CN114700079A - Catalyst for preparing methyl formate by catalyzing synthesis gas in one step and preparation method and application thereof - Google Patents

Catalyst for preparing methyl formate by catalyzing synthesis gas in one step and preparation method and application thereof Download PDF

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CN114700079A
CN114700079A CN202210414059.XA CN202210414059A CN114700079A CN 114700079 A CN114700079 A CN 114700079A CN 202210414059 A CN202210414059 A CN 202210414059A CN 114700079 A CN114700079 A CN 114700079A
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catalyst
synthesis gas
layer
methyl formate
preparing
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CN114700079B (en
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郭淑静
葛元征
张磊
陈佑涛
张玉娟
吴小园
刘星
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Shaanxi Yanchang Petroleum Group Co Ltd
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    • 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
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Abstract

The invention discloses a catalyst for preparing methyl formate by catalyzing synthesis gas in one step, which consists of an independent catalyst layer A, an isolated layer and a catalyst layer B; the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3MOx, M is at least one of Ce, Zr, Mn and Mg, x is in the oxidation state of the metal element MThe desired number of oxygen atoms; the catalyst layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, and the catalyst layer B comprises the following components in percentage by total weight of 100 percent: 5-12% of Cu, 0.5-2% of an auxiliary agent and the balance of a carrier; the auxiliary agent is at least one of K, Mg, La or Ce. Meanwhile, the invention also discloses a preparation method and application of the catalyst. The preparation method of the catalyst provided by the invention is simple, and the preparation process is environment-friendly; the one-step method for preparing the methyl formate by catalyzing the synthesis gas under the gas-solid phase condition is realized, and the reaction condition is mild.

Description

Catalyst for preparing methyl formate by catalyzing synthesis gas in one step and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of methyl formate, and particularly relates to a catalyst for preparing methyl formate by catalyzing synthesis gas in one step, and a preparation method and application thereof.
Background
Methyl formate has double reactivity of aldehyde and ester, is called as a basic structural unit of C1 chemistry, can industrially produce formic acid, acetic acid, ethylene glycol, dimethyl carbonate, methyl glycolate, formylation reagent in organic synthesis and the like from the methyl formate, and the reaction conditions of the processes are mild. In addition, methyl formate can also be used as a high octane additive for gasoline. In the agricultural field, it can be used as insecticide, bactericide, fumigant for grain crops, tobacco treating agent, fruit drying agent, etc. In the medical field, methyl formate is used as a raw material for synthesizing medicines such as sulfamethazine and the like.
The synthesis method of the methyl formate mainly comprises the following steps: (1) the esterification method, in which methyl formate is synthesized from formic acid and methanol under the catalysis of concentrated sulfuric acid, has been eliminated abroad due to the process lag, serious equipment corrosion and high cost. (2) The methanol carbonylation method is characterized in that methanol reacts with CO under the action of strong alkaline catalysts such as sodium methoxide or potassium methoxide and the like to generate methyl formate. The method has the advantages that anhydrous methanol is required to be used, the CO concentration requirement is high, and the production cost of the methyl formate is high. (3) The methanol dehydrogenation method is used for dehydrogenating methanol on a Cu-based catalyst and other catalysts to generate methyl formate, and the method is difficult to break through thermodynamic limitations. (4) Methanol and CO2Hydro-condensation process, process CO2The conversion rate is low, and the yield of methyl formate is low. (5) Direct synthesis of synthesis gas, direct conversion of synthesis gasThe preparation of methyl formate is a typical atom-economic reaction. The method has few production steps and low energy consumption, and is the most promising method for synthesizing the methyl formate.
