CN114700079B - Catalyst for preparing methyl formate by catalytic synthesis gas one-step method and preparation method and application thereof - Google Patents

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

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CN114700079B
CN114700079B CN202210414059.XA CN202210414059A CN114700079B CN 114700079 B CN114700079 B CN 114700079B CN 202210414059 A CN202210414059 A CN 202210414059A CN 114700079 B CN114700079 B CN 114700079B
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catalyst
synthesis gas
methyl formate
catalytic layer
preparing
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CN114700079A (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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    • 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
    • B01J23/78—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
    • B01J23/83—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
    • B01J35/19—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • 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

Abstract

The invention discloses a catalyst for preparing methyl formate by a one-step method of catalytic synthesis gas, which consists of an independent catalytic layer A, an isolation layer and a catalytic layer B; the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -MOx, M is at least one of Ce, zr, mn, mg, x being the number of oxygen atoms required to satisfy the oxidation state of the metal element M; the catalytic layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, wherein the content of each component is as follows, based on 100% of the total weight: cu 5-12%, auxiliary agent 0.5-2%, and carrier for the rest; 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; realizes the one-step preparation of methyl formate by catalyzing synthesis gas under the gas-solid phase condition, and has mild reaction condition.

Description

Catalyst for preparing methyl formate by catalytic synthesis gas one-step method and preparation method and application thereof
Technical Field
The invention belongs to the technical field of methyl formate preparation, and particularly relates to a catalyst for preparing methyl formate by a one-step method of catalytic synthesis gas, and a preparation method and application thereof.
Background
Methyl formate has dual reactivity of aldehyde and ester, called as a basic structural unit of C1 chemistry, and can be industrially produced into formic acid, acetic acid, ethylene glycol, dimethyl carbonate, methyl glycolate, formylating reagent in organic synthesis and the like from methyl formate, and the reaction conditions of the processes are mild. In addition, methyl formate can also be used as a gasoline high octane additive. In the agricultural field, can be used as pesticide, bactericide, cereal crop fumigant, tobacco treatment agent, fruit drying agent and the like. In the medical field, methyl formate is used as a raw material for synthesizing medicaments such as sulfamethazine and the like.
The synthesis method of methyl formate mainly comprises the following steps: (1) The esterification method, which synthesizes methyl formate by passing formic acid and methanol under the catalysis of concentrated sulfuric acid, has serious equipment corrosion and high cost due to the lag of the process, and has been eliminated abroad. (2) Methanol is reacted with CO under high pressure under the action of strong alkaline catalyst such as sodium methoxide or potassium methoxide to produce methyl formate. The method must use absolute methanol, and has high CO concentration requirement, so that the production cost of methyl formate is high. (3) In the methanol dehydrogenation method, methanol is dehydrogenated on a Cu-based catalyst to generate methyl formate, and the method is difficult to break through thermodynamic limitation. (4) Methanol and CO 2 Hydrogenation condensation method, and CO 2 The conversion rate is low, and the yield of methyl formate is low. (5) Direct synthesis of synthesis gas, direct conversion of synthesis gas to methyl formate is a typical atom-economical reaction. The method has few production steps and low energy consumption, and is the most promising in the methyl formate synthesis method.
Research on direct preparation of methyl formate by a one-step synthesis gas method is mainly focused on the field of low-temperature liquid phase synthesis. Patent US 5384335 reports that CuCr and alkali/alkaline earth metal composite catalysts catalyze synthesis gas to directly synthesize methyl formate under the liquid phase condition of 4.0-6.5MPa at 100-160 ℃. Patent CN 1050116 reports the synthesis of methyl formate from synthesis gas in a one-step process under low temperature liquid phase conditions in a copper chromium catalyst and sodium methoxide system. Patent CN 103949268B reports one-step synthesis of methyl formate from synthesis gas catalyzed by copper-manganese and zirconium-based solid alkali oxide catalysts in liquid phase. These patents all catalyze synthesis gas methyl formate under liquid phase condition, the product separation is complex, some require alkali metal or alkaline earth metal alkoxide, and the purity requirement for the reactants is high, which becomes the bottleneck of the technical development.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing methyl formate by catalyzing synthesis gas through a one-step method, and a preparation method and application thereof.
