Octene aldehyde liquid phase hydrogenation catalyst and preparation method thereof

Abstract

The application discloses a preparation method of an octene aldehyde liquid-phase hydrogenation catalyst, and the preparation method comprises the following steps: (1) adding a weak acid into a salt solution containing silver, magnesium and aluminum, uniformly stirring, then adding a glycerol aldehyde, continuously stirring until a colloid is formed, grinding the colloid to obtain a powder, sieving, and roasting to obtain a carrier; and (2) preparing a precursor solution containing nickel and zinc, placing the precursor solution and the carrier in an ultrasonic container to shake, pouring the shaken solution into a well-sealed ball mill tank, ball milling, and then drying and roasting to obtain the catalyst. The catalyst is prepared by adding a silver-containing compound when the carrier is prepared and the ball milling method, so that the selectivity and stability of the catalyst are improved.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, specifically to an octenal liquid-phase hydrogenation catalyst and its preparation method. Background Technology

[0002] Octyl alcohol, as an important chemical product, has a wide range of applications in pharmaceuticals, dyes, plasticizers, and pesticides. With the rapid development of my country's national economy, octanol will play an increasingly important and irreplaceable role in our production and daily life. The main industrial preparation process of octanol is as follows: First, using syngas and propylene as raw materials, carbonyl synthesis is carried out under the action of a rhodium phosphine catalyst to produce mixed butyraldehyde (n-butyraldehyde and isobutyraldehyde). N-butyraldehyde undergoes condensation and dehydration under the action of a catalyst to produce octenal, which is then hydrogenated under the action of a catalyst to produce octanol. Currently, the aldehyde hydrogenation catalysts used in domestic butyraldehyde and octanol plants mainly rely on imports, which are expensive, resulting in high product costs. Therefore, further accelerating the research and development of aldehyde hydrogenation catalysts, promoting the localization of aldehyde hydrogenation catalysts, and accelerating the development of the fine chemical industry are urgent problems that need to be solved.

[0003] Patent CN201210219300.X discloses a method for preparing an aldehyde liquid-phase hydrogenation catalyst. The catalyst has a nickel content of 15% to 30% by mass and is prepared by co-precipitation: (1) The prepared nickel nitrate solution is added to a reaction vessel with a stirring paddle and heated to 50°C to 70°C. It is then neutralized and precipitated with an alkaline precipitant for 15 to 30 minutes, with an endpoint pH of 7.0 to 7.3. Then, it is aged at 60°C to 75°C for 20 to 50 minutes to fix the crystal form. (2) After aging, the precipitate is added to silica sol and stirred at 60°C to 90°C for 30 to 80 minutes to allow the silica sol to combine with the precipitate to form a stable and uniform slurry. (3) After washing and filtering, the filter cake is dried. The dried filter cake is ground, water and binder are added and extruded into strips. Then, it is calcined at 400°C to 700°C to obtain the aldehyde hydrogenation catalyst. The preparation process of this patented catalyst is simple and easy to implement, and it solves the problem of unstable catalyst performance. However, the selectivity of this catalyst needs to be improved.

[0004] Patent CN202110291957.6 discloses a catalyst for the liquid-phase hydrogenation of alkenes and aldehydes, its preparation method, and its uses. The catalyst comprises, by mass percentage: NiO 10-30%, MgO 0.5-15%, TiO2 0.5-15%, with the balance being γAl2O3; wherein the support is MgO-TiO2-γAl2O3, and the active component is Ni. This catalyst exhibits high activity and selectivity, has a simple preparation method, and uses inexpensive raw materials, making it suitable for the liquid-phase hydrogenation of alkenes and aldehydes. However, the catalyst suffers from poor stability, resulting in a short catalyst lifespan. Summary of the Invention

[0005] To address the problems of complex and difficult-to-control preparation methods for octenal liquid-phase hydrogenation catalysts in existing technologies, as well as poor catalyst stability and selectivity, this invention provides an octenal liquid-phase hydrogenation catalyst and its preparation method.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A method for preparing an octenal liquid-phase hydrogenation catalyst, the method comprising the following steps:

[0008] (1) Add a weak acid to a salt solution containing silver, magnesium and aluminum, stir evenly, add glyceraldehyde, continue stirring until a colloid is formed, grind the colloid to obtain a powder, sieve and calcine to obtain a carrier.

