WO2013078872A1

WO2013078872A1 - Method for preparing a catalyst used for one-carbon chemical reactions through coprecipitation

Info

Publication number: WO2013078872A1
Application number: PCT/CN2012/079014
Authority: WO
Inventors: 张燚; 刘意; 陈建峰
Original assignee: 北京化工大学
Priority date: 2011-12-02
Filing date: 2012-07-23
Publication date: 2013-06-06
Also published as: CN102489340B; CN102489340A

Abstract

A method for preparing a catalyst used for one-carbon chemical reactions through coprecipitation belongs to the technical field of catalysts and comprises the following steps: at 0-150°C, pretreating soluble metal compounds with an alcohol; after the pretreatment, diluting the alcoholic solution of the metal compounds with water; then slowly mixing the solution with a precipitant and feeding the mixture into a precipitation reactor for a coprecipitation reaction at 0-120°C and at a pH value of 7-13; after the coprecipitation reaction, performing ageing, suction filtration, washing, drying, roasting, tableting, pelleting and reduction, to obtain the catalyst with high catalytic performance and used for one-carbon chemical reactions of Fischer-Tropsch synthesis, methanol synthesis, methane reformation and the like. The precipitation catalyst prepared according to the present invention is high in catalytic activity, reaches a high conversion rate, and has stable reaction performance.

Description

Method for preparing catalyst for one-carbon chemical reaction by coprecipitation method

Technical field

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.

technical background

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.

Say

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. And 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.

In the mid-1970s, the concept of C 1 chemistry was first proposed in Japan. At the same time, Monsanto Company of the United States used low-pressure methanol carbonylation to obtain acetic acid technology for industrial applications; US Mobile Chemical Company ZSM-5 molecular sieve catalyst was successfully applied to methanol conversion to gasoline; Middle East, Canada and other countries with abundant natural gas production, The production capacity of natural gas methanol has been accelerated, resulting in a large amount of methanol entering the market. Therefore, in recent years, C1 Chemistry has not only studied syngas, but also studied methanol as an important basic raw material to synthesize a series of basic organic products based on ethylene. Chemical Products.

A carbon chemical industry is actually a new generation of coal chemical and natural gas chemical industry. At present, 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.

Summary of the invention

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. A method of preparing a catalyst containing one or more metal elements. The advantages of the coprecipitation method are as follows: First, a nano-powder material having uniform chemical composition is directly obtained by various chemical reactions in the solution, and second, it is easy to prepare a nano-powder material having a small particle size and a uniform distribution.

Another feature of the invention resides in the pretreatment of a certain amount of metal compound with various alcohols. In order to improve the particle size distribution uniformity and improve the performance of the powder samples, and to reduce the particle size, we have improved the coprecipitation method in order to separate the nucleation and growth processes of the grains, rapidly nucleate and grow. In the process of precipitation, 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. Preparation of 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;

Say

A novel method for preparing a catalyst by a coprecipitation method, comprising the steps of:

(1) pretreating the water-soluble metal compound by alcohol, 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(Κ^%;

(2) The concentration of the metal compound is between 0.1% by weight and 40% by weight;

[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;

(4) The precipitate is suction filtered, washed and dried. The drying temperature is 40 150 Ό, the temperature is 4 - 48 hours, and then placed in a muffle furnace for roasting. The baking temperature is 200-80 () Γ, 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.

In 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 Φ precipitation method, the steps of which are as follows

(1) pretreating the water-soluble metal compound with an alcohol, 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%;

(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

Between the Γ, 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 ;;

(4) The precipitate is suction filtered, washed and dried, dried at 40 15 CTC, kept at a constant temperature for 4 - 48 hours, and then placed in a muffle furnace for calcination at a temperature of 200-800 for 2-20 hours; Tableting, granulation, reduction to obtain a shaped catalyst:

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.

The method for preparing an iron-based catalyst by the above precipitation method, wherein 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

(1) pretreating a water-soluble metal compound with an alcohol, 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% _;

(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 ;;

(4) The precipitate is filtered, washed and dried, and the drying temperature is 40·- 150ΐ:', 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. One, two or several of various isoforms of alcohol.

