WO2013078872A1 - 一种共沉淀法制备用于一碳化学反应的催化剂的方法 - Google Patents

一种共沉淀法制备用于一碳化学反应的催化剂的方法 Download PDF

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WO2013078872A1
WO2013078872A1 PCT/CN2012/079014 CN2012079014W WO2013078872A1 WO 2013078872 A1 WO2013078872 A1 WO 2013078872A1 CN 2012079014 W CN2012079014 W CN 2012079014W WO 2013078872 A1 WO2013078872 A1 WO 2013078872A1
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catalyst
temperature
precipitation
metal compound
preparing
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French (fr)
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张燚
刘意
陈建峰
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Beijing University of Chemical Technology
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J23/78—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 alkali- or alkaline earth 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J23/8892—Manganese
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a novel catalyst preparation process, and in particular to a method for preparing a carbon chemical catalyst by a coprecipitation method.
  • the catalyst preparation method can be widely applied to a one-carbon chemical reaction catalyst such as Fischer-Tropsch synthesis, methanol synthesis and methane reforming, and belongs to the technical field of catalysts.
  • the reaction in which the reactant contains only one carbon atom during the chemical reaction is collectively referred to as a one-carbon chemistry.
  • the main purpose of carbon chemistry is to save coal and oil resources, generate more fuel with less carbon raw materials, and provide it to humans.
  • One carbon chemistry begins with a hydrocarbon reaction.
  • a compound containing one carbon atom - alkane (CH 4 ), syngas (CO and H 2 ), C () 2 , C chat, HCH0, etc. as the initial reactants, should be synthesized into a series of important chemical raw materials.
  • the chemistry of fuel The one-carbon species of carbon-based chemistry is CO and H 2 , which are readily available from any carbon-bearing resource. This is the biggest reason why one-carbon chemistry can be at the heart of the future chemical industry.
  • a carbon chemical industry is actually a new generation of coal chemical and natural gas chemical industry.
  • the products mainly include liquid fuels and fuel additives, low-carbon olefins, synthetic low-carbon alcohols, and also include six major chemical products such as methanol and its products, formaldehyde and its series of products.
  • the key to grasping the chemistry of a carbon is the catalyst, so how to develop an excellent catalyst affects the success or failure of a carbon chemistry.
  • the precipitation method usually involves mixing different chemical components in a solution state, adding a suitable precipitant to the mixture to prepare a precursor precipitate, and then drying or calcining the precipitate to obtain a corresponding powder particle.
  • the coprecipitation method used in the present invention means that one or more cations are contained in the solution, and they are homogeneously present in the solution, and a precipitating agent is added. After the precipitation reaction, a uniform precipitation of various components can be obtained.
  • Another feature of the invention resides in the pretreatment of a certain amount of metal compound with various alcohols.
  • the coprecipitation method in order to separate the nucleation and growth processes of the grains, rapidly nucleate and grow.
  • the size of the particles It is determined by the nucleation rate and the rate of nuclear growth, so the performance of the precipitated particles can be controlled by controlling the nucleation rate and the rate of nuclear growth : > Due to the presence of alcohol in the precipitation solution, the concentration of the precipitation solution is changed, and the formation of the precipitation solution is effectively controlled.
  • the nuclear velocity while the alcohol solution is coated around the grains, inhibits the rate of nuclear growth and prevents secondary agglomeration of the particles, thereby obtaining a uniform particle size distribution and a suitable particle size.
  • the object of the present invention is to provide a preparation method of a novel catalyst for a one-carbon chemical reaction, which can be applied to a Fischer-Tropsch synthesis drill-based catalyst and an iron-based catalyst, a methane reforming nickel-based catalyst and a drill-based catalyst, and a methanol synthesis.
  • a carbon-based chemical reaction catalyst such as a copper-based catalyst, a copper oxide-based catalyst, and a cobalt-based catalyst.
  • the main object of the present invention can be achieved by the following technical solutions;
  • a novel method for preparing a catalyst by a coprecipitation method comprising the steps of:
  • the pretreatment temperature is controlled between () and 150 ,, and the time is between 0.1 and 8 hours, and the alcohol solution of the metal compound is obtained, and the concentration is 10 wt. %- ⁇ 8( ⁇ %;
  • the concentration of the metal compound is between 0.1% by weight and 40% by weight;
  • step (3) The solution obtained in the step (2) is slowly mixed with the precipitating agent and poured into the precipitation reactor to control the precipitation temperature between 0 and 120 ° C, and the pH value is between 7 and 13; 48 hours, the aging temperature is between 0 8 (TC;
  • the precipitate is suction filtered, washed and dried.
  • the drying temperature is 40 150 ⁇ , the temperature is 4 - 48 hours, and then placed in a muffle furnace for roasting.
  • the baking temperature is 200-80 () ⁇ , constant temperature 2- 20 hours. And then obtained by compression, granulation and reduction to obtain a shaped catalyst:
  • the alcohol in the above step (1) may be one of various isomers of methanol, ethanol, propanol, butanol, pentanol, propylene glycol, propanol, butanediol, polyethylene glycol and the above alcohols. kind, two or several.
  • the precipitating agent may be one of potassium carbonate, sodium carbonate, ammonium carbonate, urea, and ammonia water.
  • the precipitant is added in the form of a solution at a concentration of lwt% 50% by weight.
  • the metal compound comprises one of iron, copper, cobalt, nickel, zinc, manganese, lanthanum, magnesium, aluminum, zirconium, a soluble compound of two or more metals, preferably at least containing iron, copper, cobalt, nickel One kind.
  • step (3) the feeding method of the solution and the precipitating agent is added, reverse added and cocurrent, preferably cocurrent precipitation.
  • a method for preparing an iron-based catalyst by a ⁇ precipitation method the steps of which are as follows
  • the pretreatment temperature is controlled between 0 150 Torr, and the time is 0. 1-8 small HT, obtaining an alcohol solution of the metal compound, the concentration is 10 wt% - 80 wt%;
  • the concentration of the metal compound is between 0.1% by weight and 40% by weight;
  • step (3) slowly mixing the solution obtained in step (2) with the precipitant into the precipitation reactor to control the temperature of the lake at 0-120 Instruction manual
  • the PH value is between 7-13; after the end of the precipitation, aging for 2-48 hours, the aging temperature is between 0-80 ;;
  • the method for preparing an iron-based catalyst by the above precipitation method may be methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerin, butanediol, polyethylene glycol and the like.