A catalyst for preparing methyl formate by a one-step method of catalyzing synthesis gas consists of an independent catalytic layer A, an isolation layer and a catalytic layer B;
the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -MOx, wherein the metal oxide comprises the following components in percentage by weight based on 100% of the total weight of Cu, zn, al, M: 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, mg, and x is the number of oxygen atoms required for meeting the oxidation state of the metal element M;
the isolation layer is quartz sand;
the catalytic layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, wherein the content of each component is as follows, based on 100% of the total weight: cu 5-12%, auxiliary agent 0.5-2%, and carrier for the rest; the auxiliary agent is at least one of K, mg, la or Ce, the carrier is graphene, carbon nano tube or active carbon, and the specific surface area of the carrier is more than 200 m 2 /g。
Preferably, the mass ratio of the catalytic layer A to the catalytic layer B is 1: (1-4) 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 methyl formate by catalyzing synthesis gas through a one-step method comprises the following steps:
(1) Preparation of a metal oxide catalyst:
(11) Simultaneously dripping a salt solution of the metal Cu, zn, al, M and a precipitant solution into water at the temperature of 60-90 ℃, and controlling the pH value of the system to 7.0-9.5 by controlling the dripping speed of the precipitant solution;
(12) Continuing aging reaction for 2 hours at 60-90 ℃, and then washing, drying, roasting, tabletting, forming and screening to obtain the metal oxide catalyst;
(2) Preparation of Cu-based catalyst:
(21) Dissolving 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 a metal oxide catalyst according to a proportion to obtain a catalytic layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalytic layer B.
Preferably, in step (11), the salt solution of the metal Cu, zn, al, M is a nitrate or chloride salt solution of the corresponding metal, and the total ion concentration of the metal Cu, zn, al, M is 0.1-1mol/L.
Preferably, in the step (11), the precipitant solution is 0.1-1mol/L NaOH solution, na 2 CO 3 Solutions or KOH solutions.
Preferably, in the step (2), the copper salt and the auxiliary precursor are nitrate or chloride salts of the corresponding metals, and the ratio of the carrier to the solution a is 1g: (30-60) mL.
Preferably, in the step (12) and the step (22), the drying condition is that the drying is carried out at 90-150 ℃ for 6-15 hours, and the sieving is carried out by a 20-80 mesh sieve; in the step (12), the roasting condition is that roasting is carried out for 3-10 hours at 300-500 ℃.
The application of the catalyst in preparing methyl formate by catalyzing synthesis gas through a one-step method is specifically as follows: filling a catalytic layer B, an insulating layer and a catalytic layer A in the catalyst into a fixed bed reactor from bottom to top in sequence in layers, introducing hydrogen-containing gas for reduction and activation, adjusting the reaction temperature to 200-260 ℃, and then switching the pressure of the introduced synthesis gas to be increased to 0.5-2MPa for reaction.
Preferably, the conditions of reduction and activation are that the reduction temperature is 250-350 ℃, the reduction time is 1-8 hours, and the reduction pressure is normal pressure; CO: H in the synthesis gas 2 The volume ratio of (1-4) is 1; the space velocity of the synthesis gas relative to the catalytic layer A is 100-5000h -1 。
Preferably, the hydrogen-containing gas consists of 5-50% of hydrogen 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.
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) 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 atomic economic reaction.
Detailed Description
Example 1
1. A catalyst for preparing methyl formate by a one-step method of catalyzing synthesis gas consists of 2.0g of an independent catalytic layer A, 1mL of an isolation layer and 2.0g of a catalytic layer B;
the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -ZrO 2 The weight ratio of the Cu, zn, al, zr in the metal oxide is as follows: cu: zn: al: zr=50:30:4:16;
the isolation layer is quartz sand;
the catalytic layer B is a Cu-based catalyst and 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 m 2 The carbon nano tube per gram comprises the following components in percentage by weight of 100 percent: cu 10%, auxiliary La 1%, and the rest is carrier carbon nano tube, marked as 1.0La10Cu/CNTs.
