Multi-component supported catalyst as well as preparation method and application thereof

Abstract

The invention provides a multi-component supported catalyst as well as a preparation method and application thereof, and belongs to the technical field of catalysts. The invention provides a multi-component supported catalyst which comprises main active metal, a cocatalyst component and an oxide carrier, the main active metal comprises Cu and Ag, the cocatalyst component comprises one or more of Cs, Y, Ga, In, Zn and Ni, and the oxide carrier comprises SiO2. By adding the cocatalyst component and Ag, the interaction between Cu and the oxide carrier is enhanced to promote dispersion of Cu, so that the catalytic activity is improved, and the conversion rate of methanol is increased. Data of the embodiment shows that the multi-component supported catalyst can be applied to a reaction for preparing methyl formate through methanol coupling and producing high-purity hydrogen as a byproduct under the continuous carrier-gas-free condition of a fixed bed, shows excellent catalytic activity and high selectivity, has a long service life and has a good industrial application prospect.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a multi-component supported catalyst, its preparation method, and its application. Background Technology

[0002] Methanol is an important energy platform molecule in the chemical industry. It is considered a promising general energy candidate and a key product for creating added value from coal, helping to solve energy, transportation, and ecological problems. Furthermore, in C1 chemistry, methanol is used as a raw material for the production of aldehydes, ethers, alcohols, esters, and olefins. Methyl formate, an ester chemical substance, is a common intermediate in C1 chemistry, and its wide range of applications has attracted increasing interest from researchers. Methyl formate is a colorless, odorous, volatile liquid and an important organic synthesis intermediate with a wide range of uses. Starting from methyl formate, its chemical properties can be used to produce formic acid, formamide, dimethylformamide, and phosgene; it can also be used to synthesize acetic acid, methyl acetate, and acetic anhydride; and it can be used to produce dimethyl carbonate and ethylene glycol. Methyl formate can be used as a raw material for organic synthesis, a solvent for cellulose acetate, a bactericide, a fumigant, an insecticide, and a grain and tobacco treatment agent. In pharmaceuticals, it is commonly used as a raw material for the synthesis of drugs such as methyl pyrimidine sulfonate, methoxypyrimidine sulfonate, and the antitussive dextromethorphan. Compared with related preparation methods, the direct dehydrogenation of methanol to methyl formate is considered a highly efficient, economical, and environmentally friendly alternative due to its simple technology and low equipment investment. The core and key to this method lies in the development of a highly efficient catalyst. Noble metal catalysts exhibit excellent catalytic performance, but due to their high price and deactivation, they are not suitable for widespread industrial application. By comparison, transition metal copper catalysts have both economic advantages and excellent catalytic activity, making them ideal catalysts for methanol dehydrogenation. In the process of methanol dehydrogenation to methyl formate synthesis, the preparation method and performance of the support have a significant impact on the activity and selectivity of Cu-based catalysts. Compared with other oxide supports, SiO2-supported nano-copper catalysts are more favorable for methanol dehydrogenation to methyl formate due to their low basicity and weak base centers. However, Cu-based catalysts have poor stability and suffer from low catalytic activity. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a multi-component supported catalyst, its preparation method, and its application. The multi-component supported catalyst provided by this invention exhibits good catalytic activity and high methanol conversion rate.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a multi-component supported catalyst, comprising a main active metal, a co-catalyst component, and an oxide support. The main active metal includes Cu and Ag, the co-catalyst component includes one or more of Cs, Y, Ga, In, Zn, and Ni, and the oxide support includes SiO2.

[0006] Preferably, the mass of Cu is 0.5 to 10% of the mass of the oxide support, and the mass of Ag is 0.05 to 5% of the mass of the oxide support.

[0007] Preferably, the mass of Cu is 8.38% of the mass of the oxide support, and the mass of Ag is 0.265 to 1.06% of the mass of the oxide support.

[0008] Preferably, the mass of the co-catalyst component is 0.05 to 5% of the mass of the oxide support.