The research of directly preparing methyl formate by a synthesis gas one-step method mainly focuses on the field of low-temperature liquid-phase synthesis. Patent US 5384335 reports that CuCr and alkali metal/alkaline earth metal composite catalyst catalyze synthesis gas to directly synthesize methyl formate under the liquid phase conditions of 100-160 ℃ and 4.0-6.5 MPa. Patent CN 1050116 reports that synthesis gas is used for synthesizing methyl formate in one step under low temperature liquid phase condition in a copper chromium catalyst and sodium methoxide system. Patent CN 103949268B reports that methyl formate is synthesized by catalyzing synthesis gas in one step under the liquid phase condition of copper manganese and zirconium based solid alkali oxide catalyst. These patents all catalyze synthesis gas methyl formate under liquid phase conditions, the product separation is complex, some alkoxides of alkali metals or alkaline earth metals are needed, the requirement on the purity of reactants is high, and these become bottlenecks in the technology development.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the catalyst for preparing the methyl formate by catalyzing the synthesis gas in one step, and the preparation method and the application thereof.
A catalyst for preparing methyl formate by catalyzing synthesis gas in one step comprises an independent catalyst layer A, an isolation layer and a catalyst layer B;
the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3-MOx, wherein the total weight of Cu, Zn, Al and M in the metal oxide is 100%, and the content of each component is as follows: 40-55% of Cu, 20-30% of Zn, 4-8% of Al and the balance of M; m is at least one of Ce, Zr, Mn and Mg, and x is the oxygen atom number required by the oxidation state of the metal element M;
the isolation layer is made of quartz sand;
the catalyst layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, and the catalyst layer B comprises the following components in percentage by total weight of 100 percent: 5-12% of Cu, 0.5-2% of an auxiliary agent and the balance of a carrier; the auxiliary agent is at least one of K, Mg, La or CeThe carrier is graphene, carbon nano tube or activated carbon, and the specific surface area of the carrier is more than 200 m2/g。
Preferably, the mass ratio of the catalytic layer a to the catalytic layer B is 1: (1-4), and the ratio of the catalytic layer A to the insulating layer is (1.5-2) g: (0.5-2) mL.
The preparation method of the catalyst for preparing the methyl formate by the catalytic synthesis gas one-step method comprises the following steps:
(1) preparation of metal oxide catalyst:
(11) simultaneously dropwise adding salt solutions of Cu, Zn, Al and M and a precipitant solution into water at 60-90 ℃, and controlling the pH value of the system to 7.0-9.5 by controlling the dropwise adding speed of the precipitant solution;
(12) continuing to perform aging reaction at 60-90 ℃ for 2h, and then washing, drying, roasting, tabletting and forming, and screening to obtain a metal oxide catalyst;
(2) preparation of a Cu-based catalyst:
(21) dissolving a copper salt and an auxiliary agent precursor in water or ethanol to form a solution A;
(22) adding the carrier into the solution A, performing ultrasonic treatment for 0.5-2h, stirring at room temperature until no liquid exists in the container, drying, tabletting, forming, and sieving;
(3) preparing a catalyst:
weighing metal oxide catalysts according to a proportion to obtain a catalyst layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalyst layer B.
Preferably, in the step (11), the salt solution of the metals Cu, Zn, Al and M is nitrate or chloride solution of the corresponding metals, and the total ion concentration of the metals Cu, Zn, Al and M is 0.1-1 mol/L.
Preferably, in step (11), the precipitant solution is 0.1-1mol/L NaOH solution, Na2CO3Solution or KOH solution.
Preferably, in the step (2), the copper salt and the auxiliary agent precursor are nitrates or chlorides of corresponding metals, and the ratio of the carrier to the solution a is 1 g: (30-60) mL.
Preferably, in the step (12) and the step (22), the drying condition is drying for 6-15h at 90-150 ℃, and the sieve is used for sieving by a sieve with 20-80 meshes; in the step (12), the roasting condition is that roasting is carried out for 3-10h at the temperature of 300-500 ℃.