  • One, two or more of various isomers of alcohol may be methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerin, butanediol, polyethylene glycol and the like.
  • One, two or more of various isomers of alcohol may be methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerin, butanediol, polyethylene glycol and the like.
  • One, two or more of various isomers of alcohol may be methanol, ethanol, propanol, butanol, pentan
  • the metal compound comprises a soluble compound of an active component iron and a soluble compound of one or more metals of copper, cobalt, manganese, magnesium, zinc, and a soluble compound including a nitrate compound And one or more of an acetic acid compound, a carbonyl compound, an alcoholic compound, a sulfuric acid compound, and an oxalic acid compound.
  • the method for preparing an iron-based catalyst by a precipitation method is one or more of potassium carbonate, sodium carbonate, ammonium carbonate, urea, and ammonia water.
  • a method for preparing a copper-based catalyst by a precipitation method the steps of which are as follows
  • the pretreatment temperature is controlled between 0-15 CTC, and the time is between 0.1 and -8 hours, and an alcohol solution of the metal compound is obtained, and the concentration is l (1 ⁇ 2 t% -8) ( rt% ;
  • the concentration of the metal compound is between 0.1% by weight and 40% by weight;
  • step (3) slowly mixing the solution obtained in step (2) with the precipitant into the precipitation reactor, controlling the precipitation temperature between 0--120 C, pH between 7 and 13; aging 2-48 after precipitation Hours, the aging temperature is between 0-80 ;;
  • the precipitate is filtered, washed and dried, and the drying temperature is 40 ⁇ - 150 ⁇ :', the temperature is 4 - 48 hours, and then placed in a muffle furnace for roasting, the baking temperature is 20G-800 °C, Constant temperature 2-20 hours; then tableting, granulating, reduction to obtain a shaped catalyst;
  • the method for preparing a copper-based catalyst by the above precipitation method may be methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, propane: triol, butanediol, polyethylene glycol and the like.
  • the method for preparing a copper-based catalyst by a precipitation method includes the active component copper and a soluble compound of one or more of zinc, aluminum, zirconium and hafnium, and the soluble compound includes nitrate, acetate, One or more of a carbonyl compound, an alcoholate salt, a sulfate salt, and an oxalate salt.
  • the method for preparing a copper-based catalyst by the above precipitation method wherein the precipitating agent is potassium carbonate, sodium carbonate, ammonium carbonate, urea, ammonia One or several of the water.
  • a method for preparing a cobalt-based catalyst by a precipitation method the steps of which are as follows
  • the concentration of the metal compound is in the range of 0. lwt% - 4 (1 ⁇ 2 [%;
  • the precipitate is filtered, washed and dried, dried at a temperature of 40 150 ⁇ , at a constant temperature of 4 48 hours, and then placed in a muffle furnace for roasting at a temperature of 200 80 CT C and a constant temperature of 20 20 hours; Forming the catalyst by tableting, granulating and reducing;
  • the method for preparing a cobalt-based catalyst by the above precipitation method may be methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerin, butanediol, polyethylene glycol and the above alcohol.
  • the method for preparing a cobalt-based catalyst by the above precipitation method comprises the compound of cobalt of an active component and one or more compounds of nickel, manganese, lanthanum and aluminum, and the compound comprises a nitrate, an acetate and a carbonyl compound.
  • One or more of the alcoholic acid oxalic acid a is one or more of the alcoholic acid oxalic acid a.
  • the method for preparing a base catalyst by the above precipitation method wherein the precipitating agent is one or more of potassium carbonate, cesium carbonate, ammonia carbonate, and urea ammonia.
  • a method for preparing a nickel-based catalyst by a precipitation method the steps of which are as follows
  • the alcohol solution of the metal compound is obtained at a concentration of 10% by weight to 80% by weight;
  • the concentration of the metal compound is between 0.1% by weight and 40% by weight;
  • step (3) slowly mixing the solution obtained in step (2) with the precipitant into the precipitation reactor, controlling the precipitation temperature to be between 0 and 120, and the enthalpy value is between 7 and 13; aging for 2 48 hours after the precipitation, aging The temperature is between 0--80 ⁇ ;
  • the precipitate is suction filtered, washed and dried, dried at a temperature of 40-150 ° C, kept at a constant temperature for 4 - 48 hours, and then placed in a muffle furnace for calcination at a temperature of 200 800 ° C and a constant temperature of 2 20 Hours; after compression, granulation, reduction to obtain a shaped catalyst;
  • the method for preparing a nickel-based catalyst by a precipitation method may be methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, propanol, butanediol, polyethylene glycol, polyethylene glycol.
  • the method for preparing a nickel-based catalyst by the above precipitation method wherein the metal compound comprises a compound of the active component nickel and one or more soluble compounds of copper, cerium, magnesium and zirconium, and the soluble compound comprises vinegar, vinegar One or more of an acid salt, a carbonyl compound, an alcoholate salt, a sulfate salt, or an oxalate salt.
  • the method for preparing a nickel-based catalyst by the above precipitation method wherein the precipitating agent is one or more of potassium carbonate, uranium carbonate, ammonium carbonate, urea, and ammonia.
  • the precipitation catalyst prepared by the present invention can catalyze a very high conversion rate of the living month.
  • the precipitated catalyst prepared by the present invention has a relatively stable reaction property.
  • the catalyst preparation material of the invention is cheap and easy to obtain, the preparation process is simple, the catalyst product has low cost, and is suitable for industrial production.
  • the catalyst preparation method of the present invention is not limited to any specific one-carbon reaction catalyst, but the present invention will be described below with respect to at least one one-carbon reaction catalyst. However, the scope of protection of the present invention is not limited thereto.
