Preparation method of catalyst for dehydration condensation reduction reaction and obtained product and application

Abstract

The invention discloses a kind of preparation method and products obtained therefrom and application of dehydration condensation reduction reaction catalyst, comprise the steps:Activated carbon is tiled in fixed bed, then the mixed solution of copper nitrate, zinc nitrate and zirconium nitrate is continuously passed into fixed bed, mixed solution is fully contacted with activated carbon layer;The activated carbon after being fully contacted with mixed solution is roasted, and the activated carbon of load copper oxide zinc oxide zirconium oxide is obtained;The activated carbon of load copper oxide zinc oxide zirconium oxide is scattered in organic solvent, then vulcanizing agent is added to carry out sulfurization reaction, after reaction, filtering, washing, drying, obtain dehydration condensation reduction reaction catalyst.Catalyst preparation method of the present invention is easy to operate, and cost is low, and environmental pollution is small, can be applied to the dehydration condensation reduction reaction of multiple ketones or aldehydes and amine, improves the selectivity of reaction, reduces the product of side reaction, catalytic effect is good, with industrial development prospect.

Description

Technical Field

[0001] The present invention relates to a preparation method of a catalyst for dehydration condensation reduction reaction and the obtained product, and also relates to application of the catalyst in condensation hydrogenation reaction of aldehyde or ketone and amine. Background Art

[0002] The dehydration condensation reduction of aldehydes and ketones with amines is crucial for the preparation of primary, secondary, and tertiary amines. Organic amines are widely used in pesticides, pharmaceuticals, dyes, surfactants, rubber additives, and other fields, playing a vital role in industrial and agricultural production and daily life.

[0003] Catalytic hydrogenation is a very traditional method, which involves dehydration condensation of carbonyl compounds with amines in a reducing atmosphere and over a reducing catalyst in the presence of a hydrogenation catalyst, such as nickel, palladium, or platinum, to obtain the target amine.

[0004] With the increasing application of the dehydration condensation reduction reaction between aldehydes and ketones and amines, research on this topic has intensified. Metal-supported catalysts offer high catalytic activity in dehydration condensation reduction reactions, resulting in a wide variety of hydrogenation byproducts. In particular, in the synthesis of the mainstream antioxidant 4020, approximately 17% of the raw material methyl isobutyl ketone (MIBK) is hydrogenated to methyl isobutyl carbinol (MIBC) using copper as a catalyst. Initially, these catalysts exhibit strong hydrocracking properties and high activity, which can lead to excessively rapid reactions and potentially overheating, damaging the catalyst and reactor. This increases safety risks, increases production costs, and reduces efficiency. Summary of the Invention

[0005] In order to improve the problems existing in existing catalysts, the present invention provides a method for preparing a catalyst for a dehydration condensation reduction reaction and the resulting catalyst. The present invention uses a special process to load copper oxide-zinc oxide-zirconium oxide onto activated carbon, which can appropriately weaken the hydrogenation catalytic performance of the catalyst, regulate the selectivity in the chemical reaction, reduce the side reactions of the dehydration condensation reduction reaction, and improve the yield of the main product.

[0006] The present invention is achieved through the following technical solutions:

[0007] A method for preparing a catalyst for a dehydration condensation reduction reaction, the method comprising the following steps:

[0008] (1) Activated carbon is spread flat on a fixed bed, and then a mixed solution of copper nitrate, zinc nitrate, and zirconium nitrate is continuously introduced into the fixed bed to ensure that the mixed solution is in full contact with the activated carbon layer;

[0009] (2) calcining the activated carbon after being fully contacted with the mixed solution to obtain activated carbon loaded with copper oxide-zinc oxide-zirconium oxide;

[0010] (3) The activated carbon loaded with copper oxide-zinc oxide-zirconium oxide is dispersed in an organic solvent, and then a sulfiding agent is added to carry out a sulfidation reaction. After the reaction, the mixture is filtered, washed, and dried to obtain a catalyst for a dehydration condensation reduction reaction.

