Composite catalyst and use thereof

Abstract

This invention discloses a composite catalyst and its application. The composite catalyst is a Pd / MgO-ZrO₂-Hβ catalyst. It is prepared by first adding an alkaline solution to a system containing Hβ molecular sieves, magnesium ions, and zirconium ions to obtain a precipitate. The precipitate is then filtered, dried, ground, and calcined to obtain a MgO-ZrO₂-Hβ composite support. The MgO-ZrO₂-Hβ composite support is then mixed with a palladium-containing solution and allowed to stand. After drying and reduction with a reducing agent, the Pd / MgO-ZrO₂-Hβ composite catalyst is obtained. In this invention, MgO provides basic sites, the ZrO₂-Hβ molecular sieve composite system possesses both acidic sites and a good pore structure, and Pd serves as the active hydrogenation center. The composite catalyst of this invention exhibits good mechanical strength and thermal stability and can be reused multiple times. Furthermore, the composite catalyst provided by this invention, with its unique pore structure and distribution of acid and basic sites, facilitates the suppression of side reactions and improves product selectivity. The composite catalyst of this invention can be applied to the preparation of compounds that simultaneously undergo aldol condensation and catalytic hydrogenation reactions.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, and in particular to a composite catalyst and its application. Background Technology

[0002] Multi-step reactions can often be shortened to a single-step reaction by using composite catalysts. For example, the aldol condensation between low molecular weight ketones and ketones or aldehydes, followed by catalytic hydrogenation, can extend the carbon chain and prepare larger molecular weight ketones, alcohols, and other compounds such as MIAK, MIBK, MAK, and MIPK. These compounds can be prepared using composite catalysts in a one-step process.

[0003] However, in the existing one-step process, ketones and aldehydes undergo severe side reactions such as self-condensation and over-condensation during condensation, dehydration and hydrogenation, generating a large number of complex byproducts. This results in low yield of the target product, difficulty in subsequent separation and purification of the target product, and rapid deactivation of the multifunctional catalyst. Its low selectivity, complex side reactions, stringent catalyst requirements, difficult process optimization and high separation and purification costs limit its industrial application and economic competitiveness. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a composite catalyst and its application, wherein the composite catalyst is a ternary catalytic system, has good stability, the active components are not easily lost, it can be reused, and it is suitable for application in the preparation of compounds that simultaneously have aldol condensation reaction and catalytic hydrogenation reaction.

[0005] To address the aforementioned technical problems, a first aspect of the present invention provides a composite catalyst, denoted as Pd / MgO-ZrO2-Hβ, obtained by the following method: S1. An alkaline solution is added to a system containing Hβ molecular sieve, magnesium ions and zirconium ions to obtain a precipitate. The precipitate is filtered, dried, ground and calcined to obtain a MgO-ZrO2-Hβ composite carrier. S2. The MgO-ZrO2-Hβ composite support obtained in S1 is mixed with a palladium-containing solution and allowed to stand. After drying and reduction with a reducing agent, the Pd / MgO-ZrO2-Hβ composite catalyst is obtained.

[0006] In this invention, MgO provides basic sites to promote the aldol condensation reaction; the ZrO2-Hβ molecular sieve composite system possesses both acidic sites and a good pore structure, which is beneficial for the dehydration reaction; Pd acts as an active hydrogenation center, promoting the catalytic hydrogenation reaction; the composite catalyst of this invention has good mechanical strength and thermal stability, and the active components are not easily lost during the reaction, allowing for repeated use; furthermore, the composite catalyst provided by this invention, with its unique pore structure and acid / basic site distribution, can effectively suppress side reactions and improve the selectivity of the target product. The preparation method of the composite catalyst of this invention is simple and suitable for industrial production.

[0007] In one specific scheme, in S1, the system containing Hβ molecular sieve, magnesium ions and zirconium ions is obtained by mixing a suspension containing Hβ molecular sieve with a metal salt solution containing magnesium ions and zirconium ions, wherein the volume ratio of the suspension containing Hβ molecular sieve to the metal salt solution is 1:0.5-1.5.