  • Iron-based catalyst puncturing Weighing ferric nitrate, copper nitrate, potassium nitrate, manganese nitrate, magnesium nitrate, in a molar ratio of 200:3:4:100:20 and propanol to a concentration of 10 ⁇ 1; Pretreatment, heating to 150 ° C with stirring, 1 hour after constant temperature, until the solution is cooled to room temperature, adding a certain amount of water, preparing a solution with a concentration of 3 wt%, mixing well, and slowly mixing with the sodium carbonate solution into the precipitate In the reactor, the pH of the precipitate was controlled at 10 and the precipitation temperature was 90 °C. The precipitate was aged for 2 hours and the aging temperature was 70 °C.
  • the precipitate was suction filtered, washed, dried, dried at a temperature of 80 Torr, and kept at a constant temperature of 48 liters, and then placed in a muffle furnace for calcination at a temperature of 5 GCTC for 5 hours. After tableting and granulation, a catalyst is obtained.
  • the reaction conditions were 3G0 ° C, 1, 5 MPa, 250 () h - s (V / V), and the reaction results are shown in Table 1.
  • Catalyst preparation weigh iron nitrate, copper nitrate, potassium nitrate, manganese nitrate, magnesium nitrate, and prepare a 3 wt% aqueous solution at a molar ratio of 200:3:4:100:20. After mixing, it is added to the precipitation reactor. Adding uranium carbonate solution to the precipitation reaction In the device, the pH of the precipitate is controlled at 8, and the precipitation temperature is 60 °C. 0 After the precipitation, the aging is 2 small S, i, and the aging temperature is 30 °C. The precipitate was suction filtered, washed and dried. The drying temperature was 120 Torr, the temperature was kept for 12 hours, and then placed in a muffle furnace for calcination at a temperature of 600 ° C for 2 hours. Further, by tableting and granulation, a shaped catalyst is obtained.
  • Example 1 90.9 Book 4.2 4. i 91.4 Comparative Example 1 50.7 5.3 10, 2 84.5
  • Example 2
  • Preparation of copper-based catalyst Weigh copper nitrate and zinc nitrate, and prepare a copper nitrate zinc nitrate solution with a molar ratio of 1:1 and pentanol to a total concentration of 303 ⁇ 4%, and preheat in a vessel and stir to 30 °C. After the constant temperature of 8 hours, the solution is cooled to room temperature, and a certain amount of water is added to prepare a copper nitrate zinc nitrate solution with a concentration of 15%. After mixing uniformly, it is slowly mixed with the ammonia aqueous solution into the precipitation reactor to control the precipitation PH.
  • the precipitation temperature is 10 ( ⁇ aging for 10 hours after the end of precipitation, the aging temperature is 6 (rC.
  • the precipitate is filtered, washed and dried, the drying temperature is 120 ° C, the temperature is kept for 10 hours, then put into the horse
  • the furnace was calcined at a calcination temperature of 400 ° C for 3 hours, and then subjected to tableting and granulation to obtain a shaped catalyst.
  • Preparation Weigh copper nitrate and zinc nitrate, prepare a concentration of 15% copper nitrate zinc nitrate aqueous solution at a molar ratio of 1:1, and slowly mix with the urea solution into the precipitation reactor to control the precipitation enthalpy at 9, precipitation temperature of 50 ° C after 30 hours aging ⁇ precipitation, the aging temperature is 25 ':. C. the precipitate was filtered off sleeve, washed with dry in a clean, dry in a temperature of 100 TJ temperature for 24 hours, and put into a muffle furnace? The medium is calcined, the calcination temperature is 400 Torr, and the temperature is kept for 3 hours. After compression and granulation, a molding catalyst is obtained.
  • Preparation of nickel-based catalyst Weigh nickel nitrate and magnesium nitrate. The monthly molar ratio is 1:4 and the butanediol is formulated into a solution with a total concentration of 80% by weight. Stir and heat in a container to 60 ⁇ , after a constant temperature of 0.5 book, wait The solution is cooled to room temperature, a certain amount of water is added, and a solution of 40% by weight of nickel nitrate and magnesium nitrate is prepared. After mixing uniformly, it is slowly mixed with the ammonium carbonate solution into the precipitation reactor to control the pH of the precipitate at 12, the precipitation temperature. Is 120. C. After the end of the precipitation, the mixture was aged for 48 hours, and the aging temperature was 5C.
  • the precipitate was suction filtered, washed and dried.
  • the drying temperature was 150 Torr, the temperature was kept for 24 hours, and then placed in a muffle furnace for calcination at a temperature of 70 CTC for 2 hours. Further, by tableting and granulation, a shaped catalyst is obtained.
  • reaction gas CO (1/1) was introduced to initiate a methane reforming reaction.
  • the reaction conditions were 700 ° C, 0. IMPa, lOOOOh - ;
  • Catalyst preparation Weigh nickel nitrate and magnesium nitrate, and prepare a concentration of 40wt9 nickel nitrate and magnesium nitrate solution at a molar ratio of 1:4. After mixing, add to the precipitation reactor containing ammonium carbonate solution to control the pH value of the precipitate. 12, the precipitation temperature is 65 ° (:. After aging, the aging temperature is 48 hours, the aging temperature is 60 ° C. The precipitate is filtered, washed and dried, dried; the drying temperature is 120 ⁇ , the temperature is 15 hours, and then placed in the muffle furnace The medium is calcined, the calcination temperature is 400, and the temperature is kept for 5 hours. After compression and granulation, a shaped catalyst is obtained.
  • Cobalt-based catalyst preparation weigh octacarbonyl bis-cobalt, manganese nitrate, molar ratio of 1: 4 and glycerol to a concentration of 20 wt% octacarbonyl bis-cobalt manganese nitrate solution, pre-treating in a container, stirring and heating to 120 ⁇ , after 1.5 hours of constant temperature, wait until the solution is cooled to room temperature, add a certain amount of water, and prepare a concentration of 10 3 ⁇ 4 "[% of cobalt nitrate solution, mix well, slowly mix with sodium carbonate solution into the precipitation reactor, control The pH of the precipitate is 10, and the precipitation temperature is 7 () ° C.
  • the aging is 20 hours, and the aging temperature is 70.
  • the precipitate is suction filtered, washed and dried, and the drying temperature is 90 ⁇ , the temperature is 48 hours, and then placed.