The application of the catalyst in the one-step preparation of methyl formate by catalyzing synthesis gas is as follows: and filling the catalyst layer B, the isolation layer and the catalyst layer A in the catalyst into a fixed bed reactor in a layered manner from bottom to top in sequence, introducing hydrogen-containing gas for reduction activation, adjusting the reaction temperature to 200-260 ℃, and then switching to introduce synthesis gas and boosting the pressure to 0.5-2MPa for reaction.
Preferably, the reduction activation conditions comprise that the reduction temperature is 250-350 ℃, the reduction time is 1-8h, and the reduction pressure is normal pressure; h is CO in the synthesis gas2The volume ratio of (1-4) to (1); the space velocity of the synthesis gas relative to the catalyst layer A is 100--1。
Preferably, the hydrogen-containing gas consists of 5-50% by volume of hydrogen and balance of balance gas, and the balance gas is nitrogen, helium or argon; the flow rate of the hydrogen-containing gas is 20-100 mL/min.
The invention has the advantages that:
(1) the preparation method of the catalyst provided by the invention is simple, and the preparation process is environment-friendly;
(2) the method realizes the one-step preparation of methyl formate by catalyzing synthesis gas under the gas-solid phase condition, has mild reaction condition and simple process, and belongs to efficient atom economic reaction.
Detailed Description
Example 1
1. A catalyst for catalyzing synthesis gas to prepare methyl formate in one step comprises an independent catalyst layer A2.0 g, an isolation layer 1mL and a catalyst layer B2.0 g;
the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3-ZrO2In the metal oxide, the weight ratio of Cu, Zn, Al and Zr is as follows: cu, Zn, Al, Zr =50:30:4: 16;
the isolation layer is made of quartz sand;
the catalyst layer B is CThe u-based catalyst consists of Cu, an auxiliary agent and a carrier, wherein the auxiliary agent is La, and the carrier has a specific surface area of more than 200 m2The content of each component is as follows according to 100 percent of the total weight of the carbon nano tube: cu 10%, auxiliary La 1% and the balance carrier carbon nano-tubes, and the mark is 1.0La10 Cu/CNTs.
2. The preparation method of the catalyst for preparing the methyl formate by the catalytic synthesis gas one-step method comprises the following steps:
(1) preparation of metal oxide catalyst:
(11) preparing a salt solution with the total metal ion concentration of 1mol/L from copper nitrate, zinc nitrate, aluminum nitrate and zirconium nitrate, and preparing a sodium carbonate solution with the total metal ion concentration of 0.1mol/L as a precipitator; simultaneously dripping the salt solution and the precipitant into deionized water at 75 ℃, and controlling the pH value of the system to 7.0-8.0 by controlling the dripping speed of the precipitant solution;
(12) continuously carrying out aging reaction for 2h at 75 ℃, then washing, drying for 10h at 110 ℃, roasting for 4h at 350 ℃ in a muffle furnace, tabletting, molding, sieving and sieving with a 40-60-mesh sieve to obtain CuO-ZnO-Al2O3-ZrO2A metal oxide catalyst;
(2) preparation of a Cu-based catalyst:
(21) dissolving copper nitrate and lanthanum nitrate in ethanol to form a solution A;
(22) according to the weight ratio of 1 g: adding the carrier carbon nano tube into the solution A by 60mL, carrying out ultrasonic treatment for 2h, stirring at room temperature until no liquid exists in the container, drying at 90 ℃ for 15h, tabletting, forming, and sieving by 40-60 meshes;
(3) preparing a catalyst:
weighing metal oxide catalysts according to a proportion to obtain a catalyst layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalyst layer B.
3. The application of the catalyst in the one-step preparation of methyl formate by catalyzing synthesis gas is as follows: filling a catalyst layer B, an isolation layer and a catalyst layer A in the catalyst into a fixed bed reactor in a layering manner from bottom to top, introducing hydrogen-containing gas at the flow rate of 30mL/min, and carrying out reduction activation for 2 hours at the normal pressure of 250 ℃, wherein the volume of the hydrogen-containing gas accounts for the volume of the hydrogen-containing gas10% hydrogen and the balance nitrogen; then regulating the reaction temperature to 220 ℃, switching to introduce synthetic gas and boosting the pressure to 2MPa for reaction; h is CO in the synthesis gas2The volume ratio of (A) to (B) is 2: 1; the space velocity of the synthesis gas relative to the catalyst layer A is 1500h-1On-line analysis of all components of the gas chromatograph was performed, and the results are shown in table 1.
