Copper-containing catalyst, and preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of chemical catalysts. Disclosed are a copper-containing catalyst, and a preparation method therefor and a use thereof. The method comprises: (1) carrying out a first reaction on an aluminum-magnesium solution and a first precipitant to obtain a first product system; (2) carrying out a second reaction on a copper-zinc-nickel source solution, a second precipitant, and the first product system to obtain a second product system; (3) carrying out a third reaction on the second product system and an organosilane modifier to obtain a third product system, and carrying out separation treatment on the third product system to obtain a gel; and (4) calcining the gel to obtain the copper-containing catalyst. Therefore, the high-temperature stability and anti-soaking performance of the catalyst can be improved, thereby prolonging the service life of the catalyst at a high temperature, and the catalyst has excellent hydrogenation activity and product selectivity for aldehydes or esters.

Description

Copper-containing catalyst and preparation method and application thereof

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202411120995.5, filed on August 15, 2024, entitled “Copper-containing catalyst and preparation method and application thereof”, the content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the technical field of chemical catalysts, in particular to a copper-containing catalyst and a preparation method and application thereof. BACKGROUND

[0004] Aldehydes and esters are usually hydrogenated by using copper-containing catalysts. The existing copper-containing catalysts for liquid-phase hydrogenation of aldehydes and esters are usually prepared by co-precipitation method. The main process is to precipitate copper-containing compounds, and then to calcine to convert the precipitate into an oxide.

[0005] CN106132542A discloses a hydrogenation catalyst and a preparation method thereof. The prepared Cu-Zn catalyst is suitable for hydrogenation of aldehydes, ketones, and esters of carboxylic acids or fatty acids (particularly fatty acid methyl esters) to corresponding alcohols, and hydrogenation of esters of dicarboxylic anhydrides or diacids to diols. The preparation method includes precipitating metal nitrate with sodium carbonate to form its carbonate, then filtering the precipitate, washing, and spray drying to obtain an uncalcined material. This method is simple, but the catalyst is prone to pulverization during long-term operation.

[0006] CN105709760A discloses a copper-chromium catalyst, a preparation method and application thereof. The preparation method includes the following steps: (1) preparing a copper-chromium mixed solution and an alkaline solution; (2) co-precipitating the copper-chromium mixed solution and the alkaline solution at 20-70℃, maintaining the pH value of the precipitation system at 4-7, and using 30%-60% of the total amount of copper-chromium solution; (3) adding citric acid to the remaining copper-chromium solution, the addition amount being 1.5:1-0.2:1 of the mass of citric acid to the volume of the remaining copper-chromium solution, and continuing to co-precipitate with the alkaline solution, wherein the precipitation system is increased by 10-30℃ compared to the reaction temperature of step (2), and the precipitation reaction pH value is increased by 0.5-1.5; (4) heating the reaction product solution to 80-100℃ to make it lose water and become a gel; (5) drying the gel at 120-150℃ to become a dry gel; (6) grinding the dry gel into a fine powder, adding ethanol and igniting, and the product after combustion is the prepared copper-chromium catalyst.

[0007] The catalyst can be used for hydrogenation of esters to prepare alcohols. Since it uses a chromium-containing catalyst system, it is not environmentally friendly.

[0008] CN112973710A discloses a copper-chromium catalyst, a preparation method thereof and a method for preparing alkanol by hydrogenating enal or aldehyde, the preparation method comprising: providing an aqueous solution containing copper salt and chromium salt as a reaction solution, heating and gelatinizing to obtain a precursor; wherein the anion in the copper salt and / or the chromium salt contains nitrate, the reaction solution contains an additive, and the additive is a reducing substance and / or a raw material capable of decomposing to produce a reducing substance during heating and gelatinizing; drying and calcining the precursor to obtain the copper-chromium catalyst. The catalyst prepared by the process has a small specific surface area.

[0009] CN113797933A discloses a preparation method of a copper-chromium catalyst, comprising: (1) mixing copper oxalate and chromium oxalate with water and then reacting to obtain a gel; (2) sequentially drying and calcining the gel obtained in step (1) to obtain the copper-chromium catalyst. The preparation process is relatively simple, and the harshness of the operation conditions for preparing the catalyst is reduced, but the specific surface area of the prepared catalyst is small.

[0010] CN115364861A discloses a hydrogenation catalyst composition, its application and a method for synthesizing ethylene glycol by hydrogenating dimethyl oxalate. In the preparation method, copper salt and nickel salt are used as the reaction solution, ammonia is used as the precipitating agent, then SiO2 carrier is added, stirring, ammonia evaporation, filtration, washing and calcination are performed to obtain the catalyst precursor. The preparation method is simple, the prepared catalyst has high activity, and the stability of the catalyst is poor, and the catalyst is prone to loss during long-period operation of the device.

[0011] The liquid-phase hydrogenation process of aldehydes and esters has the advantages of simple process flow, low investment and low energy consumption, but has high requirements for the strength and high-temperature stability of the catalyst, and a new preparation method of the hydrogenation catalyst is urgently needed to improve the high-temperature stability, catalytic activity and selectivity of the hydrogenation catalyst, and improve the environmental friendliness of the preparation process. SUMMARY

[0012] The present application provides a copper-containing catalyst, a preparation method and application thereof to solve the problems of poor high-temperature stability, poor catalyst immersion resistance, and further improved catalytic activity and selectivity of the existing catalyst for hydrogenation of aldehydes and esters.

[0013] To achieve the above-mentioned purpose, the first aspect of the present application provides a preparation method of a copper-containing catalyst, comprising:

[0014] (1) a solution containing an aluminum source and a magnesium source is subjected to a first reaction with a first precipitating agent to obtain a first product system;

[0015] (2) a solution containing a copper source, a zinc source and a nickel source, a second precipitating agent and the first product system are subjected to a second reaction to obtain a second product system;

[0016] (3) the second product system is subjected to a third reaction with an organosilane modifier to obtain a third product system, and the third product system is subjected to separation treatment to obtain a gel;

[0017] (4) the gel is subjected to calcination to obtain the copper-containing catalyst.

[0018] The second aspect of the present application provides a copper-containing catalyst prepared by the preparation method of the first aspect.

[0019] The third aspect of the present application provides application of the copper-containing catalyst of the second aspect in an aldehyde hydrogenation reaction or an ester hydrogenation reaction.

[0020] By the preparation method provided by the present application, the copper-containing catalyst prepared has a high specific surface area, pore volume and average pore diameter, and the catalyst has a magnesium-aluminum spinel structure and a surface hydrophobic silicon component, which can improve the high-temperature stability and immersion resistance of the catalyst, reduce the pulverization and component loss of the catalyst during use, prolong the service life of the catalyst at high temperature, and improve the selective adsorption of the catalyst to the molecules of the reaction raw material (aldehyde or ester), reduce the occurrence of side reactions, and improve the selectivity of the hydrogenation product. DETAILED DESCRIPTION

[0021] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The endpoints of the ranges and any values can be approximated to a tolerance of ± 0.1% or 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, about any value or integer thereof within the scope of the range, to the nearest unit provided the foregoing is not already the unit. For ranges including these endpoints, the range is understood to include the endpoints.

[0022] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are merely illustrative and are not to be used to limit the present application.

[0023] The first aspect of the present application provides a preparation method of a copper-containing catalyst, and the method comprises:

[0024] (1) a solution containing an aluminum source and a magnesium source is subjected to a first reaction with a first precipitant to obtain a first product system;

[0025] (2) a solution containing a copper source, a zinc source and a nickel source, a second precipitant and the first product system are subjected to a second reaction to obtain a second product system;

[0026] (3) subjecting the second product system to a third reaction with an organosilane modifier to obtain a third product system, and subjecting the third product system to a separation treatment to obtain a gel;

[0027] (4) subjecting the gel to calcination to obtain the copper-containing catalyst.