[0009] (2) Prepare a precursor solution containing nickel and zinc, place the precursor solution and the carrier in an ultrasonic container and shake, then pour it into a well-sealed ball mill jar, and after ball milling, dry and calcin to obtain the catalyst.

[0010] Furthermore, the salt solution containing silver, magnesium and aluminum in step (1) is a nitrate solution, and the molar ratio of silver, magnesium and aluminum is 0.05-0.1∶0.5-1.5∶10.

[0011] Furthermore, in step (1), the weak acid is citric acid, and the addition of citric acid makes the pH of the salt solution containing silver, magnesium and aluminum 4-4.5.

[0012] Furthermore, in step (1), the volume of glyceraldehyde is 0.1-0.4 times the volume of the salt solution;

[0013] Preferably, the volume of the glyceraldehyde is 0.2 times the volume of the salt solution.

[0014] Further, in step (1), when adding citric acid, the mixture is stirred at room temperature. After adding glyceraldehyde, the mixture is stirred at room temperature for 4 hours. Then, it is placed in a water bath at 95°C and heated and stirred until a gel is formed.

[0015] Furthermore, in step (1), the powder passes through an 80-100 mesh sieve, and the calcination conditions are as follows: in an air atmosphere, the powder is first heated to 500°C at a heating rate of 6°C / min in a muffle furnace and then pre-calcined for 3.5 hours, and then heated to 900°C at a heating rate of 4°C / min and calcined for 5 hours.

[0016] Further, in step (2), the precursor solution of nickel and zinc is a nitrate solution, and the concentration ratio of the nickel and zinc nitrate solution is 30-50 g / L: 10-15 g / L;

[0017] Preferably, the concentration ratio of the nickel and zinc nitrate solution is 50 g / L: 15 g / L.

[0018] Furthermore, in step (2), the ultrasonic container is vibrated for 3-5 hours.

[0019] Further, in step (2), the volume ratio of the carrier to the precursor solution is 1:1, the diameter of the grinding balls during the ball milling process is 1 mm and 5 mm, the volume ratio of the grinding balls to the precursor solution is 3:1, the rotation speed of the ball mill is 800 r / min, and the ball milling time is 8 h; the calcination process is carried out by heating to 600°C at a rate of 5°C / min and holding for 3 h to obtain the catalyst.

[0020] Preferably, the ratio of the number of grinding balls with diameters of 1 mm and 5 mm during the ball milling process is 1:1.

[0021] A catalyst prepared according to any of the above preparation methods.

[0022] The present invention has the following beneficial effects:

[0023] 1. The octenal liquid-phase hydrogenation catalyst provided by the present invention modifies the support by adding trace amounts of heavy metals and magnesium during the support preparation process. Under the premise of not excessively increasing the catalyst preparation cost, the addition of heavy metal silver significantly improves the selectivity of octanol in the octenal liquid-phase reaction of the catalyst.

[0024] 2. The octenal liquid-phase hydrogenation catalyst provided by the present invention uses ball milling in the preparation process. By using an appropriate number of grinding balls and a ratio of grinding balls with different diameters, the active components can be well loaded onto the support. Compared with the conventional impregnation method, the catalyst exhibits excellent activity and stability.

[0025] 3. The preparation method of the catalyst wastewater treatment agent provided by the present invention has a simple preparation process, readily available raw materials, and low production cost. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments.

[0027] The chemical reagents described in the following embodiments of the present invention can all be purchased directly from the market.

[0028] Example 1

[0029] (1) Weigh AgNO3, Mg(NO3)2·6H2O and Al(NO3)3·9H2O according to the molar ratio of silver, magnesium and aluminum of 0.05∶1∶10 and dissolve them in 100mL of deionized water. Stir thoroughly until the mixture is homogeneous. Then add citric acid to the above nitrate solution to make the pH 4. Continue stirring at room temperature for about half an hour.

[0030] After the citric acid is thoroughly mixed in the nitrate solution, glyceraldehyde is added. The volume of glyceraldehyde is 0.2 times that of the nitrate solution. The mixture is stirred for 4 hours. Then, it is transferred to a 95°C water bath to evaporate the aqueous solvent until a gel is formed. The gel is then dried in a 120°C oven for 24 hours to obtain a dry gel material. The dry gel material is ground and passed through a 100-mesh sieve. It is then pre-calcined in a muffle furnace at 500°C (heating rate 6°C / min) for 3.5 hours, and then calcined at 900°C (heating rate 4°C / min) for 5 hours to obtain the carrier.