2. The preparation method of the catalyst for preparing methyl formate by catalyzing synthesis gas through a one-step method comprises the following steps:
(1) Preparation of a metal oxide catalyst:
(11) Preparing copper nitrate, zinc nitrate, aluminum nitrate and zirconium nitrate into a salt solution with the total metal ion concentration of 1mol/L, and simultaneously 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) Aging at 75deg.C for 2 hr, washing, oven drying at 110deg.C for 10 hr, and muffle furnaceRoasting for 4 hours at the temperature of 350 ℃, tabletting, forming, screening, and sieving with a 40-60 mesh sieve to obtain CuO-ZnO-Al 2 O 3 -ZrO 2 A metal oxide catalyst;
(2) Preparation of Cu-based catalyst:
(21) Copper nitrate and lanthanum nitrate are dissolved in ethanol to form solution A;
(22) According to 1g: adding carrier carbon nanotube into solution A by 60mL, performing ultrasonic treatment for 2h, stirring at room temperature until no liquid exists in the container, drying at 90 ℃ for 15h, tabletting, shaping, and sieving with 40-60 meshes;
(3) Preparing a catalyst:
weighing a metal oxide catalyst according to a proportion to obtain a catalytic layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalytic layer B.
3. The application of the catalyst in preparing methyl formate by catalyzing synthesis gas through a one-step method is specifically as follows: filling a catalytic layer B, an insulating layer and a catalytic layer A in the catalyst into a fixed bed reactor from bottom to top in sequence in layers, introducing hydrogen-containing gas at a flow rate of 30mL/min, and performing normal pressure reduction and activation for 2 hours at 250 ℃, wherein the hydrogen-containing gas consists of hydrogen with a volume ratio of 10% and the balance of nitrogen; then adjusting the reaction temperature to 220 ℃, and switching to charge the synthesis gas to boost the pressure to 2MPa for reaction; CO: H in the synthesis gas 2 Is 2:1 by volume; the space velocity of the synthesis gas relative to the catalytic layer A is 1500h -1 The gas chromatography whole components were analyzed on line and the results are shown in Table 1.
Example 2
1. A catalyst for preparing methyl formate by a one-step method of catalyzing synthesis gas consists of 2.0g of an independent catalytic layer A, 2mL of an isolation layer and 3.0g of a catalytic layer B;
the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -CeO 2 The weight ratio of the Cu, zn, al, ce in the metal oxide is as follows: cu: zn: al: ce=55:26:4:15;
the isolation layer is quartz sand;
the catalytic layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, and the catalyst layer B is a catalystThe auxiliary agent is K and Mg, and the specific surface area of the carrier is more than 200 m 2 The active carbon per gram comprises the following components in percentage by weight of 100 percent: cu 5%, auxiliary agent K0.5%, auxiliary agent Mg 1.5%, and carrier active carbon for the rest, marked as 0.5K1.5Mg5Cu/AC.
2. The preparation method of the catalyst for preparing methyl formate by catalyzing synthesis gas through a one-step method comprises the following steps:
(1) Preparation of a metal oxide catalyst:
(11) Preparing copper nitrate, zinc nitrate, aluminum chloride and cerium nitrate into a salt solution with the total metal ion concentration of 0.5mol/L, and preparing 1mol/L potassium hydroxide solution as a precipitant; at 90 ℃, the salt solution and the precipitant are simultaneously dripped into deionized water, and the pH value of the system is controlled to 8.0-9.0 by controlling the dripping speed of the precipitant solution;
(12) Aging at 90deg.C for 2 hr, washing, oven drying at 90deg.C for 15 hr, calcining at 450deg.C in muffle furnace for 4 hr, tabletting, sieving with 40-60 mesh sieve to obtain CuO-ZnO-Al 2 O 3 -CeO 2 A metal oxide catalyst;
(2) Preparation of Cu-based catalyst:
(21) Copper nitrate, potassium chloride and magnesium chloride are dissolved in water to form a solution A;
(22) According to 1g: adding carrier active carbon into the solution A by 50mL, performing ultrasonic treatment for 0.5h, stirring at room temperature until no liquid exists in a container, drying at 110 ℃ for 10h, tabletting, shaping, and sieving with 20-40 meshes;
(3) Preparing a catalyst:
weighing a metal oxide catalyst according to a proportion to obtain a catalytic layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalytic layer B.