[0028] The inventors of the present application have found in research that, by constructing a magnesium-aluminum spinel structure in the preparation process of the catalyst, the high-temperature stability of the catalyst can be significantly improved, and the service life of the catalyst at high temperature can be prolonged, and the prepared catalyst has excellent hydrogenation activity and product selectivity.

[0029] According to the present application, in the preparation method of the copper-containing catalyst, the organosilane modifier has a hydrophobic effect, so that the prepared catalyst has excellent anti-soaking ability, thereby improving the long-period stability of the reaction. In the present application, the anti-soaking ability refers to the ability of the catalyst to resist the soaking damage of the liquid (especially water) in the reaction raw material to the catalyst. In some preferred embodiments of the present application, the organosilane modifier can be selected from at least one of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate and cetyltrimethylammonium bromide.

[0030] According to the present application, it is further preferred that the organosilane modifier can be selected from methyl orthosilicate and / or ethyl orthosilicate, and most preferably methyl orthosilicate.

[0031] According to the present application, in the preparation method of the copper-containing catalyst, the substance of the first precipitant and the second precipitant is limited to be relatively wide, as long as it can be precipitated with the aluminum source, the magnesium source, the copper source, the zinc source and the nickel source in the solution to obtain the corresponding metal-containing precipitate. In the present application, the selection of the precipitant in the art can be used, including but not limited to sodium carbonate, ammonium carbonate, sodium bicarbonate, ammonium bicarbonate, oxalic acid, oxalate and the like.

[0032] According to one preferred embodiment of the present application, the first precipitant and the second precipitant are each independently selected from oxalic acid and / or oxalate, which is beneficial to be removed by sintering in the subsequent step, thereby reducing the generation of waste water in the preparation process.

[0033] In the present application, preferably, the oxalate can be selected from ammonium oxalate and / or hydrogen ammonium oxalate, and further preferably ammonium oxalate.

[0034] According to the present application, in the preparation method of the copper-containing catalyst, the aluminum source is a soluble salt of aluminum, the magnesium source is a soluble salt of magnesium, the copper source is a soluble salt of copper, the zinc source is a soluble salt of zinc, the nickel source is a soluble salt of nickel, and the aluminum source is a soluble salt of aluminum. In the present application, the "soluble" can adopt the general understanding of solubility in the art, i.e. capable of substantially complete dissolution in a solvent.

[0035] According to the present application, in the preparation method of the copper-containing catalyst, the substance of the aluminum source is limited to be wide, and a conventional soluble aluminum salt can be used, which can include but is not limited to at least one of aluminum nitrate, aluminum sulfate and aluminum chloride. Preferably, the aluminum source is aluminum nitrate.

[0036] According to the present application, in the preparation method of the copper-containing catalyst, the substance of the magnesium source is limited to be wide, and a conventional soluble magnesium salt can be used, which can include but is not limited to at least one of magnesium nitrate, magnesium sulfate and magnesium chloride. Preferably, the magnesium source is magnesium nitrate.

[0037] According to the present application, in the preparation method of the copper-containing catalyst, the substance of the copper source is limited to be wide, and a conventional soluble copper salt can be used, which can include but is not limited to at least one of copper nitrate, copper sulfate and copper chloride. Preferably, the copper source is copper nitrate.

[0038] According to the present application, in the preparation method of the copper-containing catalyst, the substance of the zinc source is limited to be wide, and a conventional soluble zinc salt can be used, which can include but is not limited to at least one of zinc nitrate, zinc sulfate and zinc chloride. Preferably, the zinc source can be zinc nitrate.

[0039] According to the present application, in the preparation method of the copper-containing catalyst, the substance of the nickel source is limited to be wide, and a conventional soluble nickel salt can be used, which can include but is not limited to at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel bicarbonate. Preferably, the nickel source is nickel nitrate.

[0040] According to the present application, in the preparation method of the copper-containing catalyst, the solution containing the aluminum source and the magnesium source can be prepared by dissolving the aluminum source and the magnesium source in a first solvent. Preferably, in the solution containing the aluminum source and the magnesium source, the total molar concentration of Mg 2+ and Al 3+ is 1-3 mol / L.

[0041] According to the present application, in the preparation method of the copper-containing catalyst, the solution containing the copper source, the zinc source and the nickel source can be prepared by dissolving the copper source, the zinc source and the nickel source in a second solvent. Preferably, in the solution containing the copper source, the zinc source and the nickel source, the total molar concentration of Cu 2+ , Zn 2+ and Ni2+ The total molar concentration of the copper-containing catalyst is 1-1.5 mol / L.

[0042] According to the present application, in the preparation method of the copper-containing catalyst, the first precipitant and the second precipitant are preferably fed in the form of a solution, and the first precipitant and the second precipitant can be respectively prepared into a precipitant solution with the third solvent before being fed.

[0043] According to the present application, the first solvent, the second solvent and the third solvent each have a wide selection range, and can be water, alcohol or an alcohol-water mixture, preferably an ethanol aqueous solution with a concentration of 40-60 wt%, but are not limited thereto. In the present application, the first solvent, the second solvent and the third solvent can be the same or different, and are preferably the same.

[0044] According to the present application, in the preparation method of the copper-containing catalyst, the feeding amount of the aluminum source, the magnesium source, the copper source, the zinc source, the nickel source and the organosilane modifier satisfies the molar ratio of the aluminum source in terms of aluminum element: the magnesium source in terms of magnesium element: the copper source in terms of copper element: the zinc source in terms of zinc element: the nickel source in terms of nickel element: the organosilane modifier in terms of silicon element is (0.2-1.2):(0.05-0.5):1:(0.6-3.9):(0.1-1):(0.3-0.65).

[0045] According to the present application, in the preparation method of the copper-containing catalyst, the feeding amount of the aluminum source, the magnesium source, the copper source, the zinc source, the nickel source and the organosilane modifier satisfies the molar ratio of the aluminum source in terms of aluminum element: the magnesium source in terms of magnesium element: the copper source in terms of copper element: the zinc source in terms of zinc element: the nickel source in terms of nickel element: the organosilane modifier in terms of silicon element is (0.2-1.2):(0.05-0.5):1:(0.6-3.9):(0.1-1):(0.3-0.65).

[0046] According to the present application, in the preparation method of the copper-containing catalyst, the feeding amount of the aluminum source, the magnesium source, the copper source, the zinc source, the nickel source and the organosilane modifier satisfies the molar ratio of the aluminum source in terms of aluminum element: the magnesium source in terms of magnesium element: the copper source in terms of copper element: the zinc source in terms of zinc element: the nickel source in terms of nickel element: the organosilane modifier in terms of silicon element is (0.2-1.2):(0.05-0.5):1:(0.6-3.9):(0.1-1):(0.3-0.65).

[0047] According to the present application, in the preparation method of the copper-containing catalyst, in step (1), the first reaction can be carried out by mixing the solution containing the aluminum source and the magnesium source with the first precipitant. In the first reaction, magnesium ions and aluminum ions form magnesium-aluminum crystal nuclei to obtain a first product system. The conditions of the first reaction include: the pH value of the reaction system is ≥9, preferably 9-9.5; and the reaction temperature is 80-90°C, preferably 85-90°C.