  • the muffle furnace was calcined at a calcination temperature of 350 ° C for 20 hours, and then subjected to tableting and granulation to obtain a shaped catalyst.
  • the above catalyst lg ⁇ hydrogen was reduced in a fixed bed, the reduction conditions were 500 C, 0. IMPa, 50 () 0 h - 1 (V / V), constant temperature 10 h. After the reduction was completed, the reduced catalyst was cooled to room temperature in a nitrogen stream, and then nitrogen was switched to synthesis gas (3 ⁇ 4/C( ).5), and the Fischer-Tropsch synthesis reaction was started.
  • the reaction conditions were 250 ° C, 1.5 MPa, 2500b - 1 (V / V - ), and the reaction results are shown in Table 4.
  • Catalyst preparation Weigh octacarbonyl bis(cobalt), manganese nitrate, and prepare a concentration l (t% of octacarbonylcobalt cobalt, ⁇ octyl acid aqueous solution in a molar ratio of 1:4, and mix it evenly, then add it to the precipitation reactor. Then, the uranium carbonate solution is added to the precipitation reactor, and the control temperature is 10, and the precipitation temperature is 60° C. After aging, the aging is 2 hours, and the aging temperature is 30° C. The precipitate is filtered, washed, and dried. The drying temperature was 80, the temperature was kept for 4 hours, and then calcined in a muffle furnace, and the calcination temperature was 500 V, and the temperature was kept for 2 hours. Then, the catalyst was obtained by tableting and granulation.
  • the above catalyst lg. hydrogen is reduced in a fixed bed, the reducing condition is O. lMPa, 5000h ⁇ (Y / V), constant temperature 10h.
  • the reduced catalyst was cooled to room temperature in a nitrogen stream, and then nitrogen was switched to synthesis gas (iV'COO.5) to start the Fischer-Tropsch synthesis reaction.
  • the reaction conditions were 300. C, 1.5 MPa, 25 [) 0 h - 1 (V / V), the reaction results are shown in Table 4.
  • Example 1 84.5 8.2 4.4 91.4 Comparative Example 1 48.1 15.8 9, 1 75.1

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Abstract

一种共沉淀法制备用于一碳化学反应的催化剂的方法，属于催化剂技术领域。包括如下步骤：在0-150℃下利用醇预处理可溶性金属化合物，预处理后，再用水将金属化合物的醇溶液稀释，然后与沉淀剂慢慢混合进入沉淀反应器中在温度0-120℃、pΗ值7-13之间进行共沉淀反应，沉淀反应结束后经老化、抽滤、洗涤、干燥、焙烧，压片、造粒、还原，获得高催化性能的用于费托合成、甲醇合成、甲烷重整等一碳化学反应的催化剂，本发明所制备的沉淀催化剂催化活性很髙，转化率能达到较高水平，并且具有较为稳定的反应性能。

Description

一种共沉淀法制备用于一碳化学反应的催化剂的方法
技术领域
本发明涉及一种新型催化剂制备方法， 具体地说涉及一种共沉淀法制备一碳化学催化剂 的方法。 该催化剂制备方法可广泛应用于费托合成、 甲醇合成和甲烷重整等一碳化学反应催 化剂， 属于催化剂技术领域。
技术背景