[0009] Preferably, the mass of the co-catalyst component is 0.1% to 0.53% of the mass of the oxide support.

[0010] This invention also provides a method for preparing the multi-component supported catalyst described in the above technical solution, comprising the following steps:

[0011] A sol is obtained by mixing a metal salt solution, an organosilicon ester, and ammonia water; the metal salt solution contains a main active metal and a co-catalyst component.

[0012] The sol was aged to obtain a gel;

[0013] The gel was dried and calcined sequentially to obtain the multi-component supported catalyst.

[0014] Preferably, the organosilicon ester includes one or more of methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate.

[0015] Preferably, the aging is carried out by heating, and the heating temperature is 30-100°C for 3-30 hours.

[0016] Preferably, the drying temperature is 60–150°C and the drying time is 1–15 h; the calcination temperature is 300–800°C and the calcination time is 3–20 h.

[0017] The present invention also provides the application of the multi-component supported catalyst described in the above technical solution or the multi-component supported catalyst prepared by the above technical solution in the reaction of methanol coupling to methyl formate.

[0018] This invention provides a multi-component supported catalyst, comprising a main active metal, a co-catalyst component, and an oxide support. The main active metal includes Cu and Ag, the co-catalyst component includes one or more of Cs, Y, Ga, In, Zn, and Ni, and the oxide support includes SiO2.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] This invention enhances the interaction between Cu and the oxide support by adding a co-catalyst component and Ag, thereby promoting Cu dispersion and improving catalytic activity, thus increasing the conversion rate of methanol. Data from the examples show that the multi-component supported catalyst of this invention can be applied to the methanol coupling to methyl formate reaction with high-purity hydrogen as a byproduct under continuous fixed-bed, carrier-free conditions, exhibiting excellent catalytic activity and high selectivity, a long service life, and promising prospects for industrial application.

[0021] This invention also provides a method for preparing the multi-component supported catalyst described in the above technical solution. The preparation method of this invention is simple to operate and suitable for industrial application. Attached Figure Description

[0022] Figure 1 The stability test curves of the multi-component supported catalyst prepared in Example 1 are shown.

[0023] Figure 2 The stability test curves of the multi-component supported catalyst prepared in Example 6 are shown.

[0024] Figure 3 The stability test curves of the multi-component supported catalyst prepared in Example 7 are shown.

[0025] Figure 4 The stability test curves are for the supported catalyst prepared in Comparative Example 1. Detailed Implementation

[0026] This invention provides a multi-component supported catalyst, comprising a main active metal, a co-catalyst component, and an oxide support. The main active metal includes Cu and Ag, the co-catalyst component includes one or more of Cs, Y, Ga, In, Zn, and Ni, and the oxide support includes SiO2.

[0027] In this invention, both the main active metal and the cocatalyst component are preferably nanoparticles, and both the main active metal and the cocatalyst component are loaded on the oxide support.

[0028] In this invention, the mass of Cu is preferably 0.5-10% of the mass of the oxide support, specifically 8.38%, and the mass of Ag is preferably 0.05-5% of the mass of the oxide support, specifically 0.265%, 0.53%, 1.06%, 2%, 3%, 4%, or 5%.

[0029] In this invention, the mass of the co-catalyst component is preferably 0.05% to 5% of the mass of the oxide support, specifically 0.10%, 0.265%, 0.43%, 0.49%, 0.53%, 1.06%, 2%, 3%, 4%, or 5%.

[0030] In this invention, the oxide support is preferably amorphous silicon dioxide obtained by hydrolysis of organosilicon esters.

[0031] This invention also provides a method for preparing the multi-component supported catalyst described in the above technical solution, comprising the following steps:

[0032] A sol is obtained by mixing a metal salt solution, an organosilicon ester, and ammonia water; the metal salt solution contains a main active metal and a co-catalyst component.

[0033] The sol was aged to obtain a gel;

[0034] The gel was dried and calcined sequentially to obtain the multi-component supported catalyst.