[0048] According to the present application, in the preparation method of the copper-containing catalyst, in step (2), the second reaction can be carried out by mixing the solution of the copper-containing source, the zinc source and the nickel source, the second precipitant and the first product system. In the second reaction, the co-precipitation of copper, zinc and nickel is carried out with the magnesium-aluminum crystal nucleus as the precipitation center, to obtain a second product system. The conditions of the second reaction include: the pH value of the reaction system is ≥7, preferably 7.5-7.8; the reaction temperature is 80-90℃, preferably 85-90℃.

[0049] According to the present application, in the preparation method of the copper-containing catalyst, in step (3), the third reaction can be carried out by mixing the second product system with the organosilane modifier. Through the third reaction, a hydrophobic silicon layer is formed on the surface of the second reaction product, to obtain a third product system. The conditions of the third reaction include: the reaction temperature is 80-95℃, preferably 80-90℃, and the reaction time is 10-40min, preferably 20-30min.

[0050] According to the present application, in the preparation method of the copper-containing catalyst, in step (3), the separation treatment includes evaporating and condensing the third product system until the product gel is obtained, and collecting and recycling the solvent obtained by condensation.

[0051] According to the present application, in the preparation method of the copper-containing catalyst, in step (4), before the calcination, the gel is preferably subjected to a drying treatment.

[0052] According to the present application, in the preparation method of the copper-containing catalyst, in step (4), through the calcination, the gel is converted into an oxide, and the salt and water in the gel are removed, to obtain the black powder as the copper-containing catalyst. The conditions of the calcination include: the calcination is carried out in an air or oxygen atmosphere, the calcination temperature is 350-400℃, and the calcination time is 180-360min.

[0053] According to the present application, in the preparation method of the copper-containing catalyst, in step (4), the calcination product (i.e. the black powder) obtained after the calcination can be directly used as the catalyst product. In addition, preferably, the calcination product can be mixed with graphite, and then subjected to a tabletting and forming treatment, to obtain the formed product as the catalyst product. In this way, the copper component in the catalyst product obtained in this way has good dispersity and higher mechanical strength. Preferably, the weight ratio of the calcination product to graphite is 1:(0.01-0.05).

[0054] The second aspect of the present application provides a copper-containing catalyst prepared by the preparation method of the first aspect.

[0055] According to the present application, the copper-containing catalyst prepared by the preparation method has a specific chemical composition, and the copper-containing catalyst comprises copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide and silicon dioxide, wherein the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide is 100:(66-400):(10-75):(3-25):(20-86):(24-47).

[0056] Preferably, the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide is 100:(120-260):(20-34):(3-17):(24-27):(25-45).

[0057] According to the present application, the copper-containing catalyst prepared by the preparation method meets the specific chemical composition described above, and has a high specific surface area, pore volume and average pore diameter, specifically, the specific surface area of the catalyst is ≥55m 2 / g, the pore volume is ≥0.34mL / g, and the average pore diameter is ≥16nm, while the catalyst has a magnesium-aluminum spinel structure and a surface hydrophobic silicon component. By constructing a magnesium-aluminum spinel structure, the high-temperature stability of the catalyst can be improved, by introducing a hydrophobic silicon component on the surface of the catalyst, the immersion resistance of the catalyst can be improved, the pulverization of the catalyst during use and the loss of catalyst components can be reduced, the service life of the catalyst at high temperature can be prolonged, and under the synergistic action of the components in the catalyst and the large catalyst pore diameter, the selective adsorption of the catalyst to the reaction raw material (aldehyde or ester) molecules can be improved, the occurrence of side reactions can be reduced, and the selectivity of the hydrogenation product can be improved.

[0058] In the present application, the specific surface area of the catalyst is determined by the method specified in “GB / T 19587 Gas Adsorption BET Method for Determining Specific Surface Area of Solid Substances”.

[0059] In the present application, the pore volume and average pore diameter of the catalyst are determined by the method specified in “GB / T 21650.2 Mercury Intrusion Method and Gas Adsorption Method for Determining Pore Size Distribution and Porosity of Solid Materials Part 2: Gas Adsorption Method for Analysis of Mesopores and Macropores”.

[0060] The third aspect of the present application provides the use of the copper-containing catalyst of the second aspect in an aldehyde hydrogenation reaction or an ester hydrogenation reaction.

[0061] According to the present application, the copper-containing catalyst provided by the present application can be used as a hydrogenation catalyst for the liquid-phase hydrogenation of aldehydes or esters. The catalyst has excellent stability under high-temperature reaction conditions (100-200℃), the effective components are not easily lost, the service life is long, and excellent hydrogenation activity and product selectivity can be achieved.

[0062] According to the present application, the aldehyde is preferably a C4-C10 Aldehydes, such as butyraldehyde, 2-ethyl-2-hexanal, 2-propyl-2-heptenal, hydroxyneopental, isodecanal, etc.

[0063] According to the present invention, the ester is preferably C4-C. 10 Esters, such as dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, ethylene carbonate, acetate, etc.

[0064] The present invention will be described in detail below through examples. Unless otherwise specified, the following examples and comparative examples are all conventional methods; the reagents and materials used are commercially available unless otherwise specified.

[0065] Example 1

[0066] (1) A solution containing aluminum and magnesium sources (aluminum nitrate, magnesium nitrate, and a 50% by weight ethanol solution) is obtained by thoroughly mixing the two sources. 3+ and Mg 2+ The total molar concentration of the mixture was 2 mol / L and preheated to 90°C. The mixture was added to the reactor in a parallel flow with an ammonium oxalate solution (ammonium oxalate was thoroughly mixed with a 50% by weight ethanol solution and preheated to 90°C) to carry out the first reaction (the pH of the reaction system was controlled at 9.0-9.5 and the reaction temperature was 90°C) to obtain the first product system.

[0067] (2) A solution containing copper, zinc, and nickel sources (copper nitrate, zinc nitrate, nickel nitrate, and a 50% by weight ethanol solution) is obtained by thoroughly mixing the solutions. 2+ Zn 2+ and Ni 2+ The total molar concentration is 1.5 mol / L and preheated to 90°C), ammonium oxalate solution (ammonium oxalate and 50% by weight ethanol solution are thoroughly mixed and preheated to 90°C) are added to the reaction vessel of step (1) to carry out a second reaction with the first product system (the pH of the reaction system is controlled at 7.5-7.8 and the reaction temperature is 90°C) to obtain the second product system;

[0068] (3) Add methyl orthosilicate to the above second product system, stir at 90°C for 30 min to carry out the third reaction, and obtain the third product system;

[0069] The above third product system was subjected to evaporation and condensation treatment until a product gel was obtained, and the ethanol and water mixture obtained during the condensation process was collected and recovered.

[0070] The molar ratio of the aluminum nitrate (calculated as aluminum element) : the magnesium nitrate (calculated as magnesium element) : the copper nitrate (calculated as copper element) : the zinc nitrate (calculated as zinc element) : the nickel nitrate (calculated as nickel element) : the tetramethyl orthosilicate (calculated as silicon element) in the above raw materials is 0.46:0.12:1:1.92:0.26:0.5;

[0071] (4) The gel of the above product is dried, and then calcined at 380°C for 240 min in an air atmosphere to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1:0.02, and then tablet-shaped molding is performed to obtain a catalyst (denoted as CAT-1).

[0072] The composition of the catalyst CAT-1 includes copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, and the weight ratio of the copper oxide: the zinc oxide: the aluminum oxide: the magnesium oxide: the nickel oxide: the silicon dioxide: the graphite is 100:197:30:6:25:38:8.