化学反应过程中反应物只含一个碳原子的反应统称为一碳化学。 ·碳化学的主要目的是 节约煤炭和石油资源， 用少的碳原料生成多的燃料 ·， 提供给人类。
说
一碳化学是从一碳氢化反应开始的。以含一个碳原子的化合物—— ^烷 (CH4)、合成气（CO 和 H2)、 C()2 、 C聊、 HCH0等为初始反应物， 反月应合成一系列重要的化工原料和燃料的化学。 一碳化学的基千物质是 CO和 H2， 是从任何含碳资源都能够容易得到的， 这是一碳化学能够处 于未来化学产业的核心的最大理由。
20世纪 70年代中期， 首先在日本提出了 C 1化学的概念。 与此同时， 美国孟山都公司用 低压甲醇羰基化制取醋酸技术获得工业应用；美国莫比尔化学公司 ZSM— 5分子筛催化剂成功 地应用于甲醇转化制汽油； 中东、 加拿大等天然气产量丰富的国家， 由天然气制甲醇生产能 力加速提高， 导致大量甲醇进入市场 因此， 近年来 C 1化学不仅研究以合成气， 而且也研究 以甲醇作为重要的基础原料， 来合成一系列以乙烯为基础原料生产的基本有机化工产品。
一碳化工实际上就是一种新一代的煤化工和天然气化工。 目前产品主要包括液体燃料与 燃料添加剂、 低碳烯烃、 合成低碳醇， 也包括甲醇及其系列产品、 甲醛及其系列产品等六大 类化工产品。 把握一碳化学的关键是催化剂， 因此如何开发优良的催化剂左右着一碳化学的 成败。
发明内容
沉淀法通常是在溶液状态下将不同化学成分的物质混合， 在混合液中加入适当的沉淀剂 制备前驱倖沉淀物 >再将沉淀物进行干燥或锻烧， 从而制得相应的粉体颗粒》
本发明采用的共沉淀法是指在溶液中含有一种或多种阳离子，它们以均相存在于溶液中， 加入沉淀剂， 经沉淀反应后， 可得到各种成分的均一的沉淀， 它是制备含有一种或一种以上 金属元素的催化剂的方法。 共沉淀法的优点在于： 其一是通过溶液中的各种化学反应直接得 到化学成分均一的纳米粉体材料， 其二是容易制备粒度小而且分布均匀的纳米粉体材料。
本发明的另一特征在于利用各种醇预处理一定量的金属化合物。 为了提高制备粉末样品 的粒子尺度分布均匀程度和改善性能， 降低粒子尺寸， 我们对共沉淀法进行了改进， 目的在 于将晶粒的成核和生长过程分开， 快速大量成核， 均勾生长。 在沅淀过程中， 颗粒的大小主 要由成核速度和核增长速度决定的， 因此通过控制成核速度和核增长速度就可以控制沉淀颗 粒的性能:> 由于沉淀溶液中醇的存在， 改变了沉淀溶液的浓度， 有效控制了成核速度， 同时 醇溶液包覆在晶粒周围， 抑制了核增长的速度， 防止颗粒的二次团聚， 从而获得了均匀的粒 子尺度分布以及合适的粒子尺寸。
本发明的目的是提供一种用于一碳化学反应的新型催化剂的制备方法， 该方法可以应用 于费托合成钻基催化剂和铁基催化剂、 甲烷重整镍基催化剂和钻基催化剂、 合成甲醇铜基催 化剂、 CO氧化铜基催化剂和钴基催化剂等一碳化学反应催化剂的制备。
本发明的主要目的可以通过以下技术方案实现；
说
一种共沉淀法制备催化剂的新方法， 其特征在于， 包括以下步骤：
( 1 ) 利用醇预处理可水溶性的金属化合月物， 预处理温度控制在 （)-- 150 Ό之间， 时间在 0. 1-8小时， 得到金属化合物的醇溶液书， 浓度为 10wt%- ·8(Κ^%;
( 2 ) 再用水将金属化合物的醇溶液稀释到适宜浓度，金属化合物的浓度在 0. lwt%-40wt% 之间；
〔3 ) 将步骤（2)所得溶液与沉淀剂慢慢混合迸入沉淀反应器中，控制沉淀温度在 0-120 "C之间, PH值在 7-13之间； 沉淀结束后老化 2- 48小时， 老化温度在 0 8(TC之间;
(4) 将沉淀抽滤、 洗涤干净后干燥， 干燥温度为 40 150Ό , 恒温 4 -48小时， 再放入 马弗炉中焙烧， 焙烧温度为 200- ·80()Γ , 恒温 2- 20小时; 再经压片、 造粒， 还原 获得成型催化剂：
上述步骤（1 ) 中醇可以为甲醇、 乙醇、 丙醇、 丁醇、 戊醇 乙二醇， 丙二醇， 丙 醇、 丁二醇、 聚乙二醇以及以上醇的各种异构体中的一种、 两种或几种。
所述沉淀剂可以为碳酸钾、 碳酸钠、 碳酸氨、 尿素、 氨水中的一种。 沉淀剂以溶液的形 式加入， 浓度在 lwt% 50wt%。
所述金属化合物包括铁、 铜、 钴、 镍、 锌、 锰、 铈、 镁、 铝、 锆中的一种、 两种或几种 金属的可溶性化合物， 优选至少含有铁、 铜、 钴、 镍中的一种。
步骤 （3) 中溶液与沉淀剂的加料方式正加、 反加和并流， 优选为并流共沉淀。
一禾 Φ沉淀法制备铁基催化剂的方法， 其步骤如下，
( 1 ) 利用醇预处理可水溶性的金属化合物， 预处理温度控制在 0 150Ό之间， 时间在 0. 1-8小 HT, 得到金属化合物的醇溶液， 浓度为 10wt%- 80wt%;
(2) 再用水将金属化合物的醇溶液稀释到适宜浓度， 金属化合物的浓度在 0. lwt% 40wt%之间;
(3 ) 将步骤（2)所得溶液与沉淀剂慢慢混合进入沉淀反应器中，控制沆淀温度在 0-120 说 明 书
Γ之间， PH值在 7-13之间； 沉淀结束后老化 2-48小时， 老化温度在 0- 80Γ之 间；
(4 ) 将沉淀抽滤、 洗涤千净后干燥， 干燥温度为 40 15CTC , 恒温 4 - -48小时, 再放入 马弗炉中焙烧， 焙烧温度为 200-800 恒温 2-20小时； 再经压片、 造粒， 还原 获得成型催化剂：
上述沉淀法制备铁基催化剂的方法其预处理的醇可以为甲醇、 乙醇、 丙醇、 丁醇、 戊醇、 乙二醇， 丙二醇， 丙—三醇、 丁二醇、 聚乙二醇以及以上醇的各种异构体中的一种、 两种或几 种。
上述沉淀法制备铁基催化剂的方法， 所述金属化合物包括活性组分铁的可溶性化合物以 及助剂铜、 钴、 锰、 镁、 锌的一种或几种金属的可溶性化合物， 可溶性化合物包括硝酸化合 物、 醋酸化合物、 羰基化合物、 醇氧基化合物、 硫酸化合物、 草酸化合物中的一种或几种。