[0031] (2) Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were weighed according to the concentration ratio of nickel and zinc nitrate solution of 50 g / L: 15 g / L and dissolved in 100 mL of deionized water to obtain precursor solution. The precursor solution and the carrier were placed in an ultrasonic container and shaken for 3 h. After shaking, the mixture was poured into the ball mill jar of a well-sealed planetary ball mill. The volume ratio of the grinding balls to the volume of the precursor solution was 3:1. The diameter of the grinding balls during the ball milling process was 1 mm and 5 mm. The number of grinding balls of the two different diameters was the same. The rotation speed of the ball mill jar was 800 r / min and the ball milling time was 8 h.

[0032] After ball milling, the grinding balls and wet material were removed from the mill jar. The grinding balls were rinsed with deionized water, and then the rinsing liquid and wet material were filtered together. The filter cake was dried in a vacuum drying oven at a vacuum degree of -0.05 MPa, a temperature of 120℃, and a time of 15 hours. The dried material was then calcined in a muffle furnace at a temperature of 600℃ for 5 hours at a rate of 5℃ / min, followed by a holding time of 3 hours to obtain the catalyst.

[0033] Example 2

[0034] (1) Weigh AgNO3, Mg(NO3)2·6H2O and Al(NO3)3·9H2O according to the molar ratio of silver, magnesium and aluminum of 0.1∶1∶10 and dissolve them in 100mL of deionized water. Stir thoroughly until the mixture is homogeneous. Then add citric acid to the above nitrate solution to make the pH 4.5. Continue stirring at room temperature for about half an hour.

[0035] After the citric acid is thoroughly mixed in the nitrate solution, glyceraldehyde is added. The volume of glyceraldehyde is 0.1 times the volume of nitrate. The mixture is stirred for 4 hours. Then, it is transferred to a 95°C water bath to evaporate the aqueous solvent until a gel is formed. The gel is then dried in a 120°C oven for 24 hours to obtain a dry gel material. The dry gel material is ground and passed through a 100-mesh sieve. It is then placed in a muffle furnace and pre-calcined at 500°C (heating rate 6°C / min) for 3.5 hours, and then calcined at 900°C (heating rate 4°C / min) for 5 hours to prepare the carrier.

[0036] (2) Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were weighed according to the concentration ratio of nickel and zinc nitrate solution of 30g / L:15g / L and dissolved in 100mL of deionized water to obtain precursor solution. The precursor solution and the carrier were placed in an ultrasonic container with equal volume and shaken for 3h. After shaking, it was poured into the ball mill jar of a well-sealed planetary ball mill. The volume ratio of grinding balls to precursor solution was 3:1. The diameter of grinding balls during ball milling was 1mm and 5mm. The number of grinding balls of the two different diameters was the same. The rotation speed of the ball mill jar was 800r / min and the ball milling time was 8h.

[0037] After ball milling, the grinding balls and wet material were removed from the mill jar. The grinding balls were rinsed with deionized water, and then the rinsing liquid and wet material were filtered together. The filter cake was dried in a vacuum drying oven at a vacuum degree of -0.05 MPa, a temperature of 120℃, and a time of 15 hours. The dried material was then calcined in a muffle furnace at a temperature of 600℃ for 5 hours at a rate of 5℃ / min, followed by a holding time of 3 hours to obtain the catalyst.

[0038] Example 3

[0039] (1) Weigh AgNO3, Mg(NO3)2·6H2O and Al(NO3)3·9H2O according to the molar ratio of silver, magnesium and aluminum of 0.05∶0.5∶10 and dissolve them in 100mL of deionized water. Stir thoroughly until the mixture is homogeneous. Then add citric acid to the above nitrate solution to make the pH 4. Continue stirring at room temperature for about half an hour.

[0040] After the citric acid is thoroughly mixed in the nitrate solution, glyceraldehyde is added. The volume of glyceraldehyde is 0.4 times that of the nitrate solution. The mixture is stirred for 4 hours. Then, it is transferred to a 95°C water bath to evaporate the aqueous solvent until a gel is formed. The gel is then dried in a 120°C oven for 24 hours to obtain a dry gel material. The dry gel material is ground and passed through a 100-mesh sieve. It is then pre-calcined in a muffle furnace at 500°C (heating rate 6°C / min) for 3.5 hours, and then calcined at 900°C (heating rate 4°C / min) for 5 hours to obtain the carrier.