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

(1) pretreating a water-soluble metal compound with an alcohol, the pretreatment temperature is controlled between 0 and 450 ° C, and the time is at 0. 1-8, and the alcohol solution of the metal compound is obtained at a concentration of 1 (kt%- 80wt%;

(2) The concentration of the metal compound is in the range of 0. lwt% - 4 (1⁄2 [%;

(3) slowly mixing the solution obtained in the step (2) with the precipitant into the precipitation reactor, controlling the precipitation temperature to be between 0 and 120 Torr, and the enthalpy value is between 7 and 13; after aging, the aging is 2 48 hours. The aging temperature is 0 · 80 Ό

Between

(4) The precipitate is filtered, washed and dried, dried at a temperature of 40 150 Ϊ, 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. One, two or several of various isomers.

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.

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;

(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--80Ό;

(4) 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. One, two or more of the diol and various isomers of the above alcohol.

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.

Say

The main advantage of the invention is that -

(1) The precipitation catalyst prepared by the present invention can catalyze a very high conversion rate of the living month.

(2) The precipitated catalyst prepared by the present invention has a relatively stable reaction property.

(3) 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.

detailed description

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.

Example I

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 above catalyst lg was reduced in a fixed bed with a synthesis gas (C0/3⁄4=1), and the reduction conditions were 500 Ό, 0. IMPa, 5000h- ^: (V/V), and the temperature was kept for 10 hours. 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 (H ₂ /C0 = 1) to start the Fischer-Tropsch synthesis reaction. The reaction conditions were 3G0 ° C, 1, 5 MPa, 250 () h - ^s (V / V), and the reaction results are shown in Table 1.

Contrast 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.

Lg above-mentioned catalyst reduced with synthesis gas (C0 / H ₂ = 1) in a fixed bed, the reduction condition is _{500, 0. lMPa? 5 ()} 00h- '(V / V), temperature 10h. 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 (/C04) to start the Fischer-Tropsch synthesis reaction. The reaction conditions were 300 Torr, L 5 MPa, 2500 h (V/V), and the reaction results are shown in Table 1.

Table 1 Fischer-Tropsch synthesis catalyst reaction results

CO conversion rate selectivity (C- !Ήθ1 %)

Catalyst

(%) Month CH ₄ c ₂ — ₄ C _5†

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 value is 7, the precipitation temperature is 10 (Π 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.

Take the above catalyst 1 ₈ ) 3⁄4 mixture ^ ( ) / ¥ ( ) = 5: 95) by 150. (:, 18 (TC 210Ό 240Ό and after reduction temperature program in a fixed bed, to cool the reducing gas is switched to synthesis gas _{(V (H 2) / V} (C0) / V (C0 2) / V (N? ₂ ) -65,9/27.1/2.9/4.1) , Start the methanol synthesis reaction. The reaction conditions are 210 °C - 270 °C ·, 5, OMPa, δΟΟΙ ^ν/ν), and the reaction results are shown in Table 2. 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.

Take the above catalyst 1 _§ ] 3⁄4 mixture (¥ ( ) / ¥ ( ) = 5: 95) according to 150, 180 ° C, 210 ° C and 240 ° C temperature program in the fixed bed after reduction, cooling 'will restore Gas switching to syngas (V (H ₂ ) /V (CO) /V (C0 ₂ ) /Y (Ν ₂ ) =65, 9/27. 1/2.9/4. 1) , Start the methanol synthesis reaction. The reaction conditions are 21 CTC-270 ° C, δ, OMPa, 500 h - ^; ( ' V ) ' The reaction results are shown in Table 2.

Table 2 Reaction results of methanol synthesis catalyst

Catalyst CO conversion hydrocarbon selectivity (%) co ₂ selectivity (%) methanol alcohol selectivity, (%) Example 2 28.9 1.89 4.31 93.26 Comparison of two 2 18, 7 1.46 3.50 94.53

Example 3

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 Ό, 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.

0.2 g of the above catalyst was placed in a quartz tube reactor, and after reduction at 700 ° C for 3 hours with hydrogen gas, a reaction gas CO (1/1) was introduced to initiate a methane reforming reaction. The reaction conditions were 700 ° C, 0. IMPa, lOOOOh - ^;

Contrast two 3

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 Ό, 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.