[0011] Furthermore, in step (1), the specific surface area of the activated carbon is 1250-1350 m2 / g.

[0012] Furthermore, in step (1), the thickness of the activated carbon layer on the fixed bed is 1.3-1.8 cm.

[0013] Furthermore, in step (1), the mixed solution is obtained by mixing copper nitrate, zinc nitrate, zirconium nitrate and water, and there is no special requirement for the mixing order of the raw materials.

[0014] Furthermore, in step (1), the concentration of copper nitrate in the mixed solution is 1-5 g / 100 ml, for example, 1 g / 100 ml, 2 g / 100 ml, 3 g / 100 ml, 4 g / 100 ml, 5 g / 100 ml. Preferably, the concentration of copper nitrate is 3 g / 100 ml.

[0015] Furthermore, in step (1), the concentration of zinc nitrate in the mixed solution is 3-7 g / 100 ml, for example, 3 g / 100 ml, 4 g / 100 ml, 5 g / 100 ml, 6 g / 100 ml, 7 g / 100 ml. Preferably, the concentration of zinc nitrate is 4 g / 100 ml.

[0016] Furthermore, in step (1), the concentration of zirconium nitrate in the mixed solution is 1-5 g / 100 ml, for example, 1 g / 100 ml, 2 g / 100 ml, 3 g / 100 ml, 4 g / 100 ml, 5 g / 100 ml. Preferably, the concentration of zirconium nitrate is 2 g / 100 ml.

[0017] Furthermore, in step (1), the mixed solution passes through the activated carbon layer at a certain speed so that the metal salt in the mixed solution is fully in contact with the activated carbon, thereby achieving the loading of the metal salt on the activated carbon. The flow rate of the mixed solution is 1-10 ml / min, for example, 1 ml / min, 2 ml / min, 3 ml / min, 4 ml / min, 5 ml / min, 6 ml / min, 7 ml / min, 8 ml / min, 9 ml / min, 10 ml / min, and preferably 5 ml / min.

[0018] Furthermore, in step (1), the temperature of the mixed solution when in contact with the activated carbon layer is 25-45° C., for example, 25° C., 30° C., 35° C., 40° C., preferably 35° C. The contact time of the mixed solution with the activated carbon layer is 0.5-2 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, preferably 1 h.

[0019] Furthermore, in step (1), the final loading amount of the nitrate on the activated carbon can be controlled by controlling the concentration, flow rate, and contact time of the mixed solution. In a specific embodiment of the present invention, the final loading amount of copper nitrate on the activated carbon is 10-12%, the loading amount of zinc nitrate on the activated carbon is 7-8%, and the loading amount of zirconium nitrate on the activated carbon is 5-7%. The loading amount is calculated as the mass of the nitrate / (the total mass of the activated carbon and the nitrate)*100%.

[0020] Furthermore, in step (2), the calcination can be carried out in a muffle furnace under an air atmosphere.

[0021] Furthermore, in step (2), the calcination temperature is 400-800°C, for example, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, preferably, the calcination temperature is 500°C.

[0022] Furthermore, in step (2), the roasting time is 2-6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, and preferably, the roasting time is 4 hours.

[0023] Furthermore, in step (3), the copper oxide-zinc oxide-zirconium oxide loaded activated carbon obtained by calcination can be dispersed in an organic solvent by stirring, ultrasound, etc., and the organic solvent is an alcohol, such as methanol, ethanol, isopropanol, etc., preferably methanol.

[0024] Furthermore, in step (3), the mass ratio of the copper oxide-zinc oxide-zirconium oxide loaded activated carbon to the organic solvent is 1:6-10, for example, 1:6, 1:7, 1:8, 1:9, 1:10.

[0025] Furthermore, in step (3), the vulcanizing agent is at least one of dimethyl sulfide, dodecanethiol, dimethyl sulfoxide, diphenyl sulfide, and diphenyl disulfide, preferably a mixture of diphenyl sulfide and diphenyl disulfide.