[0041] (2) Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were weighed according to the concentration ratio of nickel and zinc nitrate solution of 50 g / L: 10 g / L and dissolved in 100 mL of deionized water to obtain precursor solution. The precursor solution and the carrier were placed in an ultrasonic container with equal volume and shaken for 3 h. After shaking, it was poured into the ball mill jar of a well-sealed planetary ball mill. The volume ratio of the grinding balls to the precursor solution was 3:1. The diameter of the grinding balls during the ball milling process was 1 mm and 5 mm. The number of grinding balls of the two different diameters was the same. The rotation speed of the ball mill jar was 800 r / min and the ball milling time was 8 h.

[0042] After ball milling, the grinding balls and wet material were removed from the mill jar. The grinding balls were rinsed with deionized water, and then the rinsing liquid and wet material were filtered together. The filter cake was dried in a vacuum drying oven at a vacuum degree of -0.05 MPa, a temperature of 120℃, and a time of 15 hours. The dried material was then calcined in a muffle furnace at a temperature of 600℃ for 5 hours at a rate of 5℃ / min, followed by a holding time of 3 hours to obtain the catalyst.

[0043] Example 4

[0044] (1) Weigh AgNO3, Mg(NO3)2·6H2O and Al(NO3)3·9H2O according to the molar ratio of silver, magnesium and aluminum of 0.05∶1.5∶10 and dissolve them in 100mL of deionized water. Stir thoroughly until the mixture is homogeneous. Then add citric acid to the above nitrate solution to make the pH 4. Continue stirring at room temperature for about half an hour.

[0045] After the citric acid is thoroughly mixed in the nitrate solution, glyceraldehyde is added. The volume of glyceraldehyde is 0.2 times that of the nitrate solution. The mixture is stirred for 4 hours. Then, it is transferred to a 95°C water bath to evaporate the aqueous solvent until a gel is formed. The gel is then dried in a 120°C oven for 24 hours to obtain a dry gel material. The dry gel material is ground and passed through a 100-mesh sieve. It is then pre-calcined in a muffle furnace at 500°C (heating rate 6°C / min) for 3.5 hours, and then calcined at 900°C (heating rate 4°C / min) for 5 hours to obtain the carrier.

[0046] (2) Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were weighed according to the concentration ratio of nickel and zinc nitrate solution of 50 g / L: 15 g / L and dissolved in 100 mL of deionized water to obtain precursor solution. The precursor solution and the carrier were placed in an ultrasonic container with equal volume and shaken for 5 h. After shaking, it was poured into the ball mill jar of a well-sealed planetary ball mill. The volume ratio of grinding balls to precursor solution was 3:1. The diameter of grinding balls during ball milling was 1 mm and 5 mm. The number of grinding balls of the two different diameters was the same. The rotation speed of the ball mill jar was 800 r / min and the ball milling time was 8 h.

[0047] After ball milling, the grinding balls and wet material were removed from the mill jar. The grinding balls were rinsed with deionized water, and then the rinsing liquid and wet material were filtered together. The filter cake was dried in a vacuum drying oven at a vacuum degree of -0.05 MPa, a temperature of 120℃, and a time of 15 hours. The dried material was then calcined in a muffle furnace at a temperature of 600℃ for 5 hours at a rate of 5℃ / min, followed by a holding time of 3 hours to obtain the catalyst.

[0048] Example 5

[0049] (1) Weigh AgNO3, Mg(NO3)2·6H2O and Al(NO3)3·9H2O according to the molar ratio of silver, magnesium and aluminum of 0.05∶1∶10 and dissolve them in 100mL of deionized water. Stir thoroughly until the mixture is homogeneous. Then add citric acid to the above nitrate solution to make the pH 4. Continue stirring at room temperature for about half an hour.

[0050] After the citric acid is thoroughly mixed in the nitrate solution, glyceraldehyde is added. The volume of glyceraldehyde is 0.2 times that of the nitrate solution. The mixture is stirred for 4 hours. Then, it is transferred to a 95°C water bath to evaporate the aqueous solvent until a gel is formed. The gel is then dried in a 120°C oven for 24 hours to obtain a dry gel material. The dry gel material is ground and passed through a 100-mesh sieve. It is then pre-calcined in a muffle furnace at 500°C (heating rate 6°C / min) for 3.5 hours, and then calcined at 900°C (heating rate 4°C / min) for 5 hours to obtain the carrier.