[0073] The specific surface area, pore volume and pore size of the catalyst CAT-1 are shown in Table 1.

[0074] Example 2

[0075] (1) A solution containing aluminum and magnesium sources (aluminum nitrate and magnesium nitrate are fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, wherein the total molar concentration of Al 3+ and Mg 2+ is 2 mol / L, and is preheated to 90°C) is added into a reaction kettle together with an ammonium oxalate solution (ammonium oxalate is fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and is preheated to 90°C) to perform a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C) to obtain a first product system;

[0076] (2) A solution containing copper, zinc and nickel sources (copper nitrate, zinc nitrate and nickel nitrate are fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, wherein the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ is 1.5 mol / L, and is preheated to 90°C), an ammonium oxalate solution (ammonium oxalate is fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and is preheated to 90°C) are added into the reaction kettle of step (1) to perform a second reaction with the above first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C) to obtain a second product system;

[0077] (3) Tetramethyl orthosilicate is added into the above second product system, and a third reaction is performed at 90°C for 30 min to obtain a third product system;

[0078] The third product system is subjected to evaporation and condensation until a product gel is obtained, and the mixture of ethanol and water condensed in the process is collected and recovered;

[0079] The molar ratio of the aluminum nitrate (calculated as aluminum element) : magnesium nitrate (calculated as magnesium element) : copper nitrate (calculated as copper element) : zinc nitrate (calculated as zinc element) : nickel nitrate (calculated as nickel element) : tetramethyl orthosilicate (calculated as silicon element) in the above raw materials is 0.39:0.06:1:2.53:0.26:0.6;

[0080] (4) The product gel is dried, and then calcined at 380°C for 240 min in an air atmosphere to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1:0.02, and then tablet-pressed to obtain a catalyst (denoted as CAT-2).

[0081] The composition of the catalyst CAT-2 includes copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, and the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:259:25:17:25:45:9.

[0082] The specific surface area, pore volume and pore size of the catalyst CAT-2 are shown in Table 1.

[0083] Example 3

[0084] (1) A solution containing aluminum and magnesium sources (aluminum nitrate and magnesium nitrate are fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and the total molar concentration of Al 3+ and Mg 2+ is 2 mol / L, and the solution is preheated to 85°C) is added into a reaction kettle together with an ammonium oxalate solution (ammonium oxalate is fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and the solution is preheated to 85°C) to perform a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 85°C), to obtain a first product system;

[0085] (2) A solution containing copper, zinc and nickel sources (copper nitrate, zinc nitrate and nickel nitrate are fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ is 1.5 mol / L, and the solution is preheated to 85°C), an ammonium oxalate solution (ammonium oxalate is fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and the solution is preheated to 85°C) are added into the reaction kettle of step (1) to perform a second reaction with the above first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 85°C), to obtain a second product system;

[0086] (3) adding tetramethyl orthosilicate into the above-mentioned second product system, stirring at 85℃ for 30min to carry out a third reaction, and obtaining a third product system;

[0087] carrying out evaporation and condensation treatment on the above-mentioned third product system until a product gel is obtained, and collecting and recycling the mixed solution of ethanol and water obtained by condensation in the process;

[0088] In the above-mentioned raw materials, the molar ratio of aluminum nitrate calculated by aluminum element, magnesium nitrate calculated by magnesium element, copper nitrate calculated by copper element, zinc nitrate calculated by zinc element, nickel nitrate calculated by nickel element, and tetramethyl orthosilicate calculated by silicon element is 0.52:0.06:1:1.39:0.28:0.34;

[0089] (4) drying the above-mentioned product gel, and then calcining in air atmosphere at 380℃ for 240min to obtain a black powder, mixing the black powder with graphite according to a weight ratio of 1:0.02, and then carrying out tabletting forming treatment to obtain a catalyst (denoted as CAT-3).

[0090] The composition of the catalyst CAT-3 includes copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide, and graphite, wherein the weight ratio of copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide, and graphite is 100:142:34:3:27:26:7.

[0091] The specific surface area, pore volume, and pore size test results of the catalyst CAT-3 are shown in Table 1.

[0092] Example 4

[0093] (1) adding a solution containing aluminum source and magnesium source (aluminum nitrate, magnesium nitrate, and 50wt% ethanol solution are fully mixed to obtain, wherein the total molar concentration of Al 3+ and Mg 2+ is 2mol / L, and preheated to 90℃) and ammonium oxalate solution (ammonium oxalate and 50wt% ethanol solution are fully mixed to obtain, and preheated to 90℃) into the reaction kettle in parallel flow to carry out a first reaction (controlling the pH value of the reaction system to be 9.0-9.5, and the reaction temperature to be 90℃), and obtaining a first product system;

[0094] (2) adding a solution containing copper source, zinc source, and nickel source (copper nitrate, zinc nitrate, and nickel nitrate are fully mixed with 50wt% ethanol solution to obtain, wherein the total molar concentration of Cu 2+ , Zn 2+ , and Ni 2+The total molar concentration of the aluminum nitrate, the magnesium nitrate, the copper nitrate, the zinc nitrate, the nickel nitrate and the methyl orthosilicate is 1.5 mol / L, and the solution is preheated to 90°C. The ammonium oxalate solution is obtained by mixing ammonium oxalate and an ethanol solution with a concentration of 50% by weight, and is preheated to 90°C. The solution and the ammonium oxalate solution are added into the reactor of step (1) in parallel flow to react with the first product system to obtain a second product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C);

[0095] (3) The methyl orthosilicate is added into the second product system, and a third reaction is carried out at 90°C for 30 min to obtain a third product system;

[0096] The third product system is subjected to evaporation and condensation treatment until a product gel is obtained, and the mixture of ethanol and water obtained by condensation in the process is collected and recovered.

[0097] In the above raw materials, the molar ratio of the aluminum nitrate (calculated by aluminum element) : the magnesium nitrate (calculated by magnesium element) : the copper nitrate (calculated by copper element) : the zinc nitrate (calculated by zinc element) : the nickel nitrate (calculated by nickel element) : the methyl orthosilicate (calculated by silicon element) is 0.31:0.09:1:1.2:0.27:0.41.

[0098] (4) The product gel is dried, and then calcined in an air atmosphere at 380°C for 240 min to obtain a black powder. The black powder and graphite are mixed according to a weight ratio of 1:0.02, and then tablet molding treatment is carried out to obtain a catalyst (denoted as CAT-4).

[0099] The composition of the catalyst CAT-4: copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, and the weight ratio of the copper oxide: the zinc oxide: the aluminum oxide: the magnesium oxide: the nickel oxide: the silicon dioxide: the graphite is 100:123:20:5:25:31:6.

[0100] The specific surface area, the pore volume and the pore size of the catalyst CAT-4 are shown in Table 1.

[0101] Example 5

[0102] (1) A solution containing an aluminum source and a magnesium source (aluminum nitrate, magnesium nitrate and an ethanol solution with a concentration of 50% by weight are mixed to obtain a solution, and the total molar concentration of Al 3+ and Mg 2+ is 2 mol / L, and the solution is preheated to 90°C) and an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight are mixed to obtain a solution, and the solution is preheated to 90°C) are added into a reactor in parallel flow to carry out a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C) to obtain a first product system.