丄述沉淀法制备铁基催化剂的方法所述沉淀剂为碳酸钾、 碳酸钠、 碳酸氨、 尿素、 氨水 中的一种或几种。
一种沉淀法制备铜基催化剂的方法， 其步骤如下，
( 1 ) 利用醇预处理可水溶性的金属化合物， 预处理温度控制在 0-15CTC之间， 时间在 0. 1 - -8小时， 得到金属化合物的醇溶液， 浓度为 l(½t% -8( rt%;
(2) 再用水将金属化合物的醇溶液稀释到适宜浓度， 金属化合物的浓度在 0. lwt%- 40wt%之间；
(3 ) 将步骤（2)所得溶液与沉淀剂慢慢混合进入沉淀反应器中，控制沉淀温度在 0- - 120 C之间， PH值在 7-13之间； 沉淀结束后老化 2-48小时， 老化温度在 0-80 Ό之 间；
(4) 将沉淀抽滤、 洗涤千净后千燥， 千燥温度为 40·- 150ΐ:'， 恒温 4 -48小时， 再放入 马弗炉中焙烧， 焙烧温度为 20G- 800°C， 恒温 2-20小时； 再经压片、 造粒， 还原 获得成型催化剂；
上述沉淀法制备铜基催化剂的方法其预处理的醇可以为甲醇、 乙醇、 丙醇、 丁醇、 戊醇、 乙二醇， 丙二醇， 丙:三醇、 丁二醇、 聚乙二醇以及以上醇的各种异构偉中的一种、 两种或几 种。
丄述沉淀法制备铜基催化剂的方法所述金属化合物包括活性组分铜以及助剂锌、 铝、 锆、 铈中的一种或几种的可溶性化合物， 可溶性化合物包括硝酸盐、 醋酸盐、 羰基化合物、 醇氧 基盐、 硫酸盐、 草酸盐中的一种或几种。
上述沉淀法制备铜基催化剂的方法， 所述沉淀剂为碳酸钾、 碳酸钠、 碳酸氨、 尿素、 氨 水中的一种或几种。
一种沉淀法制备钴基催化剂的方法， 其其步骤如下，
( 1 ) 利用醇预处理可水溶性的金属化合物， 预处理温度控制在 0 450°C之间， 时间在 0. 1-8小 ^， 得到金属化合物的醇溶液， 浓度为 l(kt%-80wt%;
(2 ) 再用水将金属化合物的醇溶液稀释到适宜浓度， 金属化合物的浓度在 0. lwt%- 4(½[%之间；
(3 ) 将步骤（2)所得溶液与沉淀剂慢慢混合进入沉淀反应器中，控制沉淀温度在 0-120 ΐ〕之间, ΡΗ值在 7 13之间； 沉淀结束后老化 2 48小时， 老化温度在 0 ·80 Ό之 说
间；
(4) 将沉淀抽滤、 洗涤干净后千燥， 干月燥温度为 40 150Ϊ， 恒温 4 48小时， 再放入 马弗炉中焙烧， 焙烧温度为 200 80CT书C , 恒温 2 20小时； 再经压片、 造粒， 还原 获得成型催化剂；
上述沉淀法制备钴基催化剂的方法其预处理的醇可以为甲醇， 乙醇、 丙醇、 丁醇、 戊醇、 乙二醇、 丙二醇、 丙三醇、 丁二醇、 聚乙二醇以及以上醇的各种异构体中的一种、 两种或几 种。
上述沉淀法制备钴基催化剂的方法所述金属化合物包括活性组分钴的化合物以及助剂 镍、 锰、 铈、 铝中的一种或几种化合物， 化合物包括硝酸盐、 醋酸盐、 羰基化合物、 醇氧基 硫酸 草酸 a中的一种或几种。
上述沉淀法制备 ^基催化剂的方法， 所述沉淀剂为碳酸钾、 碳酸钧、 碳酸氨、 尿素 氨 水中的一种或几种。
一种沉淀法制备镍基催化剂的方法， 其歩骤如下，
( 1 ) 利用醇预处理可水溶性的金属化合物， 预处理温度控制在 0- ·150 之间， 时间在 0. 1-8小时， 得到金属化合物的醇溶液， 浓度为 10wt%- 80wt%;
(2 ) 再用水将金属化合物的醇溶液稀释到适宜浓度， 金属化合物的浓度在 0. lwt% 40wt%之间;
(3 ) 将步骤（2)所得溶液与沉淀剂慢慢混合进入沉淀反应器中，控制沉淀温度在 0 120 之间， ΡΗ值在 7- -13之间； 沉淀结束后老化 2 48小时， 老化温度在 0- -80Ό之 间；
(4) 将沉淀抽滤、 洗涤千净后千燥， 干燥温度为 40- 150°C , 恒温 4 - 48小时， 再放入 马弗炉中焙烧， 焙烧温度为 200 800°C , 恒温 2 20小时； 再经压片、 造粒， 还原 获得成型催化剂； 丄述沉淀法制备镍基催化剂的方法其预处理的醇可以为甲醇、 乙醇、 丙醇、 丁醇、 戊醇、 乙二醇， 丙二醇， 丙 醇、 丁二醇， 聚乙二醇、 聚乙二醇以及以上醇的各种异构体中的一种、 两种或几种。
上述沉淀法制备镍基催化剂的方法， 所述金属化合物包括活性组分镍的化合物以及助剂 铜、 铈、 镁、 锆中的一种或几种可溶性化合物， 可溶性化合物包括 ί肖酸盐、 醋酸盐、 羰基化 合¾、 醇氧基盐、 硫酸盐、 草酸盐中的一种或几种。
上述沉淀法制备镍基催化剂的方法， 所述沉淀剂为碳酸钾、 碳酸铀、 碳酸氨、 尿素， 氨 水中的一种或几种。
说
本发明的主要优势在于-
(1 ) 本发明所制备的沉淀催化剂催化活月性很 转化率能达到较高水平。
(2) 本发明所制备的沉淀催化剂具有较为稳书定的反应性能。
(3) 本发明催化剂制备原料廉价、 易得， 制备工艺简单， 催化剂产品成本低， 适于工业 化生产
具体实施方式
本发明的催化剂制备方法， 不限定为任何具体的一碳反应催化剂， 但以下将至少就一种 一碳反应催化剂对本发明加以描述。 但本发明的保护范围并不仅限于此。
实施例 I
铁基催化剂刺备： 称取硝酸铁， 硝酸铜， 硝酸钾， 硝酸锰， 硝酸镁， 按摩尔比 200:3:4: 100:20与丙醇配制成浓度 10^1; 的溶液， 在容器中进行预处理， 搅拌加热至 150°C, 恒温 1小时后， 待溶液降至室温， 加入一定量的水， 配制成浓度 3wt%的溶液， 混合均匀后， 与碳酸钠溶液慢慢混合进入沉淀反应器中， 控制沉淀 PH值在 10, 沉淀温度为 90°C。 沉淀结 束后老化 2小时， 老化温度 70°C。 将沉淀抽滤、 洗涤千净后干燥， 干燥温度为 80ΐ〕， 恒温 48小 ， 再放入马弗炉中焙烧， 焙烧温度为 5GCTC, 恒温 5小时。 再经压片、 造粒， 获得成 型催化剂》