0.2 g of the above catalyst was placed in a quartz tube reactor, and after hydrogenation at 700 Torr for 3 hours, the reaction gas C0 ₂ /C (l/1) was introduced to start the methane reforming reaction. The reaction conditions were 700 ° C, 0. IMPa, 10000b: ¹ (V/V), and the reaction results are shown in Table 3.

Table 3 Methane reforming catalyst reaction results

Catalyst CH ₄ conversion co ₂ conversion (%·) C0/H,

(%)

Example 3 80, 9 85, 5 0.85 Instruction manual

Comparative example 3 542 6θΓ3 (TiT implementation inverted 4

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 120Ό, 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. After the precipitation, 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 Γ, 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, λ 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. 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 (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.

Table 4 Fischer-Tropsch Synthesis Catalyst Reaction Results

Catalyst CO conversion selectivity (C--mol %)

(%) Cl C _Elt

Example 1 84.5 8.2 4.4 91.4 Comparative Example 1 48.1 15.8 9, 1 75.1

Claims

Claim 1 is a method for preparing a catalyst for a one-carbon chemical reaction, which comprises the following steps:

(1) The water-soluble metal compound is pretreated with a 3⁄4 alcohol, and the pretreatment temperature is controlled between 0 and 150 Torr, and the time is 0.1 to 8 hours to obtain an alcohol solution of the metal compound at a concentration of 10 wt% - 8 Chvt %;

(2) further diluting the alcohol solution of the metal compound to a suitable concentration, and the concentration of the metal compound is between 0, lwt% and 40% by weight;

(3) Slowly mix the solution obtained in step (2) with the precipitant into the precipitation reactor, and control the precipitation temperature between 0--·Ι_20'Ό, the enthalpy value is between 7--13; aging after precipitation 2 48 hours, the aging temperature is between 0 80 ;;

(4) The precipitate is suction filtered, washed and dried. The drying temperature is 40 150 Ό, the temperature is 4 - 48 hours, and then placed in a muffle furnace for roasting. The baking temperature is 200-800 ° C, and the temperature is 2-20 hours; The final catalyst is obtained by tableting, granulating and reduction;

The alcohol in the above step (1) is methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerol, butanediol, polyethylene glycol, and various isomers of the above alcohols. One, two or several.

The method according to claim 1, wherein the precipitating agent is one or more of potassium carbonate, sodium carbonate, ammonium carbonate, urea, and ammonia.

3. The method according to claim 1, wherein the metal compound comprises one of iron, copper, cobalt, nickel, zinc, manganese, lanthanum, magnesium, aluminum, zirconium, two or more metals compound of. The method according to claim 1, wherein the compound comprises one or more of a nitrate, an acetate, a carbonyl compound, an alcoholate salt, a sulfate, and an oxalate.

5. The method according to claim 1, wherein the feeding method of the solution and the precipitating agent in the step (3) is one of positive addition, reverse addition and parallel flow. Claim

The method according to claim 5, characterized in that the feeding method of the solution and the precipitating agent in the step (3) is plus.

The method for preparing a catalyst according to any one of claims 1 to 5, wherein the catalyst is an iron-based catalyst, and the metal compound comprises an active component iron compound and an auxiliary agent of copper, cobalt, manganese, magnesium, A compound of one or more metals of zinc.

The method for preparing a catalyst according to any one of claims 1 to 5, wherein the catalyst is a copper-based catalyst, and the metal compound comprises a compound of an active component copper and an auxiliary agent of zinc, aluminum, zirconium or hafnium. One or several compounds.

The method for preparing a catalyst according to any one of claims 1 to 5, wherein the catalyst is a cobalt-based catalyst, and the metal compound comprises a compound of the active component cobalt and an auxiliary agent of nickel, manganese, lanthanum and aluminum. One or several compounds.

The method for preparing a catalyst according to any one of claims 1 to 5, wherein the catalyst is a nickel-based catalyst, and the metal compound comprises a compound of active component nickel and an auxiliary agent of copper, bismuth, magnesium, zirconium. One or a variety of soluble compounds.