[0051] (2) Ni(NO3)2·6H2O and Zn(NO3)2·6H2O were weighed according to the concentration ratio of nickel and zinc nitrate solution of 50 g / L: 15 g / L and dissolved in 100 mL of deionized water to obtain precursor solution. The precursor solution and the carrier were placed in an ultrasonic container with equal volume and shaken for 5 h. After shaking, it was poured into the ball mill jar of a well-sealed planetary ball mill. The volume ratio of grinding balls to precursor solution was 3:1. The diameter of grinding balls during ball milling was 1 mm and 5 mm. The number of grinding balls of the two different diameters was the same. The rotation speed of the ball mill jar was 800 r / min and the ball milling time was 8 h.

[0052] After ball milling, the grinding balls and wet material were removed from the mill jar. The grinding balls were rinsed with deionized water, and then the rinsing liquid and wet material were filtered together. The filter cake was dried in a vacuum drying oven at a vacuum degree of -0.05 MPa, a temperature of 120℃, and a time of 15 hours. The dried material was then calcined in a muffle furnace at a temperature of 600℃ for 5 hours at a rate of 5℃ / min, followed by a holding time of 3 hours to obtain the catalyst.

[0053] Comparative Example 1

[0054] Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O according to a magnesium to aluminum molar ratio of 1:10, dissolve them in 100mL of deionized water, and perform the other operations as in Example 1.

[0055] Comparative Example 2

[0056] AgNO3, Mg(NO3)2·6H2O and Al(NO3)3·9H2O were weighed according to the molar ratio of silver, magnesium and aluminum of 0.01:1:10 and dissolved in 100 mL of deionized water. Other operations were the same as in Example 1.

[0057] Comparative Example 3

[0058] During the ball milling process, the ratio of the number of grinding balls with diameters of 1 mm and 5 mm was 1:3, and the volume ratio of the grinding balls to the precursor solution was 1:1. Other operations were the same as in Example 1.

[0059] Comparative Example 4

[0060] In step (2), the active metal is not loaded by ball milling, but by conventional impregnation: the carrier and precursor solution are impregnated at a volume ratio of 1:1 for 8 hours, and then filtered. The filter cake is dried in a vacuum drying oven at a vacuum degree of -0.05 MPa, a temperature of 120°C, and a time of 10 hours. The dried material is then calcined in a muffle furnace at a rate of 5°C / min to 600°C for 5 hours, and then kept at that temperature for 3 hours to obtain the catalyst. Other operations are the same as in Example 1.

[0061] Catalyst performance testing

[0062] The catalysts prepared in Examples 1-5 and Comparative Examples 1-4 were reduced under a hydrogen atmosphere at a reduction temperature of 500°C and a hydrogen space velocity of 3500 h⁻¹. -1 , restore for 4 hours.

[0063] The hydrogenation reaction of octenal was carried out in a 100 mL high-pressure reactor. The specific operating steps are as follows: 30 mL of octenal was placed in the reactor, 3 g of catalyst was added, and the reactor was sealed. The mixture was then purged three times with H2. The temperature was raised to 120 °C under stirring. Once the reaction temperature was reached, H2 was introduced (reaction pressure 2.0 MPa), and the liquid hourly space velocity (LHSV) was 5.0 h⁻¹. -1 The H2 / liquid (mol / mol) ratio was 6:1, the operating pressure was 2.6 MPa, and the hydrogen gas supply was stopped after 5 hours and 100 days of reaction, respectively. The reaction solution was taken at these two time points, and the composition of the filtrate was analyzed by gas chromatography.

[0064] The specific test results are shown in Table 1.

[0065] Table 1

[0066] experiment Octenal conversion rate Octyl alcohol selectivity Example 1 99.7％ 99.8％ Example 2 98.1％ 99.6％ Example 3 99.6％ 98.8％ Example 4 99.5％ 99.5％ Example 5 98.1％ 98.7％ Comparative Example 1 95.7％ 82.2％ Comparative Example 2 97.1％ 79.6％ Comparative Example 3 95.1％ 93.5％ Comparative Example 4 93.1％ 94.3％

[0067] According to the test results in Table 1 above, it is very obvious that when samples were taken after 5 hours of reaction, the conversion rate of octenal and the selectivity of octanol were tested. It can be seen that not adding silver-containing components or changing the silver content during the preparation of the carrier does not have a particularly significant effect on the conversion rate of octenal, but it has a greater impact on the selectivity of the product octanol.