Example 2
1. A catalyst for catalyzing synthesis gas to prepare methyl formate in one step comprises an independent catalyst layer A2.0 g, an isolation layer 2mL and a catalyst layer B3.0 g;
the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3-CeO2In the metal oxide, the weight ratio of Cu, Zn, Al and Ce is as follows: cu, Zn, Al, Ce =55:26:4: 15;
the isolation layer is made of quartz sand;
the catalyst layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, the auxiliary agent is K and Mg, and the carrier has a specific surface area of more than 200 m2The active carbon comprises the following components in percentage by weight of 100 percent of the total weight: 5% of Cu, 0.5% of an auxiliary agent K, 1.5% of an auxiliary agent Mg, and the balance of carrier activated carbon, wherein the mark is 0.5 K1.5Mg5Cu/AC.
2. The preparation method of the catalyst for preparing the methyl formate by the catalytic synthesis gas one-step method comprises the following steps:
(1) preparation of metal oxide catalyst:
(11) preparing a salt solution with the total metal ion concentration of 0.5mol/L from copper nitrate, zinc nitrate, aluminum chloride and cerium nitrate, and preparing a potassium hydroxide solution with the total metal ion concentration of 1mol/L as a precipitator; simultaneously dripping the salt solution and the precipitant into deionized water at 90 ℃, and controlling the pH value of the system to 8.0-9.0 by controlling the dripping speed of the precipitant solution;
(12) continuously carrying out aging reaction for 2h at 90 ℃, then washing, drying for 15h at 90 ℃, roasting for 4h at 450 ℃ in a muffle furnace, tabletting, molding, sieving and sieving with a 40-60-mesh sieve to obtain CuO-ZnO-Al2O3-CeO2A metal oxide catalyst;
(2) preparation of a Cu-based catalyst:
(21) dissolving copper nitrate, potassium chloride and magnesium chloride in water to form a solution A;
(22) according to the weight ratio of 1 g: adding carrier activated carbon into the solution A by 50mL, carrying out ultrasonic treatment for 0.5h, stirring at room temperature until no liquid exists in the container, drying at 110 ℃ for 10h, tabletting, and sieving by a sieve of 20-40 meshes;
(3) preparing a catalyst:
weighing metal oxide catalysts according to a proportion to obtain a catalyst layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalyst layer B.
3. The application of the catalyst in the one-step preparation of methyl formate by catalyzing synthesis gas is as follows: sequentially filling a catalyst layer B, an isolation layer and a catalyst layer A in the catalyst into a fixed bed reactor layer by layer from bottom to top, introducing hydrogen-containing gas at the flow rate of 50mL/min, and carrying out reduction activation for 3 hours at the normal pressure of 300 ℃, wherein the hydrogen-containing gas consists of hydrogen accounting for 50% of the volume and the balance of helium; then regulating the reaction temperature to 200 ℃, switching and introducing synthesis gas, and boosting the pressure to 0.5MPa for reaction; h is CO in the synthesis gas2The volume ratio of (A) to (B) is 3: 1; the space velocity of the synthetic gas relative to the catalytic layer A is 2000h-1The gas chromatography was performed on-line for all components, and the results are shown in Table 1.