[0035] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0036] The present invention mixes a metal salt solution, an organosilicone ester, and ammonia water to obtain a sol; the metal salt solution contains a main active metal and a co-catalyst component.

[0037] In this invention, the metal salt solution preferably comprises three or more of the following: inorganic copper salt, inorganic silver salt, yttrium salt, gallium salt, cesium salt, indium salt, zinc salt, and nickel salt. The inorganic copper salt preferably comprises one or more of copper nitrate, copper sulfate, copper chloride, and copper acetate. The inorganic silver salt preferably comprises silver nitrate and / or silver acetate. The yttrium salt preferably comprises yttrium nitrate and / or yttrium acetate. The gallium salt preferably comprises gallium nitrate and / or gallium acetate. The cesium salt preferably comprises one or more of cesium nitrate, cesium carbonate, and cesium acetate. The indium salt preferably comprises indium nitrate and / or indium acetate. The zinc salt preferably comprises one or more of zinc nitrate, zinc acetate, and zinc sulfate. The nickel salt preferably comprises nickel nitrate and / or nickel acetate.

[0038] In this invention, the solvent for the metal salt solution preferably includes one or more of methanol, ethanol, and ethyl acetate.

[0039] In this invention, the volume ratio of the solvent to the organosilicone ester is preferably (0.5-3):1, specifically 0.5:1, 1:1, 2:1 or 3:1; the volume ratio of the metal salt solution to the organosilicone ester is preferably (0.5-2):1, specifically 0.5:1, 1:1 or 2:1.

[0040] In this invention, the organosilicon ester includes one or more of methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate.

[0041] In this invention, the ammonia water is preferably concentrated ammonia water, and the mass percentage of the concentrated ammonia water is preferably 20% to 28%.

[0042] In this invention, the mixing of the metal salt solution, organosilicon ester and ammonia preferably includes the following steps: mixing the organosilicon ester and the solvent of the metal salt solution, then adding the metal salt of the metal salt solution to obtain a mixture, and finally adding the ammonia dropwise to the mixture.

[0043] After obtaining the sol, the present invention ages the sol to obtain a gel.

[0044] In this invention, the aging is preferably carried out by heating, and the heating temperature is preferably 30 to 100°C, specifically 30, 40, 50, 60, 70, 80, 90 or 100°C, and the heating time is preferably 3 to 30 hours, specifically 3, 5, 12, 15, 20, 25 or 30 hours.

[0045] After the aging process is completed, it is preferable to further include natural cooling to ambient temperature, followed by sequential filtration and washing with deionized water until pH=7, to obtain precipitate.

[0046] After obtaining the gel, the present invention sequentially dries and calcines the gel to obtain the multi-component supported catalyst.

[0047] In this invention, the drying temperature is preferably 60–150°C, specifically 30, 40, 50, 60, 70, 80, 90, or 100°C, and the drying time is preferably 1–15 hours, specifically 1, 5, 10, 12, or 15 hours; the calcination temperature is preferably 300–800°C, specifically 300, 400, 500, 600, 700, or 800°C, and the calcination time is preferably 3–20 hours, specifically 3, 5, 8, 10, 15, or 20 hours.

[0048] In this invention, the heating rate from room temperature to the calcination temperature is preferably 5°C·min. -1 .

[0049] In this invention, the roasting is preferably carried out in air.

[0050] The present invention also provides the application of the multi-component supported catalyst described in the above technical solution or the multi-component supported catalyst prepared by the above technical solution in the reaction of methanol coupling to methyl formate.

[0051] In this invention, the reaction temperature is preferably 200 to 400°C, specifically 200, 220, 240, 300, 330 or 400°C.

[0052] In this invention, the preferred mass hourly space velocity (MHSV) of methanol in the reaction is 0.5–20 h⁻¹. -1 Specifically, it can be 0.5, 1, 4.8, 10, 15, or 20h. -1 .

[0053] In this invention, the reaction is preferably carried out under continuous fixed-bed conditions without carrier gas.