3. The application of the catalyst in preparing methyl formate by catalyzing synthesis gas through a one-step method is specifically as follows: filling a catalytic layer B, an insulating layer and a catalytic layer A in the catalyst into a fixed bed reactor in sequence from bottom to top in layers, introducing hydrogen-containing gas at a flow rate of 50mL/min, and performing normal pressure reduction and activation for 3h at 300 ℃, wherein the hydrogen-containing gas is formed by a catalyst bodyHydrogen accounting for 50% of the total volume and helium accounting for the rest; then adjusting the reaction temperature to 200 ℃, and switching to charge the synthesis gas to boost the pressure to 0.5MPa for reaction; CO: H in the synthesis gas 2 The volume ratio of (2) is 3:1; the space velocity of the synthesis gas relative to the catalytic layer A is 2000h -1 The gas chromatography whole components were analyzed on line and the results are shown in Table 1.
Example 3
1. A catalyst for preparing methyl formate by a one-step method of catalyzing synthesis gas consists of 1.5g of an independent catalytic layer A, 2mL of an isolation layer and 6.0g of a catalytic layer B;
the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -ZrO 2 -MnO 2 The weight ratio of the Cu, zn, al, zr, mn in the metal oxide is as follows: cu, zn, al, zr: mn=40:30:8:15:7;
the isolation layer is quartz sand;
the catalytic 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 m 2 Graphene/g, the contents of the components, based on 100% of the total weight, are as follows: cu 12%, auxiliary Ce 1.2%, and the rest is carrier Graphene, and is marked as 1.2Ce12Cu/Graphene.
2. The preparation method of the catalyst for preparing methyl formate by catalyzing synthesis gas through a one-step method comprises the following steps:
(1) Preparation of a metal oxide catalyst:
(11) Preparing copper nitrate, zinc chloride, aluminum nitrate, zirconium nitrate and manganese nitrate into a salt solution with the total metal ion concentration of 0.1mol/L, and simultaneously preparing a 0.3mol/L sodium hydroxide solution as a precipitant; at 60 ℃, the salt solution and the precipitant are simultaneously dripped into deionized water, and the pH value of the system is controlled to 8.5-9.5 by controlling the dripping speed of the precipitant solution;
(12) Aging at 60deg.C for 2 hr, washing, oven drying at 150deg.C for 6 hr, calcining at 500deg.C in muffle furnace for 3 hr, tabletting, sieving with 20-40 mesh sieve to obtain CuO-ZnO-Al 2 O 3 -ZrO 2 -MnO 2 Oxidation of metalsA physical catalyst;
(2) Preparation of Cu-based catalyst:
(21) Copper nitrate and cerium nitrate are dissolved in water to form a solution A;
(22) According to 1g: adding 30mL of carrier graphene into the solution A, performing ultrasonic treatment for 0.5h, stirring at room temperature until no liquid exists in a container, drying at 150 ℃ for 6h, tabletting, forming, and sieving with 60-80 meshes;
(3) Preparing a catalyst:
weighing a metal oxide catalyst according to a proportion to obtain a catalytic layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalytic layer B.
3. The application of the catalyst in preparing methyl formate by catalyzing synthesis gas through a one-step method is specifically as follows: filling a catalytic layer B, an insulating layer and a catalytic layer A in the catalyst into a fixed bed reactor from bottom to top in sequence in layers, introducing hydrogen-containing gas at the flow rate of 100mL/min, and performing normal-pressure reduction and activation for 1h at the temperature of 350 ℃, wherein the hydrogen-containing gas consists of hydrogen with the volume ratio of 5% and the balance of argon; then adjusting the reaction temperature to 260 ℃, and switching to charge the synthesis gas to boost the pressure to 1MPa for reaction; CO: H in the synthesis gas 2 Is 4:1 by volume; the space velocity of the synthesis gas relative to the catalytic layer A is 4000h -1 The gas chromatography whole components were analyzed on line and the results are shown in Table 1.