Example 3
1. A catalyst for catalyzing synthesis gas to prepare methyl formate in one step comprises an independent catalyst layer A1.5 g, an isolation layer 2mL and a catalyst layer B6.0 g;
the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3-ZrO2-MnO2In the metal oxide, the weight ratio of Cu, Zn, Al, Zr and Mn is as follows: cu, Zn, Al, Zr: mn =40:30:8:15: 7;
the isolation layer is made of quartz sand;
the catalyst layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, wherein the auxiliary agent is Ce, and the carrier has a specific surface area of more than 200 m2The graphene comprises the following components in percentage by weight of 100 percent of the total weight: 12% of Cu, 1.2% of assistant Ce and the balance of carrier graphene, and the mark is 1.2Ce12Cu/Graphene。
2. The preparation method of the catalyst for preparing the methyl formate by the catalytic synthesis gas one-step method comprises the following steps:
(1) preparation of metal oxide catalyst:
(11) preparing a salt solution with the total metal ion concentration of 0.1mol/L from copper nitrate, zinc chloride, aluminum nitrate, zirconium nitrate and manganese nitrate, and preparing a sodium hydroxide solution with the total metal ion concentration of 0.3mol/L as a precipitator; simultaneously dripping the salt solution and the precipitant into deionized water at 60 ℃, and controlling the pH value of the system to 8.5-9.5 by controlling the dripping speed of the precipitant solution;
(12) continuously carrying out aging reaction for 2h at 60 ℃, then washing, drying for 6h at 150 ℃, roasting for 3h at 500 ℃ in a muffle furnace, tabletting, molding, sieving and sieving with a 20-40 mesh sieve to obtain CuO-ZnO-Al2O3-ZrO2-MnO2A metal oxide catalyst;
(2) preparation of a Cu-based catalyst:
(21) dissolving copper nitrate and cerium nitrate in water to form a solution A;
(22) according to the weight ratio of 1 g: adding the carrier graphene into the solution A by 30mL, carrying out ultrasonic treatment for 0.5h, stirring at room temperature until no liquid exists in the container, drying at 150 ℃ for 6h, tabletting, and sieving by 60-80 meshes;
(3) preparing a catalyst:
weighing metal oxide catalysts according to a proportion to obtain a catalyst layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalyst layer B.
3. The application of the catalyst in the one-step preparation of methyl formate by catalyzing synthesis gas is as follows: sequentially filling a catalyst layer B, an isolation layer and a catalyst layer A in the catalyst into a fixed bed reactor layer by layer from bottom to top, introducing hydrogen-containing gas at the flow rate of 100mL/min, and carrying out reduction activation for 1h at the normal pressure at the temperature of 350 ℃, wherein the hydrogen-containing gas consists of hydrogen with the volume of 5% and the balance of argon; then regulating the reaction temperature to 260 ℃, switching and introducing synthesis gas, boosting the pressure to 1MPa, and reacting; h is CO in the synthesis gas2In a volume ratio of 4: 1; the space velocity of the synthesis gas relative to the catalytic layer A is4000h-1The gas chromatography was performed on-line for all components, and the results are shown in Table 1.
Example 4
1. A catalyst for preparing methyl formate by catalyzing synthesis gas in one step comprises an independent catalyst layer A2.0 g, an isolation layer 1mL and a catalyst layer B4.0 g;
the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3-MgO, wherein in the metal oxide, the weight ratio of Cu, Zn, Al and Mg is as follows: cu, Zn, Al, Mg =50:20:7: 23;
the isolation layer is made of quartz sand;
the catalyst layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, wherein the auxiliary agent is Mg, and the carrier has a specific surface area of more than 200 m2The graphene comprises the following components in percentage by weight of 100 percent of the total weight: cu 9%, an auxiliary agent Mg0.5%, and the balance being carrier Graphene, and the mark being 0.5Mg9 Cu/Graphene.