[0054] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0055] Example 1

[0056] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 25 mg of silver nitrate, and 50 mg of yttrium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-1, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.53% of the mass of the oxide support, and the co-catalyst component yttrium accounts for 0.53% of the mass of the oxide support.

[0057] Example 2

[0058] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 12.5 mg of silver nitrate, and 50 mg of yttrium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-2, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.265% of the mass of the oxide support, and the co-catalyst component yttrium accounts for 0.53% of the mass of the oxide support.

[0059] Example 3

[0060] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 50 mg of silver nitrate, and 50 mg of yttrium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-3, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 1.06% of the mass of the oxide support, and the co-catalyst component yttrium accounts for 0.53% of the mass of the oxide support.

[0061] Example 4

[0062] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 25 mg of silver nitrate, and 25 mg of yttrium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-4, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.53% of the mass of the oxide support, and the co-catalyst component yttrium accounts for 0.265% of the mass of the oxide support.

[0063] Example 5

[0064] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 25 mg of silver nitrate, and 40 mg of yttrium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-5, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.53% of the mass of the oxide support, and the co-catalyst component yttrium accounts for 0.43% of the mass of the oxide support.

[0065] Example 6

[0066] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 25 mg of silver nitrate, and 10.24 mg of gallium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-6, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.53% of the mass of the oxide support, and gallium, the co-catalyst component, accounts for 0.10% of the mass of the oxide support.

[0067] Example 7

[0068] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 25 mg of silver nitrate, and 6.57 mg of cesium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-7, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.53% of the mass of the oxide support, and the co-catalyst component cesium accounts for 0.10% of the mass of the oxide support.

[0069] Example 8

[0070] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate, 25 mg of silver nitrate, and 50 mg of indium nitrate and add them to the mixture in the round-bottom flask. Stir for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 A multi-component supported catalyst, denoted as CAT-8, is prepared in which Cu accounts for 8.38% of the mass of the oxide support, Ag accounts for 0.53% of the mass of the oxide support, and indium, the co-catalyst component, accounts for 0.49% of the mass of the oxide support.

[0071] Comparative Example 1

[0072] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate and 297.49 mg of zinc nitrate hexahydrate and add them to the mixture in the round-bottom flask, stirring for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring constantly during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 The supported catalyst, denoted as CAT-9, is obtained, wherein the mass of Cu is 8.38% of the mass of the oxide support, and the mass of the co-catalyst component zinc is 2.18% of the mass of the oxide support.

[0073] Comparative Example 2

[0074] Measure 10 mL of tetraethyl orthosilicate and 10 mL of anhydrous ethanol, add them to a 50 mL round-bottom flask, and stir for 10 min to mix thoroughly. Then weigh 950 mg of copper nitrate trihydrate and 50 mg of yttrium nitrate and add them to the mixture in the round-bottom flask, stirring for 10 min until completely dissolved to obtain a solution. Measure 2 mL of NH3·H2O and 8 mL of deionized water and mix thoroughly to obtain an alkaline solution. Then add the alkaline solution dropwise to the above salt solution, stirring continuously during the addition. After adding 5 mL of alkaline solution, a light blue suspension is obtained. Stir at room temperature for 1 h, then transfer the obtained light blue suspension to a 100 mL hydrothermal reactor, seal it, and maintain it at 80 °C for 12 h, then cool it to ambient temperature. Separate the precipitate by filtration and washing with deionized water several times (until pH = 7). Finally, dry at 100 °C overnight and calcine in air at 300 °C for 8 h (the heating rate from room temperature to the calcination temperature is 5 °C·min). -1 The supported catalyst, denoted as CAT-10, is obtained, wherein the mass of Cu is 8.38% of the mass of the oxide support, and the mass of the co-catalyst component yttrium is 0.53% of the mass of the oxide support.