[0068] The experiment found that changing the amount of grinding balls and the ratio of grinding balls of different diameters during the ball milling process had a certain impact on the conversion rate of octenal and the selectivity of octanol in the first 5 hours of the reaction, but the impact was not significant.

[0069] To test the stability of the catalyst during long-term operation, the conversion rate of octenal and the selectivity of octanol were tested after 100 days of reaction. The specific results are shown in Table 2 below.

[0070] Table 2

[0071] experiment Octenal conversion rate Octyl alcohol selectivity Example 1 95.7％ 98.4％ Example 2 94.9％ 98.2％ Example 3 90.8％ 98.1％ Example 4 95.1％ 97.8％ Example 5 97.3％ 98.5％ Comparative Example 1 88.4％ 61.4％ Comparative Example 2 90.2％ 57.8％ Comparative Example 3 40.5％ 89.3％ Comparative Example 4 55.6％ 93.1％

[0072] The test results in Table 2 show that when no silver-containing component is added or the silver content is changed during the preparation of the support, the selectivity of the catalyst for octanol is significantly reduced after 100 days of reaction, making it unsuitable for industrial production. Furthermore, changing the amount of grinding balls and the ratio of grinding balls of different diameters during ball milling significantly reduces the octenal conversion rate of the catalyst, indicating a substantial decrease in catalyst activity.

Claims

1. A method for preparing an octenal liquid-phase hydrogenation catalyst, characterized in that, The preparation method includes the following steps: (1) Add a weak acid to a salt solution containing silver, magnesium and aluminum, stir evenly, add glyceraldehyde, continue stirring until a colloid is formed, grind the colloid to obtain a powder, sieve and calcine to obtain a carrier. (2) Prepare a precursor solution containing nickel and zinc, place the precursor solution and the carrier in an ultrasonic container and shake, then pour it into a well-sealed ball mill jar, and after ball milling, dry and calcin to obtain the catalyst; The salt solution containing silver, magnesium and aluminum in step (1) is a nitrate solution, and the molar ratio of silver, magnesium and aluminum is 0.05-0.1:0.5-1.5:10; In step (1), the weak acid is citric acid. The addition of citric acid makes the pH of the salt solution containing silver, magnesium and aluminum 4-4.

5. In step (2), the volume ratio of the carrier to the precursor solution is 1:

1. The diameter of the grinding balls during the ball milling process is 1 mm and 5 mm. The volume ratio of the grinding balls to the precursor solution is 3:

1. The rotation speed of the ball mill is 800 r / min, and the ball milling time is 8 h. The calcination process is carried out by heating to 600°C at a rate of 5°C / min and holding for 3 h to obtain the catalyst. The ratio of grinding balls with diameters of 1 mm and 5 mm during the ball milling process is 1:

1.

2. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 1, characterized in that, In step (1), the volume of glyceraldehyde is 0.1-0.4 times the volume of the salt solution.

3. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 2, characterized in that, The volume of the glyceraldehyde is 0.2 times the volume of the salt solution.

4. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 1, characterized in that, In step (1), when adding citric acid, stir at room temperature. After adding glyceraldehyde, continue stirring at room temperature for 4 hours. Then place it in a water bath at 95°C and heat and stir until a gel is formed.

5. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 1, characterized in that, In step (1), the powder passes through an 80-100 mesh sieve. The calcination conditions are as follows: in an air atmosphere, the powder is first heated to 500°C at a heating rate of 6°C / min in a muffle furnace and then pre-calcined for 3.5 hours, and then heated to 900°C at a heating rate of 4°C / min and calcined for 5 hours.

6. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 1, characterized in that, In step (2), the precursor solutions for nickel and zinc are nitrate solutions, and the concentration ratio of the nickel and zinc nitrate solutions is 30-50 g / L: 10-15 g / L.

7. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 6, characterized in that, The concentration ratio of the nickel and zinc nitrate solution is 50 g / L: 15 g / L.

8. The method for preparing the octenal liquid-phase hydrogenation catalyst according to claim 1, characterized in that, In step (2), the ultrasonic container is vibrated for 3-5 hours.

9. An octenal liquid-phase hydrogenation catalyst, characterized in that, It is prepared according to any one of the preparation methods of claims 1-8 above.