2. The preparation method of the catalyst for preparing the methyl formate by the catalytic synthesis gas one-step method comprises the following steps:
(1) preparation of metal oxide catalyst:
(11) preparing copper nitrate, zinc nitrate, aluminum nitrate and magnesium chloride into a salt solution with the total metal ion concentration of 0.8mol/L, and preparing a sodium carbonate solution with the total metal ion concentration of 0.8mol/L as a precipitator; simultaneously dripping the salt solution and the precipitant into deionized water at 80 ℃, and controlling the pH value of the system to 7.0-8.0 by controlling the dripping speed of the precipitant solution;
(12) continuing to carry out aging reaction at 80 ℃ for 2h, then washing, drying at 120 ℃ for 7h, roasting in a muffle furnace at 300 ℃ for 10h, tabletting, molding, sieving and sieving with a 40-60 mesh sieve to obtain CuO-ZnO-Al2O3-a MgO metal oxide catalyst;
(2) preparation of a Cu-based catalyst:
(21) dissolving copper nitrate and magnesium chloride in ethanol to form a solution A;
(22) according to the weight ratio of 1 g: adding the carrier graphene into the solution A by 40mL, carrying out ultrasonic treatment for 1.5h, stirring at room temperature until no liquid exists in the container, drying at 120 ℃ for 8h, tabletting, and sieving by 40-60 meshes;
(3) preparing a catalyst:
weighing metal oxide catalysts according to a proportion to obtain a catalyst layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalyst layer B.
3. The application of the catalyst in the one-step preparation of methyl formate by catalyzing synthesis gas is as follows: sequentially filling a catalyst layer B, an isolation layer and a catalyst layer A in the catalyst into a fixed bed reactor layer by layer from bottom to top, and introducing hydrogen-containing gas at the flow rate of 20mL/min for reduction and activation at the temperature of 280 ℃ under normal pressure for 2h, wherein the hydrogen-containing gas consists of 30% hydrogen by volume and the balance of nitrogen; then regulating the reaction temperature to 230 ℃, switching and introducing synthesis gas, and boosting the pressure to 1.5MPa for reaction; h in the synthesis gas2The volume ratio of (A) to (B) is 1: 1; the space velocity of the synthetic gas relative to the catalytic layer A is 2000h-1The gas chromatography was performed on-line for all components, and the results are shown in Table 1.
Comparative example 1
The catalyst contained only the catalytic layer a, which was the same as in example 1.
The application of the catalyst in the synthesis gas one-step method for preparing methyl formate comprises the following steps: the catalyst was directly placed in a fixed bed reactor, otherwise as in example 1, and the results are shown in Table 1.
Comparative example 2
The catalyst contained only catalytic layer B, which was the same as in example 1.
The application of the catalyst in the one-step preparation of methyl formate from synthesis gas comprises the following steps: the catalyst was directly placed in a fixed bed reactor, otherwise as in example 1, and the results are given in Table 1.
TABLE 1 results of the reaction
Figure DEST_PATH_IMAGE001
Remarking: selectivity of methyl formate and other products to CO removal2Molar selectivity of methyl formate in the external product; others refer to small amounts of dimethyl ether, ethanol and hydrocarbons.

Claims (10)

1. A catalyst for preparing methyl formate by catalyzing synthesis gas in one step is characterized in that: the catalyst layer consists of an independent catalyst layer A, an isolated layer and a catalyst layer B;
the catalyst layer A is a metal oxide catalyst marked as CuO-ZnO-Al2O3-MOx, wherein the total weight of Cu, Zn, Al and M in the metal oxide is 100%, and the content of each component is as follows: 40-55% of Cu, 20-30% of Zn, 4-8% of Al and the balance of M; m is at least one of Ce, Zr, Mn and Mg, and x is the oxygen atom number required by the oxidation state of the metal element M;
the isolation layer is made of quartz sand;
the catalyst layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, and the catalyst layer B comprises the following components in percentage by total weight of 100 percent: 5-12% of Cu, 0.5-2% of an auxiliary agent and the balance of a carrier; the auxiliary agent is at least one of K, Mg, La or Ce, the carrier is graphene, carbon nano tube or activated carbon, and the specific surface area of the carrier is more than 200 m2/g。
2. The catalyst for catalyzing the one-step preparation of methyl formate from synthesis gas according to claim 1, wherein: the mass ratio of the catalytic layer A to the catalytic layer B is 1: (1-4), and the ratio of the catalytic layer A to the insulating layer is (1.5-2) g: (0.5-2) mL.