[0026] Furthermore, when the vulcanizing agent is a mixture of diphenyl sulfide and diphenyl disulfide, the mass ratio of diphenyl sulfide to diphenyl disulfide is 1:1-1.5, preferably 1:1.2.

[0027] Furthermore, in step (3), the mass ratio of the copper oxide-zinc oxide-zirconium oxide loaded activated carbon to the sulfiding agent is 5:0.1-1, for example, 5:0.1, 5:0.2, 5:0.3, 5:0.4, 5:0.5, 5:0.6, 5:0.7, 5:0.8, 5:0.9, 5:1.0, preferably 5:0.5.

[0028] Furthermore, in step (3), the vulcanizing agent is preferably added dropwise, and the dropwise addition time is controlled to be 2-5 min. The temperature during the dropwise addition is 25-45°C, for example, 25°C, 30°C, 35°C, 40°C, 45°C, preferably 35°C.

[0029] Furthermore, in step (3), after the vulcanizing agent is added, the reaction is continued at 25-45°C, for example, 25°C, 30°C, 35°C, 40°C, 45°C, preferably 35°C. The reaction time is 0.5-2h, for example, 0.5h, 1h, 1.5h, 2h, preferably 1h.

[0030] Furthermore, in step (3), after the sulfurization is completed, the product is filtered, washed, and dried to obtain the product of the present invention.

[0031] The catalyst for the dehydration condensation reduction reaction of the present invention has good selectivity and can be applied to the dehydration condensation reduction reaction of various ketones or aldehydes with amines. Therefore, the catalyst and its application in the dehydration condensation reduction reaction of aldehydes with amines or the dehydration condensation reduction reaction of ketones with amines also fall within the protection scope of the present invention.

[0032] The present invention has the following beneficial effects:

[0033] 1. The method of the present invention is simple to operate, has mild synthesis conditions, low risk, low cost, and little environmental pollution.

[0034] 2. The present invention uses activated carbon as a carrier, loads metallic copper ions, zinc ions, and zirconium ions, and then calcines them at high temperature to obtain a carbon-based catalyst loaded with a composite oxide. The catalyst is then sulfurized with a sulfurizing agent to deactivate the catalyst activity, resulting in the final activated carbon-supported CuO-ZnO-ZrO2-S catalyst. This catalyst is easy to purchase and transport, and its hydrogenation catalytic performance is appropriately weakened. It can be applied to the dehydration condensation reduction reaction of various ketones or aldehydes with amines, improving the reaction selectivity, reducing the production of side reaction products, and achieving excellent catalytic effects. DETAILED DESCRIPTION

[0035] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, a novel catalyst preparation method and its application method in antioxidant synthesis proposed in accordance with the present invention, its specific implementation method and its effects are described in detail as follows.

[0036] In the following examples and comparative examples, the activated carbon used was purchased from the market and had a specific surface area of 1250-1350 m2 / g.

[0037] Example 1

[0038] A method for preparing a catalyst for a dehydration condensation reduction reaction, wherein the specific synthesis steps are as follows:

[0039] Step 1: Load

[0040] Weigh 5g of activated carbon and fill it into a fixed bed with a thickness of 1.5cm. Dissolve copper nitrate, zinc nitrate, and zirconium nitrate in water and mix thoroughly to obtain a mixed solution with a copper nitrate concentration of 2g / 100ml, a zinc nitrate concentration of 4g / 100ml, and a zirconium nitrate concentration of 2g / 100ml. The mixed solution is passed through the fixed bed at a rate of 3ml / min at 35°C, allowing the activated carbon to remain in contact with the mixed solution for 1 hour. After completion, the solution is washed and the contents of copper nitrate, zinc nitrate, and zirconium nitrate in the remaining mixed solution are determined. The activated carbon loading is calculated by subtraction. The copper nitrate loading on the activated carbon is approximately 10%, the zinc nitrate loading is approximately 8%, and the zirconium nitrate loading is approximately 7%. Loading = metal salt mass / (activated carbon mass + total metal salt mass) * 100%.