[0103] (2) The solution containing copper source, zinc source and nickel source (copper nitrate, zinc nitrate, nickel nitrate and 50 wt% ethanol solution are mixed to obtain a solution, in which the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ is 1.5 mol / L, and the solution is preheated to 90°C), ammonium oxalate solution (the precipitant and 50 wt% ethanol solution are mixed to obtain a solution, which is preheated to 90°C) are added into the reactor of step (1) to react with the first product system to obtain a second product system, in which the pH value of the reaction system is controlled to be 7.5-7.8 and the reaction temperature is 90°C;

[0104] (3) The methyl orthosilicate is added into the second product system, and the third reaction is carried out at 90°C for 30 min to obtain a third product system;

[0105] The third product system is subjected to evaporation and condensation treatment until the product gel is obtained, and the mixture of ethanol and water obtained by condensation in the process is collected and recovered;

[0106] In the above raw materials, the molar ratio of aluminum nitrate (calculated by aluminum element) : magnesium nitrate (calculated by magnesium element) : copper nitrate (calculated by copper element) : zinc nitrate (calculated by zinc element) : nickel nitrate (calculated by nickel element) : methyl orthosilicate organosilane modifier (calculated by silicon element) is 0.47:0.49:1:2.23:0.22:0.62;

[0107] (4) The product gel is dried, and then calcined in air atmosphere at 380°C for 240 min to obtain a black powder. The black powder and graphite are mixed according to a weight ratio of 1:0.02, and then tablet molding treatment is carried out to obtain a catalyst (denoted as CAT-5).

[0108] The composition of the catalyst CAT-5 includes copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, and the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:228:30:25:20:47:9.

[0109] The specific surface area, pore volume and pore size of the catalyst CAT-5 are shown in Table 1.

[0110] Example 6

[0111] (1) The solution containing aluminum source and magnesium source (aluminum nitrate, magnesium nitrate and 50 wt% ethanol solution are mixed to obtain a solution, in which the total molar concentration of Al 3+ and Mg 2+The first product system was obtained by adding the solution of the copper source, the zinc source and the nickel source (nitric acid copper, nitric acid zinc and nitric acid nickel were mixed with an ethanol solution with a concentration of 50% by weight to obtain a solution, and the solution was preheated to 90°C) and the ammonium oxalate solution (ammonium oxalate was mixed with an ethanol solution with a concentration of 50% by weight to obtain a solution, and the solution was preheated to 90°C) into the reactor in parallel and performing a first reaction (the pH value of the reaction system was controlled to be 9.0-9.5, and the reaction temperature was 90°C) ;

[0112] (2) The solution containing the copper source, the zinc source and the nickel source (nitric acid copper, nitric acid zinc and nitric acid nickel were mixed with an ethanol solution with a concentration of 50% by weight to obtain a solution, and the solution was preheated to 90°C, wherein the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ was 1.5 mol / L) was added into the reactor in step (1) in parallel with the ammonium oxalate solution (ammonium oxalate was mixed with an ethanol solution with a concentration of 50% by weight to obtain a solution, and the solution was preheated to 90°C) to perform a second reaction with the first product system (the pH value of the reaction system was controlled to be 7.5-7.8, and the reaction temperature was 90°C) to obtain a second product system;

[0113] (3) The methyl orthosilicate was added into the second product system, and a third reaction was performed at 90°C for 30 min to obtain a third product system;

[0114] The third product system was subjected to evaporation and condensation treatment until a product gel was obtained, and the mixed solution of ethanol and water obtained in the process was collected and recovered;

[0115] In the above raw materials, the molar ratio of aluminum nitrate (calculated by aluminum element) : magnesium nitrate (calculated by magnesium element) : copper nitrate (calculated by copper element) : zinc nitrate (calculated by zinc element) : nickel nitrate (calculated by nickel element) : methyl orthosilicate (calculated by silicon element) was 0.22:0.14:1:1.71:0.25:0.4;

[0116] (4) The product gel was dried, and then calcined at 380°C in an air atmosphere for 240 min to obtain a black powder. The black powder was mixed with graphite at a weight ratio of 1:0.02, and then tablet molding treatment was performed to obtain a catalyst (denoted as CAT-6).

[0117] The composition of the catalyst CAT-6: copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, wherein the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite was 100:175:14:7:23:30:7.

[0118] The specific surface area, pore volume and pore size test results of the catalyst CAT-1 are shown in Table 6.

[0119] Example 7

[0120] (1) A solution containing an aluminum source and a magnesium source (aluminum nitrate, magnesium nitrate, and an ethanol solution with a concentration of 50% by weight are mixed thoroughly to obtain a solution, wherein the total molar concentration of Al 3+ and Mg 2+ is 2 mol / L, and the solution is preheated to 90°C) is added to a reaction kettle in parallel with an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight are mixed thoroughly to obtain a solution, and the solution is preheated to 90°C) to perform a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C) to obtain a first product system;

[0121] (2) A solution containing a copper source, a zinc source, and a nickel source (copper nitrate, zinc nitrate, and nickel nitrate are mixed thoroughly with an ethanol solution with a concentration of 50% by weight to obtain a solution, wherein the total molar concentration of Cu 2+ , Zn 2+ , and Ni 2+ is 1.5 mol / L, and the solution is preheated to 90°C), an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight are mixed thoroughly to obtain a solution, and the solution is preheated to 90°C) are added to the reaction kettle in step (1) in parallel with the above first product system to perform a second reaction (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C) to obtain a second product system;

[0122] (3) Tetramethyl orthosilicate is added to the above second product system, and a third reaction is performed at 90°C for 30 min to obtain a third product system;

[0123] The above third product system is subjected to evaporation and condensation treatment until a product gel is obtained, and the mixture of ethanol and water obtained by condensation in the process is collected and recovered;

[0124] In the above raw materials, the molar ratio of aluminum nitrate (calculated based on the aluminum element) : magnesium nitrate (calculated based on the magnesium element) : copper nitrate (calculated based on the copper element) : zinc nitrate (calculated based on the zinc element) : nickel nitrate (calculated based on the nickel element) : tetramethyl orthosilicate (calculated based on the silicon element) is 0.58:0.09:1:0.65:0.22:0.32;

[0125] (4) The above product gel is dried, and then calcined at 380°C in an air atmosphere for 240 min to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1:0.02, and then tablet molding treatment is performed to obtain a catalyst (denoted as CAT-7).

[0126] The composition of the catalyst CAT-7: copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide, and graphite, wherein the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:66:37:5:20:24:5.

[0127] The specific surface area, pore volume and pore diameter of the catalyst CAT-7 were tested, and the results are shown in Table 1.

[0128] Example 8

[0129] (1) A solution containing aluminum and magnesium sources (aluminum nitrate, magnesium nitrate, and an ethanol solution with a concentration of 50% by weight were mixed to obtain a solution, wherein the total molar concentration of Al 3+ and Mg 2+ was 2 mol / L, and the solution was preheated to 90°C) was added into a reaction kettle together with an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight were mixed to obtain a solution, and the solution was preheated to 90°C) to perform a first reaction (the pH value of the reaction system was controlled to be 9.0-9.5, and the reaction temperature was 90°C), to obtain a first product system;

[0130] (2) A solution containing copper, zinc and nickel sources (copper nitrate, zinc nitrate, nickel nitrate, and an ethanol solution with a concentration of 50% by weight were mixed to obtain a solution, wherein the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ was 1.5 mol / L, and the solution was preheated to 90°C), an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight were mixed to obtain a solution, and the solution was preheated to 90°C) were added into the reaction kettle of step (1) to perform a second reaction with the above-mentioned first product system (the pH value of the reaction system was controlled to be 7.5-7.8, and the reaction temperature was 90°C), to obtain a second product system;

[0131] (3) Tetramethyl orthosilicate was added into the above-mentioned second product system, and a third reaction was performed at 90°C for 30 min, to obtain a third product system;

[0132] The above-mentioned third product system was subjected to evaporation and condensation treatment until a product gel was obtained, and the mixed solution of ethanol and water obtained by condensation in the process was collected and recovered;

[0133] In the above-mentioned raw materials, the molar ratio of aluminum nitrate (calculated based on the aluminum element) : magnesium nitrate (calculated based on the magnesium element) : copper nitrate (calculated based on the copper element) : zinc nitrate (calculated based on the zinc element) : nickel nitrate (calculated based on the nickel element) : tetramethyl orthosilicate (calculated based on the silicon element) was 1.16:0.19:1:3.85:0.91:0.48;

[0134] (4) The above-mentioned product gel was dried, and then calcined in an air atmosphere at 380°C for 240 min to obtain a black powder. The black powder was mixed with graphite according to a weight ratio of 1:0.02, and then tablet molding treatment was performed, to obtain a catalyst (denoted as CAT-8).