Example 4
1. A catalyst for preparing methyl formate by a one-step method of catalyzing synthesis gas consists of 2.0g of an independent catalytic layer A, 1mL of an isolation layer and 4.0g of a catalytic layer B;
the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -MgO, said metal oxide, said Cu, zn, al, mg being present in the following weight ratio: cu: zn: al: mg=50:20:7:23;
the isolation layer is quartz sand;
the catalytic 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 m 2 Graphene/g, the contents of the components, based on 100% of the total weight, are as follows: cu 9%,auxiliary agent Mg0.5%, rest is carrier Graphene, marked as 0.5Mg9Cu/Graphene.
2. The preparation method of the catalyst for preparing methyl formate by catalyzing synthesis gas through a one-step method comprises the following steps:
(1) Preparation of a metal oxide catalyst:
(11) Preparing a salt solution with the total metal ion concentration of 0.8mol/L from copper nitrate, zinc nitrate, aluminum nitrate and magnesium chloride, and simultaneously preparing a sodium carbonate solution with the total metal ion concentration of 0.8mol/L as a precipitant; at 80 ℃, the salt solution and the precipitant are simultaneously dripped into deionized water, and the pH value of the system is controlled to 7.0-8.0 by controlling the dripping speed of the precipitant solution;
(12) Aging at 80deg.C for 2 hr, washing, oven drying at 120deg.C for 7 hr, calcining at 300deg.C in muffle furnace for 10 hr, tabletting, sieving with 40-60 mesh sieve to obtain CuO-ZnO-Al 2 O 3 -MgO metal oxide catalyst;
(2) Preparation of Cu-based catalyst:
(21) Dissolving copper nitrate and magnesium chloride in ethanol to form a solution A;
(22) According to 1g: adding carrier graphene into the solution A by 40mL, performing ultrasonic treatment for 1.5h, stirring at room temperature until no liquid exists in a container, drying at 120 ℃ for 8h, tabletting, forming, and sieving with 40-60 meshes;
(3) Preparing a catalyst:
weighing a metal oxide catalyst according to a proportion to obtain a catalytic layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalytic layer B.
3. The application of the catalyst in preparing methyl formate by catalyzing synthesis gas through a one-step method is specifically as follows: filling a catalytic layer B, an insulating layer and a catalytic layer A in the catalyst into a fixed bed reactor from bottom to top in sequence in layers, introducing hydrogen-containing gas at a flow rate of 20mL/min, and performing normal pressure reduction and activation for 2 hours at 280 ℃, wherein the hydrogen-containing gas consists of hydrogen with a volume ratio of 30% and the balance of nitrogen; then adjusting the reaction temperature to 230 ℃, and switching to charge the synthesis gas to boost the pressure to 1.5MPa for reaction; CO: H in the synthesis gas 2 The volume ratio of (1):1, a step of; the space velocity of the synthesis gas relative to the catalytic layer A is 2000h -1 The gas chromatography whole components were analyzed on line and the results are shown in Table 1.
Comparative example 1
The catalyst contained only catalytic layer a, which was the same as in example 1.
The catalyst is applied to the preparation of methyl formate by a one-step method of synthesis gas: the results of the catalyst in the direct fixed bed reactor were as in example 1 and are shown in Table 1.
Comparative example 2
The catalyst contained only catalytic layer B, which was the same as in example 1.
The catalyst is applied to the preparation of methyl formate by a one-step method of synthesis gas: the results of the catalyst in the direct fixed bed reactor were as in example 1 and are shown in Table 1.
TABLE 1 reaction results
Remarks: the selectivity of products such as methyl formate and the like is CO removal 2 Molar selectivity of methyl formate in the external product; other means small amounts of dimethyl ether, ethanol and hydrocarbons.