[0075] Application Example 1

[0076] The catalysts used in the examples and comparative examples were loaded into a fixed-bed reactor, and the catalytic dehydrogenation of methanol was carried out in the fixed bed at a reaction temperature of 240°C and a methanol mass hourly space velocity of 4.8 h⁻¹. -1 The conversion rate of methanol and the selectivity of methyl formate were measured after the reaction was stable for 24 hours. The results are shown in Table 1. It can be seen that the present invention enhances the interaction between Cu nanoparticles and the support by adding co-catalyst components and Ag, and promotes the dispersion of Cu nanoparticles, thereby improving the conversion rate and selectivity of methanol.

[0077] Table 1 Catalytic performance of the catalysts in the examples and comparative examples.

[0078] Example catalyst Methanol conversion rate / % Methyl formate selectivity / % Example 1 CAT-1 42.10％ 95.3％ Example 2 CAT-2 28.39％ 95.2％ Example 3 CAT-3 27.97％ 95.1％ Example 4 CAT-4 23.46％ 96.2％ Example 5 CAT-5 24.52％ 95.8％ Example 6 CAT-6 33.34％ 96.4％ Example 7 CAT-7 30.09％ 95.5％ Example 8 CAT-8 30.35％ 96.5％ Comparative Example 1 CAT-9 16.20％ 97.5％ Comparative Example 2 CAT-10 8.55％ 96.3％

[0079] Application Example 2

[0080] The catalysts from Examples 1, 6, 7, and Comparative Example 1 were loaded into a fixed-bed reactor for stability testing. The temperature of the methanol catalytic dehydrogenation reaction was 240°C, and the methanol mass hourly space velocity (MHSV) was 4.8 h⁻¹. -1 The methanol conversion rates of the heterogeneous catalysts in Examples 1, 6, 7 and Comparative Example 1 at different reaction times were measured as follows: Figures 1-4 As shown, Figure 1 The stability test curves are shown for the multi-component supported catalyst prepared in Example 1. Figure 2 The stability test curves are for the multi-component supported catalyst prepared in Example 6. Figure 3The stability test curves are for the multi-component supported catalyst prepared in Example 7. Figure 4 The stability test curve of the supported catalyst prepared in Comparative Example 1 shows that the multi-component supported catalyst prepared in this invention has good stability.

[0081] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A multi-component supported catalyst characterized in that, The main active metal comprises Cu and Ag, the promoter component comprises one or more of Cs, Y, Ga, In, Zn, Ni, and the oxide carrier comprises SiO2.

2. The multi-component supported catalyst according to claim 1, wherein, The mass of the Cu is 0.5-10% of the mass of the oxide carrier, and the mass of the Ag is 0.05-5% of the mass of the oxide carrier.

3. The multi-component supported catalyst of claim 2, wherein, The mass of the Cu is 8.38% of the mass of the oxide carrier, and the mass of the Ag is 0.265-1.06% of the mass of the oxide carrier.

4. The multi-component supported catalyst according to claim 1 or 2, characterized in that, The mass of the promoter component is 0.05-5% of the mass of the oxide carrier.

5. The multi-component supported catalyst of claim 4, wherein, The mass of the promoter component is 0.1-0.53% of the mass of the oxide carrier.

6. Process for the preparation of the multi-component supported catalyst according to any one of claims 1 to 5, characterized in that, The method comprises the following steps: Mixing a metal salt solution, an organosilicate and ammonia water to obtain a sol; the metal salt solution contains a main active metal and a promoter component; Aging the sol to obtain a gel; Drying and calcining the gel in sequence to obtain the multi-component supported catalyst.

7. The production method according to claim 6, wherein The organosilicate comprises one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.

8. The preparation method according to claim 6, characterized in that, The aging is performed by heating at a temperature of 30-100°C for 3-30h.

9. The preparation method according to claim 6, characterized in that, The drying is performed at a temperature of 60-150°C for 1-15h, and the calcining is performed at a temperature of 300-800°C for 3-20h.

10. Use of the multi-component supported catalyst of any one of claims 1-5 or the multi-component supported catalyst prepared by the method of any one of claims 6-9 in a reaction of coupling methanol to prepare methyl formate.

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