[0135] The composition of the catalyst CAT-8: copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, wherein the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:399:74:10:86:36:14.

[0136] The specific surface area, pore volume and pore size of the catalyst CAT-8 are shown in Table 1.

[0137] Example 9

[0138] (1) A solution containing aluminum and magnesium sources (aluminum nitrate, magnesium nitrate and an ethanol solution with a concentration of 50% by weight are mixed to obtain a solution, wherein the total molar concentration of Al 3+ and Mg 2+ is 1 mol / L, and the solution is preheated to 90°C) and an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight are mixed to obtain a solution, and the solution is preheated to 90°C) are added into a reaction kettle in parallel flow to carry out a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C), to obtain a first product system;

[0139] (2) A solution containing copper, zinc and nickel sources (copper nitrate, zinc nitrate, nickel nitrate and an ethanol solution with a concentration of 50% by weight are mixed to obtain a solution, wherein the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ is 1 mol / L, and the solution is preheated to 90°C), an ammonium oxalate solution (ammonium oxalate and an ethanol solution with a concentration of 50% by weight are mixed to obtain a solution, and the solution is preheated to 90°C) are added into the reaction kettle of step (1) in parallel flow to carry out a second reaction with the above-mentioned first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C), to obtain a second product system;

[0140] (3) Tetramethyl orthosilicate is added into the above-mentioned second product system, and a third reaction is carried out at 80°C for 40 min to obtain a third product system;

[0141] The above-mentioned third product system is subjected to evaporation and condensation treatment until a product gel is obtained, and the mixture of ethanol and water obtained by condensation in the process is collected and recovered;

[0142] In the above-mentioned raw materials, the molar ratio of aluminum nitrate (calculated based on the aluminum element): magnesium nitrate (calculated based on the magnesium element): copper nitrate (calculated based on the copper element): zinc nitrate (calculated based on the zinc element): nickel nitrate (calculated based on the nickel element): tetramethyl orthosilicate (calculated based on the silicon element) is 1.07:0.63:1:2.71:0.62:0.4;

[0143] (4) The product gel is dried, and then calcined at 380°C for 240 minutes in an air atmosphere to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1:0.02, and then tablet-pressed to form a catalyst (referred to as CAT-9).

[0144] The composition of the catalyst CAT-9: copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide, and graphite, wherein the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:277:69:32:59:30:11.

[0145] The specific surface area, pore volume, and pore size of the catalyst CAT-9 are shown in Table 1.

[0146] Comparative Example 1

[0147] (1) A solution containing aluminum and magnesium sources (aluminum nitrate and magnesium nitrate are thoroughly mixed with an ethanol solution having a concentration of 50% by weight, wherein the total molar concentration of Al 3+ and Mg 2+ is 2 mol / L, and is preheated to 90°C) is added to a reaction kettle in parallel flow with an ammonium oxalate solution (ammonium oxalate is thoroughly mixed with an ethanol solution having a concentration of 50% by weight, and is preheated to 90°C) to perform a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C) to obtain a first product system;

[0148] (2) A solution containing copper, zinc, and nickel sources (copper nitrate, zinc nitrate, and nickel nitrate are thoroughly mixed with an ethanol solution having a concentration of 50% by weight, wherein the total molar concentration of Cu 2+ , Zn 2+ , and Ni 2+ is 1.5 mol / L, and is preheated to 90°C), an ammonium oxalate solution (ammonium oxalate is thoroughly mixed with an ethanol solution having a concentration of 50% by weight, and is preheated to 90°C) are added to the reaction kettle of step (1) in parallel flow to perform a second reaction with the first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C) to obtain a second product system;

[0149] The second product system is subjected to evaporation and condensation treatment until a product gel is obtained, and the mixed solution of ethanol and water obtained by condensation in this process is collected and recovered;

[0150] In the above raw materials, the molar ratio of aluminum nitrate (calculated based on the aluminum element): magnesium nitrate (calculated based on the magnesium element): copper nitrate (calculated based on the copper element): zinc nitrate (calculated based on the zinc element): nickel nitrate (calculated based on the nickel element) is 0.46:0.12:1:1.92:0.26;

[0151] (3) The product gel is dried, and then calcined at 380°C for 240 min in an air atmosphere to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1 :0.02, and then tablet-pressed to form a catalyst (referred to as DCAT-1).

[0152] The composition of the catalyst DCAT-1 includes copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide, and graphite, and the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: graphite is 100:197:30:6:25:7.

[0153] The specific surface area, pore volume, and pore size of the catalyst DCAT-1 are shown in Table 1.

[0154] Comparative Example 2

[0155] (1) A solution containing a magnesium source (obtained by thoroughly mixing magnesium nitrate with an ethanol solution having a concentration of 50% by weight, wherein the total molar concentration of Mg 2+ is 2 mol / L, and preheated to 90°C) and an ammonium oxalate solution (obtained by thoroughly mixing ammonium oxalate with an ethanol solution having a concentration of 50% by weight, and preheated to 90°C) are added into a reaction kettle in a concurrent manner to perform a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C) to obtain a first product system;

[0156] (2) A solution containing a copper source, a zinc source, and a nickel source (obtained by thoroughly mixing copper nitrate, zinc nitrate, and nickel nitrate with an ethanol solution having a concentration of 50% by weight, wherein the total molar concentration of Cu 2+ , Zn 2+ , and Ni 2+ is 1.5 mol / L, and preheated to 90°C), an ammonium oxalate solution (obtained by thoroughly mixing ammonium oxalate with an ethanol solution having a concentration of 50% by weight, and preheated to 90°C) are added into the reaction kettle of step (1) in a concurrent manner to perform a second reaction with the first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C) to obtain a second product system;

[0157] (3) Methyl orthosilicate is added into the second product system, and a third reaction is performed by stirring at 90°C for 30 min to obtain a third product system;

[0158] The third product system is subjected to evaporation and condensation treatment until a product gel is obtained, and the mixture of ethanol and water obtained by condensation in the process is collected and recovered;

[0159] The molar ratio of magnesium nitrate (calculated as magnesium element) : copper nitrate (calculated as copper element) : zinc nitrate (calculated as zinc element) : nickel nitrate (calculated as nickel element) : methyl orthosilicate (calculated as silicon element) in the above raw materials is 0.12:1:1.92:0.26:0.5.

[0160] (4) The gel of the above product is dried, and then calcined at 380°C for 240 min in an air atmosphere to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1:0.02, and then tablet-shaped into a catalyst (denoted as DCAT-2).

[0161] The composition of the catalyst DCAT-2 includes copper oxide, zinc oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, and the weight ratio of copper oxide: zinc oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:197:6:25:38:7.3.