[0041] Step 2: Firing

[0042] The activated carbon loaded with metal ions was placed in a muffle furnace, calcined at 400° C. in an air atmosphere, and cooled after 3 hours to obtain a carbon-based copper oxide-zinc oxide-zirconium oxide catalyst.

[0043] Step 3: Vulcanization

[0044] At 25°C, 5g of a carbon-based copper oxide-zinc oxide-zirconium oxide catalyst was added to 30g of an organic solvent, ethanol, and the mixture was thoroughly stirred and dispersed evenly. Then, 0.3g of a mixture of diphenyl sulfide and diphenyl disulfide in a mass ratio of 1:1.4 was added dropwise using a pipette for 3 minutes. After the addition was complete, the mixture was sulfurized at 25°C for 0.5h, and then filtered. The solid was washed and dried in an oven to obtain the catalyst product of the present invention.

[0045] Example 2

[0046] A method for preparing a catalyst for a dehydration condensation reduction reaction, wherein the specific synthesis steps are as follows:

[0047] Step 1: Load

[0048] Weigh 5g of activated carbon and fill it in a fixed bed with a thickness of 1.5cm. Dissolve copper nitrate, zinc nitrate and zirconium nitrate in water and mix them evenly to obtain a mixed solution with a copper nitrate concentration of 3g / 100ml, a zinc nitrate concentration of 4g / 100ml and a zirconium nitrate concentration of 2g / 100ml. Pass the mixed solution through the fixed bed at a rate of 5ml / min at 35°C, so that the activated carbon and the mixed solution are in contact for 0.5h. After completion, wash and determine the contents of copper nitrate, zinc nitrate and zirconium nitrate in the remaining mixed solution. Calculate the loading of activated carbon by subtraction. The loading of copper nitrate on activated carbon is about 12%, the loading of zinc nitrate is about 7%, and the loading of zirconium nitrate is about 6%.

[0049] Step 2: Firing

[0050] The activated carbon loaded with metal ions was placed in a muffle furnace, calcined at 500° C. in an air atmosphere, and cooled after 4 hours to obtain a carbon-based copper oxide-zinc oxide-zirconium oxide catalyst.

[0051] Step 3: Vulcanization

[0052] At 25°C, 5g of a carbon-based copper oxide-zinc oxide-zirconium oxide catalyst was added to 30g of an organic solvent, methanol, and the mixture was thoroughly stirred and dispersed evenly. Then, 0.5g of a mixture of diphenyl sulfide and diphenyl disulfide in a mass ratio of 1:1.3 was added dropwise using a pipette for 3 minutes. After the addition was complete, the mixture was sulfurized at 25°C for 1 hour, and then filtered, the solid was washed, and dried in an oven to obtain the catalyst product of the present invention.

[0053] Example 3

[0054] A catalyst for dehydration condensation reduction reaction was prepared according to the method of Example 2, except that in step 3, 0.5 g of diphenyl sulfide and diphenyl disulfide with a mass ratio of 1:1.3 was replaced by 1 g of diphenyl sulfide, and the addition time was 3 min.

[0055] Example 4

[0056] A catalyst for dehydration condensation reduction reaction was prepared according to the method of Example 2, except that in step 3, 0.5 g of diphenyl sulfide and diphenyl disulfide in a mass ratio of 1:1.3 was replaced with 0.5 g of a mixture of dimethyl sulfide and diphenyl disulfide in a mass ratio of 1:1.2, and the addition time was 3 min.