3. The process for preparing a catalyst for preparing methyl formate by catalyzing synthesis gas in one step according to claim 1, wherein the process comprises the steps of: the method comprises the following steps:
(1) preparation of metal oxide catalyst:
(11) simultaneously dropwise adding salt solutions of Cu, Zn, Al and M and a precipitant solution into water at 60-90 ℃, and controlling the pH value of the system to 7.0-9.5 by controlling the dropwise adding speed of the precipitant solution;
(12) continuing to perform aging reaction at 60-90 ℃ for 2h, and then washing, drying, roasting, tabletting and forming, and screening to obtain a metal oxide catalyst;
(2) preparation of a Cu-based catalyst:
(21) dissolving a copper salt and an auxiliary agent precursor in water or ethanol to form a solution A;
(22) adding the carrier into the solution A, performing ultrasonic treatment for 0.5-2h, stirring at room temperature until no liquid exists in the container, drying, tabletting, forming, and sieving;
(3) preparing a catalyst:
weighing metal oxide catalysts according to a proportion to obtain a catalyst layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalyst layer B.
4. The method for preparing the catalyst for preparing the methyl formate by the one-step method of catalyzing the synthesis gas according to claim 3, which is characterized by comprising the following steps of: in the step (11), the salt solution of the metals Cu, Zn, Al and M is nitrate or chloride solution of the corresponding metals, and the total ion concentration of the metals Cu, Zn, Al and M is 0.1-1 mol/L.
5. The method for preparing the catalyst for preparing the methyl formate by the one-step method of catalyzing the synthesis gas according to claim 4, which is characterized by comprising the following steps of: in the step (11), the precipitant solution is 0.1-1mol/L NaOH solution and Na2CO3Solution or KOH solution.
6. The method for preparing the catalyst for preparing the methyl formate by the one-step method of catalyzing the synthesis gas according to claim 5, which is characterized by comprising the following steps of: in the step (2), the copper salt and the auxiliary agent precursor are nitrates or chlorides of corresponding metals, and the ratio of the carrier to the solution A is 1 g: (30-60) mL.
7. The method for preparing the catalyst for preparing the methyl formate by the catalytic synthesis gas one-step method according to claim 6, wherein the method comprises the following steps: in the step (12) and the step (22), the drying condition is drying for 6-15h at 90-150 ℃, and the screening is to pass through a 20-80 mesh screen; in the step (12), the roasting condition is that roasting is carried out for 3-10h at the temperature of 300-500 ℃.
8. The use of a catalyst according to claim 1 or 2 in the one-step preparation of methyl formate from catalytic synthesis gas, characterized in that: the application is as follows: and filling the catalyst layer B, the isolation layer and the catalyst layer A in the catalyst into a fixed bed reactor in a layered manner from bottom to top in sequence, introducing hydrogen-containing gas for reduction activation, adjusting the reaction temperature to 200-260 ℃, and then switching to introduce synthesis gas and boosting the pressure to 0.5-2MPa for reaction.
9. The application of the catalyst according to claim 8 in the one-step preparation of methyl formate from catalytic synthesis gas, which is characterized in that: the reduction activation conditions are that the reduction temperature is 250-350 ℃, the reduction time is 1-8h, and the reduction pressure is normal pressure; h is CO in the synthesis gas2The volume ratio of (1-4) to (1); the space velocity of the synthesis gas relative to the catalyst layer A is 100--1。
10. The use of the catalyst of claim 9 in the one-step production of methyl formate from catalytic synthesis gas, wherein: the hydrogen-containing gas consists of 5-50% of hydrogen by volume and balance gas, wherein the balance gas is nitrogen, helium or argon; the flow rate of the hydrogen-containing gas is 20-100 mL/min.
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