[0008] Preferably, the mass concentration of Hβ molecular sieve in the suspension containing Hβ molecular sieve is 1%-10%; in the metal salt solution, the molar concentration of magnesium ions is 0.08-0.8 mol / L, and the concentration of zirconium ions is 0.08-0.8 mol / L (more preferably, the concentration of zirconium ions is greater than the concentration of magnesium ions).

[0009] In this specific scheme, the suspension containing Hβ molecular sieve is obtained by dispersing Hβ molecular sieve in a solution, preferably by ultrasonic treatment during the dispersion process to improve the dispersion quality, and the solution is, for example, water; the metal ions in the metal salt solution are obtained by dissolving the metal salt in a solution (e.g., water), for example by dissolving magnesium salts such as magnesium sulfate, magnesium nitrate, and magnesium chloride in a solution, and zirconium ions are obtained by dissolving zirconium salts such as zirconia sulfate and zirconia nitrate in a solution.

[0010] In one specific embodiment, the alkaline solution in S1 is added dropwise at a rate of 1-2 mL / min. During the dropwise addition, the temperature of the system is maintained between 30-50°C. The addition of the alkaline solution is stopped when the pH of the system reaches 9-10. Preferably, the alkaline solution is ammonia (other alkaline compounds that can provide hydroxide ions can also be used if this is not desired), with a mass concentration of 5%-10%.

[0011] In this specific scheme, the alkaline solution serves to co-precipitate magnesium and zirconium ions, with the precipitate adhering to the Hβ molecular sieve. Controlling the dropping rate of the alkaline solution controls the rate of precipitation, facilitating recombination between the precipitate and the Hβ molecular sieve. When the system pH reaches 9-10, it indicates that the metal ions have completed the precipitation reaction, and the dropping of the alkaline solution is stopped.

[0012] In one specific scheme, after the alkaline solution is added in S1, the solution is allowed to stand at 30-60°C for 6-12 hours. The calcination temperature is 500℃-600℃, and the time is 4-6 hours.

[0013] In this specific scheme, after stopping the addition of alkaline solution, it is preferable to continue stirring for 1-3 hours, followed by static aging (i.e., standing at 30-60℃ for 6-12 hours) to improve the composite quality of the metal precipitate and Hβ molecular sieve. After static aging, the deposit is filtered, the filter cake is collected, washed, and dried to form a dry gel. This gel is then ground, pulverized, and calcined to convert the metal hydroxide into oxides, thereby forming a MgO-ZrO2-Hβ composite carrier. Preferably, the rate of heating to the calcination temperature is controlled between 2-5℃ / min.

[0014] In one specific embodiment, S2 contains a palladium-containing solution including chloropalladic acid solution, palladium chloride, and tetraamminepalladium chloride, wherein the mass concentration of palladium ions is 0.5-2.5%.

[0015] Preferably, the standing time is 6-15 hours; the reducing agent is hydrogen gas, and the reduction process is to introduce hydrogen gas at 300℃-400℃ for 2-5 hours.

[0016] In this specific scheme, mixing and allowing the MgO-ZrO2-Hβ composite support with a palladium-containing solution to stand facilitates the composite formation between the palladium salt and the MgO-ZrO2-Hβ composite support. After composite formation, for example, hydrogen gas is used to reduce the palladium ions attached to the MgO-ZrO2-Hβ composite support to palladium atoms, thereby forming a Pd / MgO-ZrO2-Hβ composite catalyst.

[0017] To address the aforementioned technical problems, a second aspect of the present invention is to provide the application of the aforementioned composite catalyst in a reaction that simultaneously involves aldol condensation and catalytic hydrogenation.

[0018] Preferably, the simultaneous aldol condensation reaction and catalytic hydrogenation reaction includes one or more of the following reactions: MIAK was synthesized in one step using acetone and isobutyraldehyde as raw materials. MIBK is synthesized in one step using acetone as a raw material; MAK was synthesized in one step from acetone and n-butyraldehyde.

[0019] MIPK was synthesized in one step using butanone and formaldehyde aqueous solution as raw materials.