取上述催化剂 lg用合成气（C0/¾=1)于固定床中还原， 还原条件为 500Ό , 0. IMPa, 5000h— :(V/V)， 恒温 10h。 还原完成后， 将已还原好的催化剂在氮气流中降至室温， 然后将氮 气切换成合成气（H2/C0=1),开始进行费托合成反应。反应条件为 3G0°C， 1, 5MPa, 250(〕h— s (V/V) , 反应结果见表 1。
对比倒 1
催化剂制备：称取硝酸铁，硝酸铜， 硝酸钾，硝酸锰，硝酸镁，按摩尔比 200:3:4: 100:20 配制成浓度 3wt%的水溶液， 混合均匀后， 加入沉淀反应器中， 再将碳酸铀溶液加入沉淀反应 器中， 控制沉淀 PH值在 8, 沉淀温度为 60 °C0 沉淀结束后老化 2小 S、i, 老化温度 30°C。 将 沉淀抽滤、 洗涤干净后干燥， 干燥温度为 120Ό, 恒温 12小时， 再放入马弗炉中焙烧， 焙烧 温度为 600°C, 恒温 2小时。 再经压片、 造粒， 获得成型催化剂。
取上述催化剂 lg用合成气（C0/H2=1)于固定床中还原, 还原条件为 500 , 0. lMPa? 5()00h— '(V/V), 恒温 10h。 还原完成后， 将已还原好的催化剂在氮气流中降至室温， 然后将氮 气切换成合成气（ /C04)，开始进行费托合成反应。反应条件为 300Ό, L 5MPa, 2500h^(V/V)， 反应结果见表 1。
表 1 费托合成催化剂反应结果
CO 转化说率 选择性（C- !Ήθ1 %)
催化剂
(%) 月 CH4 c2— 4 C5†
实施例 1 90.9 书 4.2 4. i 91.4 对比例 1 50.7 5.3 10, 2 84.5 实施例 2
铜基催化剂制备： 称取硝酸铜和硝酸锌， 按摩尔比为 1: 1与戊醇配制成总浓度 30¾^%的 硝酸铜硝酸锌溶液，在容器中进行预处理搅拌加热至 30°C，恒温 8小^后，待溶液降至室温， 加入一定量的水， 配制成浓度 15^%的硝酸铜硝酸锌溶液， 混合均匀后， 与氨水溶液慢慢混 合进入沉淀反应器中， 控制沉淀 PH值在 7， 沉淀温度为 10(Π 沉淀结束后老化 10小时， 老 化温度为 6(rC。 将沉淀抽滤、 洗涤千净后干燥， 干燥温度为 120°C, 恒温 10小时， 再放入马 弗炉中焙烧， 焙烧温度为 400°C, 恒温 3小时。 再经压片、 造粒， 获得成型催化剂。
取上述催化剂 18)¾混合气^( )/¥( )=5:95)按150。(：， 18(TC? 210Ό和 240Ό的升温程 序于固定床中还原后， 降温， 将还原气切换成合成气（V(H2)/V(C0)/V(C02)/V(N2) -65,9/27.1/2.9/4.1) , 开始进行甲醇合成反应。 反应条件为 210 °C - 270 °C ·, 5, OMPa , δΟΟΙ ^ν/ν), 反应结果见表 2。 催化剂制备： 称取硝酸铜和硝酸锌， 按摩尔比为 1: 1配制成浓度 15^%的硝酸铜硝酸锌 水溶液， 与尿素溶液慢慢混合进入沉淀反应器中， 控制沉淀 ΡΗ值在 9， 沉淀温度为 50°C。 沉 淀结束后老化 30小^, 老化温度为 25':C。 将沉淀袖滤、 洗涤干净后千燥， 千燥温度为 100 TJ? 恒温 24小时， 再放入马弗炉中焙烧， 焙烧温度为 400Ό, 恒温 3小时。 再经压片、 造粒， 获得成型催化剂。
取上述催化剂 1§]¾混合气（¥( )/¥( )=5:95)按150 ， 180 °C, 210'C和 240°C的升温程 序于固定床中还原后， 降温' 将还原气切换成合成气（V (H2) /V (CO) /V (C02) /Y (Ν2) =65, 9/27. 1/2.9/4. 1) , 开始进行甲醇合成反应。 反应条件为 21CTC- 270°C , δ, OMPa , 500h— ; ( ' V) ' 反应结果见表 2。
表 2 甲醇合成催化剂反应结果
催化剂 CO转化率 烃选择性 （％) co2选择性 （％) 甲醇醇选择性 、 (%) 实施例 2 28.9 1.89 4.31 93.26 对比俩 2 18, 7 1.46 3.50 94.53 说
实施例 3
镍基催化剂制备： 称取硝酸镍和硝酸镁，月按摩尔比为 1: 4与丁二醇配制成总浓度 80wt% 的溶液， 在容器中搅拌加热至 60Ό， 恒温 0.5小书时后， 待溶液降至室温， 加入一定量的水， 配制成浓度 40wt%的硝酸镍和硝酸镁溶液， 混合均匀后， 与碳酸铵溶液慢慢混合进入沉淀反 应器中， 控制沉淀 PH值在 12， 沉淀温度为 120。C。 沉淀结束后老化 48小时， 老化温度为 5C。将沉淀抽滤、洗涤干净后干燥， 干燥温度为 150Ό, 恒温 24小时， 再放入马弗炉中焙烧， 焙烧温度为 70CTC, 恒温 2小时。 再经压片、 造粒， 获得成型催化剂。
取上述催化剂 0.2g置于石英管反应器中， 用氢气在 700°C下还原 3小时后， 通入反应气 CO具（1/1) , 开始进行甲烷重整反应。 反应条件为 700°C， 0. IMPa, lOOOOh— ;綱' 反应结 果见表 3。
对比俩 3
催化剂制备： 称取硝酸镍和硝酸镁， 按摩尔比为 1: 4配制成浓度 40wt9 硝酸镍和硝酸 镁水溶液， 混合均匀后， 加入装有碳酸铵溶液的沉淀反应器中， 控制沉淀 PH值在 12, 沉淀 温度为 65° (：。 沉淀结束后老化 48小时， 老化温度为 60°C。 将沉淀抽滤、 洗涤千净后干燥； 干燥温度为 120Ό, 恒温 15小时， 再放入马弗炉中焙烧， 焙烧温度为 400 , 恒温 5小时。 再经压片、 造粒， 获得成型催化剂。