[0057] Example 5

[0058] The catalyst for dehydration condensation reduction reaction was prepared according to the method of Example 2, except that: in step 1, 5 g of activated carbon was weighed and filled in a fixed bed with a thickness of 1.5 cm. Copper nitrate, zinc nitrate and zirconium nitrate were dissolved in water and mixed evenly to obtain a mixed solution having a copper nitrate concentration of 5 g / 100 ml, a zinc nitrate concentration of 7 g / 100 ml and a zirconium nitrate concentration of 5 g / 100 ml. The mixed solution was passed through the fixed bed at a rate of 10 ml / min at 45 ° C. The activated carbon was kept in contact with the mixed solution for 0.5 h. After completion, washing was performed, and the contents of copper nitrate, zinc nitrate and zirconium nitrate in the remaining mixed solution were determined. The loading amount of the activated carbon was calculated by subtraction. The loading amount of copper nitrate on the activated carbon was about 10%, the loading amount of zinc nitrate was about 7%, and the loading amount of zirconium nitrate was about 5%.

[0059] Comparative Example 1

[0060] A method for preparing a catalyst for a dehydration condensation reduction reaction, wherein the specific synthesis steps are as follows:

[0061] Step 1: Load

[0062] Weigh 5g of activated carbon and fill it in a fixed bed with a thickness of 1.5cm. Dissolve copper nitrate, zinc nitrate and zirconium nitrate in water and mix them evenly to obtain a mixed solution with a copper nitrate concentration of 3g / 100ml, a zinc nitrate concentration of 4g / 100ml and a zirconium nitrate concentration of 2g / 100ml. Pass the mixed solution through the fixed bed at a rate of 5ml / min at 35°C, so that the activated carbon and the mixed solution are in contact for 0.5h. After completion, wash and determine the contents of copper nitrate, zinc nitrate and zirconium nitrate in the remaining mixed solution. Calculate the loading of activated carbon by subtraction. The loading of copper nitrate on activated carbon is about 12%, the loading of zinc nitrate is about 7%, and the loading of zirconium nitrate is about 6%.

[0063] Step 2: Firing

[0064] The activated carbon loaded with metal ions was placed in a muffle furnace, calcined at 500° C. in an air atmosphere, and cooled after 4 hours to obtain a carbon-based copper oxide-zinc oxide-zirconium oxide catalyst.

[0065] Comparative Example 2

[0066] A catalyst for a dehydration condensation reduction reaction was prepared according to the method of Example 2, except that in step 1, copper nitrate, zinc nitrate, and zirconium nitrate were dissolved in water and mixed uniformly to obtain a mixed solution having a copper nitrate concentration of 3 g / 100 ml, a zinc nitrate concentration of 4 g / 100 ml, and a zirconium nitrate concentration of 2 g / 100 ml. 5 g of activated carbon was added to 30 g of the mixed solution, and the mixture was stirred at 35°C for 0.5 h. After completion, the mixture was washed and the loading capacity was determined by subtraction. The loading capacity of copper nitrate on the activated carbon was approximately 8%, the loading capacity of zinc nitrate was approximately 6%, and the loading capacity of zirconium nitrate was approximately 5%.

[0067] Comparative Example 3

[0068] The catalyst for dehydration condensation reduction reaction was prepared according to the method of Example 2, except that: In step 1, 5 g of activated carbon was weighed and filled in a fixed bed with a thickness of 1.5 cm. Copper nitrate was dissolved in water and mixed evenly to obtain a solution with a copper nitrate concentration of 3 g / 100 ml. The copper nitrate solution was passed through the fixed bed at a rate of 5 ml / min at 35 ° C. The activated carbon was kept in contact with the mixed solution for 2 hours. After completion, washing was performed, and the content of copper nitrate in the remaining mixed solution was determined. The loading amount of activated carbon was calculated by subtraction, and the loading amount of copper nitrate on the activated carbon was about 17%.

[0069] Comparative Example 4

[0070] The catalyst for dehydration condensation reduction reaction was prepared according to the method of Example 2, except that: In step 1, 5 g of activated carbon was weighed and filled in a fixed bed with a thickness of 1.5 cm. Copper nitrate and zinc nitrate were dissolved in water and mixed uniformly to obtain a solution having a copper nitrate concentration of 3 g / 100 ml and a zinc nitrate concentration of 4 g / 100 ml. The copper nitrate solution was passed through the fixed bed at a rate of 5 ml / min at 35 ° C. The activated carbon was kept in contact with the mixed solution for 0.8 h. After completion, washing was performed, and the content of copper nitrate in the remaining mixed solution was determined. The loading amount of the activated carbon was calculated by subtraction. The loading amount of copper nitrate on the activated carbon was about 13%, and the loading amount of zinc nitrate was about 11%.