[0162] The test results of the specific surface area, pore volume and pore size of the catalyst DCAT-2 are shown in Table 1.

[0163] Comparative Example 3

[0164] (1) A solution containing an aluminum source (obtained by thoroughly mixing aluminum nitrate with an ethanol solution having a concentration of 50% by weight, wherein the total molar concentration of Al 3+ is 2 mol / L, and preheated to 90°C) and an ammonium oxalate solution (obtained by thoroughly mixing ammonium oxalate with an ethanol solution having a concentration of 50% by weight, and preheated to 90°C) are added into a reaction kettle in parallel flow to carry out a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C) to obtain a first product system;

[0165] (2) A solution containing a copper source, a zinc source and a nickel source (obtained by thoroughly mixing copper nitrate, zinc nitrate, nickel nitrate with an ethanol solution having a concentration of 50% by weight, wherein the total molar concentration of Cu 2+ , Zn 2+ and Ni 2+ is 1.5 mol / L, and preheated to 90°C), an ammonium oxalate solution (obtained by thoroughly mixing ammonium oxalate with an ethanol solution having a concentration of 50% by weight, and preheated to 90°C) are added into the reaction kettle of step (1) in parallel flow to carry out a second reaction with the above first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C) to obtain a second product system;

[0166] (3) Methyl orthosilicate is added into the above second product system, and a third reaction is carried out at 90°C for 30 min to obtain a third product system;

[0167] The third product system is subjected to evaporation and condensation until a product gel is obtained, and the mixture of ethanol and water condensed in the process is collected and recovered;

[0168] The molar ratio of the aluminum nitrate (calculated based on the aluminum element) : copper nitrate (calculated based on the copper element) : zinc nitrate (calculated based on the zinc element) : nickel nitrate (calculated based on the nickel element) : tetramethyl orthosilicate (calculated based on the silicon element) in the raw material is 0.46:1:1.92:0.26:0.5;

[0169] (4) The product gel is dried, and then calcined at 380°C in an air atmosphere for 240 min to obtain a black powder. The black powder is mixed with graphite at a weight ratio of 1:0.02, and then tablet-shaped into a catalyst (denoted as DCAT-3).

[0170] The composition of the catalyst DCAT-3 includes copper oxide, zinc oxide, aluminum oxide, nickel oxide, silicon dioxide, and graphite, and the weight ratio of copper oxide: zinc oxide: aluminum oxide: nickel oxide: silicon dioxide: graphite is 100:197:30:25:38:8.

[0171] The specific surface area, pore volume, and pore size of the catalyst DCAT-3 are shown in Table 1.

[0172] Comparative Example 4

[0173] (1) A solution containing an aluminum source and a magnesium source (aluminum nitrate and magnesium nitrate are fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, wherein the total molar concentration of Al 3+ and Mg 2+ is 2 mol / L, and preheated to 90°C) is added into a reaction kettle together with an ammonium oxalate solution (ammonium oxalate is fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and preheated to 90°C) to perform a first reaction (the pH value of the reaction system is controlled to be 9.0-9.5, and the reaction temperature is 90°C), to obtain a first product system;

[0174] (2) A solution containing a copper source and a nickel source (copper nitrate and nickel nitrate are fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, wherein the total molar concentration of Cu 2+ and Ni 2+ is 1.5 mol / L, and preheated to 90°C), an ammonium oxalate solution (ammonium oxalate is fully mixed with an ethanol solution with a concentration of 50% by weight to obtain, and preheated to 90°C) are added into the reaction kettle of step (1) to perform a second reaction with the first product system (the pH value of the reaction system is controlled to be 7.5-7.8, and the reaction temperature is 90°C), to obtain a second product system;

[0175] (3) adding tetramethyl orthosilicate into the second product system, stirring at 90℃ for 30 minutes to obtain a third product system;

[0176] The third product system is evaporated and condensed until a product gel is obtained, and the mixture of ethanol and water condensed in the process is collected and recovered;

[0177] In the above raw materials, the molar ratio of aluminum nitrate (calculated by aluminum element) : magnesium nitrate (calculated by magnesium element) : copper nitrate (calculated by copper element) : nickel nitrate (calculated by nickel element) : tetramethyl orthosilicate (calculated by silicon element) is 0.46:0.12:1:0.26:0.5;

[0178] (4) drying the product gel, and then calcining at 380℃ in an air atmosphere for 240 minutes to obtain a black powder, mixing the black powder with graphite according to a weight ratio of 1:0.02, and then performing tabletting forming treatment to obtain a catalyst (denoted as DCAT-4).

[0179] The composition of the catalyst DCAT-4 includes copper oxide, aluminum oxide, magnesium oxide, nickel oxide, silicon dioxide and graphite, wherein the weight ratio of copper oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide: graphite is 100:30:6:25:38:4.

[0180] The specific surface area, pore volume and pore size test results of the catalyst DCAT-4 are shown in Table 1.

[0181] Comparative Example 5

[0182] 7.6 g of copper nitrate trihydrate and 3.9 g of nickel nitrate hexahydrate were dissolved in 150 mL of deionized water at 25℃, concentrated ammonia was added until the pH value was 12, and then 17.0 g of a SiO2 carrier (Degussa AD Aerosil 380) was added, stirred, heated to 90℃ to evaporate ammonia until the pH value decreased to about 7. The obtained mixture was filtered, washed with deionized water for 3 times, dried at 120℃ overnight, and calcined at 800℃ for 4h to obtain a catalyst (denoted as DCAT-5).

[0183] The specific surface area, pore volume and pore size test results of the catalyst DCAT-5 are shown in Table 1.

[0184] Table 1

[0185] As can be seen from Table 1, the copper-containing catalyst prepared by the method of the present application has a large specific surface area, pore volume and average pore size, and the specific surface area is not less than 55m 2 / g, the pore volume is not less than 0.34 mL / g, and the average pore size is not less than 16 nm, so that the larger specific surface area can effectively improve the dispersion of the active metal phase copper, and the larger pore size is beneficial to the diffusion of reactants in the catalyst, thereby improving the hydrogenation efficiency.

[0186] Test Example

[0187] 1. Test of the immersion resistance of the catalyst

[0188] The catalysts CAT-1 to CAT-9 and DCAT-1 to DCAT-5 prepared in the above examples and comparative examples were respectively placed in an ethanol solution (containing 6% by weight of water) at 60℃ for immersion treatment for 48 h, and then taken out and dried, and the strength of the fresh catalyst before treatment and the catalyst after immersion treatment was respectively tested (the strength was measured according to the method specified in HG / T 2782, and the strength test was performed by using a ZQJ-II intelligent particle strength tester produced by Dalian Intelligent Tester Factory), and the decrease degree of the strength of the catalyst was calculated. The results are shown in Table 2.

[0189] The decrease degree of the strength of the catalyst was calculated according to the following formula: D = 100 x (N1-N2) / N1.

[0190] D is the decrease degree of the strength of the catalyst after immersion treatment, and the unit is %.

[0191] N1 is the strength of the fresh catalyst, and the unit is N / cm.

[0192] N2 is the strength of the catalyst after immersion treatment, and the unit is N / cm.

[0193] Table 2

[0194] As shown in Table 2, the strength decrease amplitude of the copper-containing catalyst prepared by the method of the present application after being immersed in an ethanol solution (containing 6% by weight of water) at 60℃ for 48 h is relatively low, which indicates that the copper-containing catalyst provided by the present application has excellent immersion resistance in a high water-containing system, and is beneficial to long-period operation.