取上述催化剂 0.2g置于石英管反应器中， 用氢气在 700Ό不还原 3小时后， 通入反应气 C02/C (l/1) , 开始进行甲烷重整反应。 反应条件为 700°C, 0. IMPa, 10000b:1 (V/V) , 反应结 果见表 3。
表 3 甲烷重整催化剂反应结果
催化剂 CH4转化率 co2转化率 (%·) C0/H,
(%)
实施例 3 80, 9 85, 5 0.85 说 明 书
对比例 3 542 6θΓ3 (TiT 实施倒 4
钴基催化剂制备：称取八羰基二钴，硝酸锰，按摩尔比为 1: 4与丙三醇配制成浓度 20wt% 的八羰基二钴硝酸锰溶液， 在容器中进行预处理， 搅拌加热至 120Ό, 恒温 1.5小时后， 待 溶液降至室温， 加入一定量的水， 配制成浓度 10¾「[%的硝酸钴溶液， 混合均匀后， 与碳酸钠 溶液慢慢混合进入沉淀反应器中， 控制沉淀 PH值在 10， 沉淀温度为 7()°C。 沉淀结束后老化 20小时, 老化温度 70 。 将沉淀抽滤、 洗涤千净后干燥， 千燥温度为 90Γ, 恒温 48小时， 再放入马弗炉中焙烧， 焙烧温度为 350'C， 恒温 20小时。再经压片、造粒， 获得成型催化剂。
取上述催化剂 lg ^氢气于固定床中还原， 还原条件为 500C， 0. IMPa, 50()0h— 1 (V/V)， 恒 温 10h。 还原完成后， 将已还原好的催化剂在氮气流中降至室温， 然后将氮气切换成合成气 (¾/C( ).5)， 幵始进行费托合成反应。 反应条件为 250°C， 1.5MPa, 2500b—1 (V/V— )， 反应结 果见表 4。 催化剂制备： 称取八羰基二钴， 硝酸锰， 按摩尔比为 1: 4配制成浓度 l( t%的八羰基二 钴钴， ί肖酸锰水溶液， 混合均匀后， 加入沉淀反应器中， 再将碳酸铀溶液加入沉淀反应器中， 控制 ^淀 ΡΗ值在 10, 沉淀温度为 60°C。 沉淀结束后老化 2小时， 老化温度 30°C。 将沉淀抽 滤、洗涤千净后干燥，干燥温度为 80 ，恒温 4小时， 再放入马弗炉中焙烧，焙烧温度为 500 V, 恒温 2小时。 再经压片、 造粒， 获得成型催化剂。
取上述催化剂 lg. 氢气于固定床中还原， 还原条件为 O. lMPa, 5000h^ (Y/V) , 恒 温 10h。 还原完成后， 将已还原好的催化剂在氮气流中降至室温， 然后将氮气切换成合成气 (iV'COO.5), 开始进行费托合成反应。 反应条件为 300。C, 1.5MPa, 25〔)0h— 1 (V/V) , 反应结 果见表 4。
表 4 费托合成催化剂反应结果
催化剂 CO转化率 选择性（C- -mol %)
(%) Cl CElt
实施例 1 84.5 8.2 4.4 91.4 对比例 1 48.1 15.8 9, 1 75.1

Claims

权 利 要 求 书 I、 一种共沉淀法制备] ¾于一碳化学反应的催化剂的方法， 其特征在于， 包括 以下歩骤：
( 1 ) 利] ¾醇预处理可水溶性的金属化合物， 预处理温度控制在 0- 150Ό之 间，时间在 0. 1 -8小时，得到金属化合物的醇溶液，浓度为 10wt%- - 8Chvt%;
(2 ) 再^水将金属化合物的醇溶液稀释到适宜浓度， 金属化合物的浓度在 0, lwt% 40wt%之间；
(3) 将步骤 （2 ) 所得溶液与沉淀剂慢慢混合进入沉淀反应器中， 控制沉淀 温度在 0- - ·Ι_20'Ό之间， ΡΗ值在 7- -13之间； 沉淀结束后老化 2 48小时， 老化温度在 0 80Ό之间；
(4) 将沉淀抽滤、 洗涤干净后干燥， 干燥温度为 40 150Ό， 恒温 4 -48小 时， 再放入马弗炉中焙烧， 焙烧温度为 200- 800°C， 恒温 2-20小时； 再经压片、 造粒， 还原获得最终催化剂；
上述步骤 （1 ) 中醇为甲醇、 乙醇、 丙醇、 丁醇、 戊醇、 乙二醇、 丙二醇、 丙三醇、 丁二醇、 聚乙二醇以及以上醇的各种异构体中的一种、 两种或几 种。
、 按照权利要求 1所述的方法， 其特征在于，所述沉淀剂为碳酸钾、碳酸钠、 碳酸氨、 尿素、 氨水中的一种或几种。
3、 按照权利要求 i所述的方法， 其特征在于， 所述金属化合物包括铁、 铜、 钴、 镍、 锌、 锰、 铈、 镁、 铝、 锆中的一种、 两种或几种金属的化合物。 、 按照权利要求 1所述的方法， 其特征在于， 所述化合物包括硝酸盐、 醋酸 盐、 羰基化合物、 醇氧基盐、 硫酸盐、 草酸盐中的一种或几种。
5、 按照权利要求 1 所述的方法， 其特征在于， 步骤 （3 ) 中溶液与沉淀剂的 加料方式为正加、 反加、 并流中的一种。 权 利 要 求 书
、 按照权利要求 5所述的方法， 其特征在于， 歩骤 （3 ) 中溶液与沉淀剂的 加料方式为正加。
、 按照权利要求 1-5所述的任一催化剂的制备方法， 其特征在于， 所述的催 化剂为铁基催化剂，金属化合物包括活性组分铁的化合物以及助剂铜、钴、 锰、 镁、 锌的一种或几种金属的化合物。
、 按照权利要求 1 -5所述的任一催化剂的制备方法， 其特征在于， 所述的催 化剂为铜基催化剂，金属化合物包括活性组分铜的化合物以及助剂锌、铝、 锆、 铈的一种或几种化合物。
、 按照权利要求 i- 5所述的任一催化剂的制备方法， 其特征在于， 所述的催 化剂为钴基催化剂，金属化合物包括活性组分钴的化合物以及助剂镍、锰、 铈、 铝中的一种或几种化合物。
0、 按照权利要求 1-5所述的任一催化剂的制备方法， 其特征在于， 所述的催 化剂为镍基催化剂，金属化合物包括活性組分镍的化合物以及助剂铜、铈、 镁、 锆中的一种或儿种可溶性化合物。
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