[0071] Application Example 1

[0072] A 100 mL autoclave was charged with 18.4 g of 4-aminodiphenylamine, 50 g of methyl isobutyl ketone, and 3 g of the catalyst from Example 2. Hydrogen was then introduced to a pressure of 3-4 MPa. The reaction temperature was controlled at 120°C for ketoamine dehydration condensation. After the hydrogen pressure dropped below 2 MPa, hydrogen was introduced to a pressure of 3-4 MPa until the hydrogen pressure ceased to decrease. After completion of the reaction, no by-product of methyl isobutyl carbinol was detected in the reaction mother liquor. The remaining ketone and water were removed under reduced pressure to yield 26.29 g of the final antioxidant product. The liquid phase purity (HPLC) was 99.2% (after deducting the ketone), and the product yield, calculated as 4-aminodiphenylamine, was 98.91%.

[0073] Application Example 2

[0074] A 100 mL autoclave was charged with 18.4 g of 4-aminodiphenylamine, 46.4 g of acetone, and 3 g of the catalyst from Example 2. Hydrogen was then introduced to a pressure of 3-4 MPa. The reaction temperature was controlled at 120°C for ketoamine dehydration condensation. After the hydrogen pressure dropped below 2 MPa, hydrogen was introduced to a pressure of 3-4 MPa until the hydrogen pressure ceased to decrease. After completion of the reaction, no byproduct isopropanol was detected in the reaction mother liquor. The remaining ketone and water were removed under reduced pressure to yield 22.34 g of the final antioxidant product. The liquid phase purity (HPLC) was 99.1% (after deducting the ketone), and the product yield, calculated as 4-aminodiphenylamine, was 98.73%.

[0075] Application Example 3

[0076] A 100mL autoclave was charged with 19.9g of 4,4-diaminodiphenylamine, 46.4g of acetone, and 3g of the catalyst from Example 2. Hydrogen was then introduced to a pressure of 3-4 MPa. The reaction temperature was controlled at 120°C for ketoamine dehydration condensation. After the hydrogen pressure dropped below 2 MPa, hydrogen was introduced to a pressure of 3-4 MPa until the hydrogen pressure ceased to decrease. After completion of the reaction, no byproduct isopropanol was detected in the reaction mother liquor. The remaining ketone and water were removed under reduced pressure to obtain 27.81g of the final antioxidant product with a liquid phase purity (HPLC) of 99.5% (after deducting the ketone). The product yield, calculated as 4,4-diaminodiphenylamine, was 98.27%.

[0077] Application Example 4

[0078] A 100 mL autoclave was charged with 10 g of 4,4-diaminodiphenylamine, 50 g of methyl isobutyl ketone, and 3 g of the catalyst from Example 2. Hydrogen was then introduced to a pressure of 3-4 MPa. The reaction temperature was controlled at 120°C for ketoamine dehydration condensation. After the hydrogen pressure dropped below 2 MPa, hydrogen was introduced to a pressure of 3-4 MPa until the hydrogen pressure ceased to decrease. After completion of the reaction, no by-product methyl isobutyl carbinol was detected in the reaction mother liquor. The remaining ketone and water were removed under reduced pressure to yield 18.18 g of the final antioxidant product with a liquid phase purity (HPLC) of 99.0% (after deducting the ketone). The yield of the product, calculated as 4,4-diaminodiphenylamine, was 99.07%.

