et activé selon ce procédé n'est pas moins efficace que les catalyseurs produits et activés par d'autres procédés connus de l'art antérieur.
PCT/RU2013/000524 2012-08-24 2013-06-20 Procédé de production de catalyseur au cobalt WO2014031030A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2012136252/04A RU2493914C1 (ru) 2012-08-24 2012-08-24 Способ получения кобальтового катализатора
RU2012136252 2012-08-24

Publications (1)

Publication Number Publication Date
WO2014031030A1 true WO2014031030A1 (fr) 2014-02-27

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Country Status (2)

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RU (1) RU2493914C1 (fr)
WO (1) WO2014031030A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020028745A1 (en) * 1999-10-15 2002-03-07 Alla Jurievna Krylova Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions
US7097786B2 (en) * 2001-02-16 2006-08-29 Conocophillips Company Supported rhodium-spinel catalysts and process for producing synthesis gas
RU2326732C1 (ru) * 2006-12-27 2008-06-20 ООО "Объединенный центр исследований и разработок" Катализатор для синтеза фишера-тропша и способ его получения
US20090023822A1 (en) * 2007-07-19 2009-01-22 Tijm Peter J Method for activating and regenerating catalyst for a fischer-tropsch synthesis reaction
RU2405625C1 (ru) * 2009-06-16 2010-12-10 Общество с ограниченной ответственностью "ИНФРА Технологии" Катализатор для синтеза углеводородов из co и h2 и способ его получения
RU2444557C1 (ru) * 2010-09-30 2012-03-10 Общество с ограниченной ответственностью "СинТоп" Способ получения синтетических жидких топлив из углеводородных газов по методу фишера-тропша и катализаторы для его осуществления

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0512791D0 (en) * 2005-06-23 2005-07-27 Johnson Matthey Plc Catalysts
RU2445161C1 (ru) * 2010-08-19 2012-03-20 Общество с ограниченной ответственностью "СинТоп" Способ активации кобальтового катализатора синтеза фишера-тропша

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020028745A1 (en) * 1999-10-15 2002-03-07 Alla Jurievna Krylova Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions
US7097786B2 (en) * 2001-02-16 2006-08-29 Conocophillips Company Supported rhodium-spinel catalysts and process for producing synthesis gas
RU2326732C1 (ru) * 2006-12-27 2008-06-20 ООО "Объединенный центр исследований и разработок" Катализатор для синтеза фишера-тропша и способ его получения
US20090023822A1 (en) * 2007-07-19 2009-01-22 Tijm Peter J Method for activating and regenerating catalyst for a fischer-tropsch synthesis reaction
RU2405625C1 (ru) * 2009-06-16 2010-12-10 Общество с ограниченной ответственностью "ИНФРА Технологии" Катализатор для синтеза углеводородов из co и h2 и способ его получения
RU2444557C1 (ru) * 2010-09-30 2012-03-10 Общество с ограниченной ответственностью "СинТоп" Способ получения синтетических жидких топлив из углеводородных газов по методу фишера-тропша и катализаторы для его осуществления

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