[0195] 2. Test of the high-temperature stability of the catalyst

[0196] The catalysts CAT-1 to CAT-9 and DCAT-1 to DCAT-5 prepared in the above examples and comparative examples were respectively placed in a heating furnace for high-temperature treatment (the temperature was increased to 500℃ at a temperature increasing rate of 100℃ / h, and then kept constant for 30 h), and the specific surface area of the fresh catalyst before high-temperature treatment and the catalyst after high-temperature treatment, and the CuO grain size in the catalyst (the CuO grain size was obtained by XRD test and calculated by using the Debye-Scherrer formula) were respectively tested. The results are shown in Table 3.

[0197] Table 3

[0198] As shown in Table 3, after the high temperature treatment, the specific surface area of the copper-containing catalyst prepared by the method of the present application decreases at a lower rate, and the CuO grain size in the catalyst increases at a smaller rate, indicating that the copper-containing catalyst provided by the present application has excellent structural stability at high temperatures, and the melting and aggregation of CuO at high temperatures is significantly inhibited.

[0199] 3. Catalytic hydrogenation performance test of 2-propyl-2-heptenal

[0200] Catalysts CAT-1 to CAT-9 and DCAT-1 to DCAT-5 prepared by the above examples and comparative examples were respectively used to perform catalytic hydrogenation test of 2-propyl-2-heptenal, and the process was as follows:

[0201] Evaluation was performed on a 200 mL fixed-bed hydrogenation evaluation device. First, the catalyst was subjected to reduction treatment, and the reduction conditions were as follows: hydrogen reduction, reduction temperature was 400℃, reduction reaction time was 4h, and nitrogen was used to cool down after the reduction reaction was completed.

[0202] The hydrogenation performance evaluation conditions were as follows: the raw material was industrial 2-propyl-2-heptenal (purity > 95.5%), the reaction temperature was 150℃, the molar ratio of hydrogen to 2-propyl-2-heptenal was 30:1, the volume space velocity of 2-propyl-2-heptenal was 0.35h -1 , and the reaction pressure was 4.0 MPa. The results are shown in Table 4.

[0203] Table 4

[0204] As shown in Table 4, under the above reaction conditions, the copper-containing catalyst prepared by the method of the present application can realize 2-propyl-2-heptenal conversion rate of not less than 99.992% at a high temperature of 150℃, and at the same time, 2-propylheptanol selectivity of not less than 98.33% during the catalytic hydrogenation reaction of 2-propyl-2-heptenal, which has a comprehensive effect advantage in hydrogenation activity and product selectivity compared with the catalyst prepared by the comparative example.

[0205] 4. Catalytic hydrogenation performance test of dimethyl oxalate

[0206] Catalysts CAT-1 to CAT-9 and DCAT-1 to DCAT-5 prepared by the above examples and comparative examples were respectively used to perform catalytic hydrogenation test of dimethyl oxalate, and the process was as follows:

[0207] Evaluation was performed on a 200 mL fixed-bed hydrogenation evaluation device. First, the catalyst was subjected to reduction treatment, and the reduction conditions were as follows: hydrogen reduction, reduction temperature was 400℃, reduction reaction time was 4h, and nitrogen was used to cool down after the reduction reaction was completed.

[0208] The hydrogenation performance evaluation conditions are as follows: the raw material is industrial dimethyl oxalate (purity > 95%), the reaction temperature is 200℃, the molar ratio of hydrogen to dimethyl oxalate is 100:1, the volume space velocity of dimethyl oxalate is 0.5h-1, and the reaction pressure is 3.0MPa. The results are shown in Table 5. -1

[0209] Table 5

[0210] As can be seen from Table 5, under the above reaction conditions, the copper-containing catalyst prepared by the method of the present application can realize that the conversion rate of dimethyl oxalate is not less than 99.991% at a high temperature of 200℃, and the selectivity of ethylene glycol is not less than 96.29%, and compared with the catalyst prepared in the comparative example, the catalyst prepared by the method of the present application has an advantage in comprehensive effect in terms of hydrogenation activity and product selectivity.

[0211] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all belong to the protection scope of the present application.​

Claims

1. A process for the preparation of a copper-containing catalyst, characterized in that, The method comprises: (1) a first reaction of a solution containing an aluminum source and a magnesium source with a first precipitant to obtain a first product system; (2) a second reaction of a solution containing a copper source, a zinc source and a nickel source, a second precipitant and the first product system to obtain a second product system; (3) a third reaction of the second product system with an organosilane modifier to obtain a third product system, and separation treatment of the third product system to obtain a gel; (4) calcination of the gel to obtain the copper-containing catalyst.

2. The production method according to claim 1, wherein, The organosilane modifier is at least one selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate and hexadecyl trimethyl ammonium bromide.

3. The production method according to claim 2, wherein, The organosilane modifier is at least one selected from the group consisting of methyl orthosilicate and / or ethyl orthosilicate.

4. The production method according to claim 1, wherein The first precipitant and the second precipitant are each independently selected from oxalic acid and / or oxalate.

5. The production method according to any one of claims 1 to 4, wherein The aluminum source is at least one selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride; and / or, the magnesium source is at least one selected from the group consisting of magnesium nitrate, magnesium sulfate and magnesium chloride; and / or, the copper source is at least one selected from the group consisting of copper nitrate, copper sulfate and copper chloride; and / or, the zinc source is at least one selected from the group consisting of zinc nitrate, zinc sulfate and zinc chloride; and / or, the nickel source is at least one selected from the group consisting of nickel nitrate, nickel sulfate, nickel chloride and basic nickel carbonate.

6. The production method according to any one of claims 1 to 4, wherein The molar ratio of the aluminum source in terms of aluminum element, the magnesium source in terms of magnesium element, the copper source in terms of copper element, the zinc source in terms of zinc element, the nickel source in terms of nickel element and the organosilane modifier in terms of silicon element is (0.2-1.2):(0.05-0.5):1:(0.6-3.9):(0.1-1):(0.3-0.65).

7. The production method according to claim 6, wherein The molar ratio of the aluminum source in terms of aluminum element, the magnesium source in terms of magnesium element, the copper source in terms of copper element, the zinc source in terms of zinc element, the nickel source in terms of nickel element and the organosilane modifier in terms of silicon element is (0.3-0.5):(0.06-0.15):1:(1.2-2.6):(0.2-0.3):(0.3-0.6).

8. The production method according to any one of claims 1 to 4, wherein The conditions of the first reaction include that the pH value of the reaction system is ≥9 and the reaction temperature is 80-90℃; and / or, the conditions of the second reaction include that the pH value of the reaction system is ≥7 and the reaction temperature is 80-90℃; and / or, the conditions of the third reaction include that the reaction temperature is 80-95℃ and the reaction time is 10-40min.

9. The copper-containing catalyst prepared by the preparation method of any one of claims 1-8.

10. The copper-containing catalyst of claim 9, wherein, The copper-containing catalyst comprises copper oxide, zinc oxide, aluminum oxide, magnesium oxide, nickel oxide and silicon dioxide, wherein the weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide is 100:(66-400):(10-75):(3-25):(20-86):(24-47).

11. The copper-containing catalyst of claim 10, wherein, The weight ratio of copper oxide: zinc oxide: aluminum oxide: magnesium oxide: nickel oxide: silicon dioxide is 100:(120-260):(20-34):(3-17):(24-27):(25-45).

12. Use of a copper-containing catalyst according to any one of claims 9 to 11 in an aldehyde hydrogenation reaction or an ester hydrogenation reaction.

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