[0079] Application Example 5

[0080] The antioxidant product was prepared according to the conditions of Application Example 1, except that the catalyst in Application Example 1 was repeatedly used. The results are shown in Table 1 below:

[0081]

[0082] Application Example 6

[0083] In a 100mL autoclave, 18.4g of 4-aminodiphenylamine, 50g of methyl isobutyl ketone, and 3g of different catalysts were added, and then hydrogen was introduced to 3-4MPa. The reaction temperature was controlled to 120°C for ketoamine dehydration condensation. After the hydrogen pressure was lower than 2Mpa, hydrogen was introduced to 3-4Mpa until the hydrogen no longer decreased. After the reaction was completed, the alcohol content in the reaction mother liquor was detected, and then the alcohol, ketone and water were removed under reduced pressure to obtain the final antioxidant product. The catalysts used and the product conditions are shown in Table 2 below.

[0084]

[0085] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been presented as a preferred embodiment as above, it is not intended to limit the present invention. Any technician familiar with this profession can make some changes or modifications to the technical contents disclosed above without departing from the scope of the technical solution of the present invention. Any simple modification, equivalent change and modification of the above embodiments based on the technical essence of the present invention that does not depart from the content of the technical solution of the present invention still falls within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a catalyst for dehydration condensation reduction reaction, characterized in that The following steps are involved: (1) Activated carbon is spread flat on a fixed bed, and then a mixed solution of copper nitrate, zinc nitrate, and zirconium nitrate is continuously introduced into the fixed bed to ensure that the mixed solution is in full contact with the activated carbon layer; (2) calcining the activated carbon after being fully contacted with the mixed solution to obtain activated carbon loaded with copper oxide-zinc oxide-zirconium oxide; (3) The activated carbon loaded with copper oxide-zinc oxide-zirconium oxide is dispersed in an organic solvent, and then a sulfiding agent is added to carry out a sulfidation reaction. After the reaction, the mixture is filtered, washed, and dried to obtain a catalyst for a dehydration condensation reduction reaction.

2. The preparation method according to claim 1, wherein: In step (1), at least one of the following conditions is included: a. The specific surface area of activated carbon is 1250-1350㎡ / g; b. The thickness of the activated carbon layer is 1.3-1.8 cm; c. The flow rate of the mixed solution is 1-10 ml / min; d. In the mixed solution, the concentration of copper nitrate is 1-5g / 100ml, the concentration of zinc nitrate is 3-7g / 100ml, and the concentration of zirconium nitrate is 1-5g / 100ml; e. The temperature of the mixed solution when in contact with the activated carbon layer is 25-45°C, and the contact time is 0.5-2h.

3. The preparation method according to claim 1 or 2, characterized in that: In step (2), the calcination is carried out in air at a temperature of 400-800° C. and a calcination time of 2-6 hours.

4. The preparation method according to claim 1, wherein: In step (3), the organic solvent is an alcohol.

5. The preparation method according to claim 4, wherein: In step (3), the organic solvent is methanol, ethanol or isopropanol.

6. The preparation method according to claim 1, wherein: In step (3), the vulcanizing agent is at least one of dimethyl sulfide, dodecanethiol, dimethyl sulfoxide, diphenyl sulfide, and diphenyl disulfide.

7. The preparation method according to claim 6, characterized in that: In step (3), the vulcanizing agent is a mixture of diphenyl sulfide and diphenyl disulfide.

8. The preparation method according to claim 1, 6 or 7, characterized in that: In step (3), the mass ratio of the copper oxide-zinc oxide-zirconium oxide loaded activated carbon to the sulfiding agent is 5:0.1-1.

9. The preparation method according to claim 1, 4, 5, 6 or 7, characterized in that: In step (3), the sulfiding agent is added dropwise for 2-5 minutes.

10. The preparation method according to claim 9, characterized in that: In step (3), the temperature for adding the vulcanizing agent is 25-45°C, and the reaction is kept warm for 0.5-2 hours after the addition is completed.

11. A catalyst prepared according to the method for preparing a catalyst for dehydration condensation reduction reaction according to any one of claims 1 to 10.

12. Use of the catalyst according to claim 11 in a dehydration condensation reduction reaction of an aldehyde with an amine or a dehydration condensation reduction reaction of a ketone with an amine.

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