Claims (9)

1. A catalyst for preparing methyl formate by a one-step method of catalytic synthesis gas is characterized in that: the catalyst consists of an independent catalytic layer A, an isolation layer and a catalytic layer B;
the catalytic layer A is a metal oxide catalyst and is marked as CuO-ZnO-Al 2 O 3 -MOx, wherein the metal oxide comprises the following components in percentage by weight based on 100% of the total weight of Cu, zn, al, M: 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, mg, and x is the number of oxygen atoms required for meeting the oxidation state of the metal element M;
the isolation layer is quartz sand;
the catalytic layer B is a Cu-based catalyst and consists of Cu, an auxiliary agent and a carrier, wherein the content of each component is as follows, based on 100% of the total weight: cu (Cu)5-12%, 0.5-2% of auxiliary agent and the balance of carrier; the auxiliary agent is at least one of K, mg, la or Ce, the carrier is graphene, carbon nano tube or active carbon, and the specific surface area of the carrier is more than 200 m 2 /g；
The mass ratio of the catalytic layer A to the catalytic layer B is 1: (1-4) the ratio of the catalytic layer a to the insulating layer is (1.5-2) g: (0.5-2) mL.
2. The method for preparing the catalyst for preparing methyl formate by catalyzing synthesis gas through one-step process as set forth in claim 1, which is characterized in that: the method comprises the following steps:
(1) Preparation of a metal oxide catalyst:
(11) Simultaneously dripping a salt solution of the metal Cu, zn, al, M and a precipitant solution into water at the temperature of 60-90 ℃, and controlling the pH value of the system to 7.0-9.5 by controlling the dripping speed of the precipitant solution;
(12) Continuing aging reaction for 2 hours at 60-90 ℃, and then washing, drying, roasting, tabletting, forming and screening to obtain the metal oxide catalyst;
(2) Preparation of Cu-based catalyst:
(21) Dissolving 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 a metal oxide catalyst according to a proportion to obtain a catalytic layer A; weighing quartz sand to obtain an isolation layer; and weighing the Cu-based catalyst to obtain a catalytic layer B.
3. The method for preparing the catalyst for preparing methyl formate by catalyzing synthesis gas to one-step method as claimed in claim 2, which is characterized in that: in the step (11), the salt solution of the metal Cu, zn, al, M is nitrate or chloride salt solution of the corresponding metal, and the total ion concentration of the metal Cu, zn, al, M is 0.1-1mol/L.
4. A method for preparing a catalyst for preparing methyl formate by catalyzing synthesis gas to one-step method according to claim 3, wherein: in the step (11), the precipitant solution is 0.1-1mol/L NaOH solution and Na 2 CO 3 Solutions or KOH solutions.
5. The method for preparing the catalyst for preparing methyl formate by catalyzing synthesis gas to one-step method according to claim 4, which is characterized in that: in the step (2), the copper salt and the auxiliary agent precursor are nitrate or chloride of corresponding metal, and the ratio of the carrier to the solution A is 1g: (30-60) mL.
6. The method for preparing the catalyst for preparing methyl formate by catalyzing synthesis gas to prepare methyl formate by one-step method according to claim 5, which is characterized in that: in the step (12) and the step (22), the drying condition is that the drying is carried out for 6-15 hours at 90-150 ℃, and the screening is that the materials are sieved by a 20-80 mesh sieve; in the step (12), the roasting condition is that roasting is carried out for 3-10 hours at 300-500 ℃.
7. Use of the catalyst of claim 1 for the one-step preparation of methyl formate from catalytic synthesis gas, characterized in that: the application is specifically as follows: filling a catalytic layer B, an insulating layer and a catalytic layer A in the catalyst into a fixed bed reactor from bottom to top in sequence in layers, introducing hydrogen-containing gas for reduction and activation, adjusting the reaction temperature to 200-260 ℃, and then switching the pressure of the introduced synthesis gas to be increased to 0.5-2MPa for reaction.
8. The use of the catalyst according to claim 7 for the one-step preparation of methyl formate from catalytic synthesis gas, wherein: the conditions of reduction and activation are that the reduction temperature is 250-350 ℃, the reduction time is 1-8h, and the reduction pressure is normal pressure; CO: H in the synthesis gas 2 The volume ratio of (1-4) is 1; the space velocity of the synthesis gas relative to the catalytic layer A is 100-5000h -1 。
9. Use of the catalyst according to claim 8 for the catalytic synthesis of methyl formate in a one-step process, characterized in that: the hydrogen-containing gas consists of hydrogen accounting for 5-50% of the volume ratio and balance gas which is nitrogen, helium or argon; the flow rate of the hydrogen-containing gas is 20-100 mL/min.
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