[0020] In this invention, MgO provides basic sites in the composite catalyst to promote the aldol condensation reaction; the ZrO2-Hβ molecular sieve composite system has both acidic sites and a good pore structure, which is beneficial for the dehydration reaction; Pd serves as an active hydrogenation center to promote the catalytic hydrogenation reaction; the composite catalyst of this invention has good mechanical strength and thermal stability, and the active components are not easily lost during the reaction, so it can be reused multiple times; in addition, the composite catalyst provided by this invention, with its unique pore structure and distribution of acid and basic sites, can effectively suppress side reactions and improve the selectivity of the target product, and the preparation method is simple and suitable for industrial production. Attached Figure Description

[0021] To more clearly illustrate the technical solution of the present invention, the accompanying drawings used in the present invention will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is the spectrum of the first experimental example in Embodiment 2 of the present invention; Figure 2 This is the spectrum of the second experimental example in Embodiment 2 of the present invention; Figure 3 This is the spectrum of the third experimental example in Embodiment 2 of the present invention; Figure 4 This is the spectrum of the fourth experimental example in Embodiment 2 of the present invention; Figure 5 This is the spectrum of the fifth experimental example in Embodiment 2 of the present invention; Figure 6 This is the spectrum of the sixth experimental example in Embodiment 2 of the present invention; Figure 7 This is the spectrum of the seventh experimental example in Embodiment 2 of the present invention; Figure 8 This is the spectrum of the eighth experimental example in Embodiment 2 of the present invention; Figure 9 This is the spectrum of the ninth experimental example in Embodiment 2 of the present invention; Figure 10 This is the spectrum of the tenth experimental example in Embodiment 2 of the present invention; Figure 11 This is the spectrum of the eleventh experimental example in Embodiment 2 of the present invention; Figure 12 This is the spectrum of the twelfth experimental example in Embodiment 2 of the present invention; Figure 13 This is the spectrum of the thirteenth experimental example in Embodiment 2 of the present invention; Figure 14 This is the spectrum of the fourteenth experimental example in Embodiment 2 of the present invention; Figure 15 This is the spectrum of the fifteenth experimental example in Embodiment 2 of the present invention; Figure 16 This is the spectrum of the sixteenth experimental example in Embodiment 2 of the present invention; Figure 17 This is the spectrum of the seventeenth experimental example in Embodiment 2 of the present invention; Figure 18 This is the spectrum of the eighteenth experimental example in Embodiment 2 of the present invention; Figure 19 This is the spectrum of the nineteenth experimental example in Embodiment 2 of the present invention; Figure 20 This is the spectrum of the twentieth experimental example in Embodiment 2 of the present invention; Figure 21 This is the spectrum of the twenty-first experimental example in Embodiment 2 of the present invention; Figure 22 This is the spectrum of the twenty-second experimental example in Embodiment 2 of the present invention; Figure 23 This is the spectrum of the twenty-third experimental example in Embodiment 2 of the present invention; Figure 24 This is the spectrum of the twenty-fourth experimental example in Embodiment 2 of the present invention; Figure 25 This is the spectrum of the twenty-fifth experimental example in Embodiment 2 of the present invention; Figure 26 This is the spectrum of the twenty-sixth experimental example in Embodiment 2 of the present invention; Figure 27 This is the spectrum of the twenty-seventh experimental example in Embodiment 2 of the present invention; Figure 28 This is the spectrum of the twenty-eighth experimental example in Embodiment 2 of the present invention. Detailed Implementation

[0023] The technical solutions of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0024] Example 1: Preparation of Composite Catalyst First preparation example: Preparation of S1, MgO-ZrO2-Hβ composite support: S11. Preparation of metal salt solution: Weigh 6.4 g of Mg(NO3)2・6H2O and 15.7 g of Zr(NO3)4・5H2O, dissolve them in 200 mL of water, and stir until completely dissolved to form a metal salt solution; S12. Preparation of molecular sieve suspension: Add 12.8 g of Hβ molecular sieve to 200 mL of water and disperse by ultrasonication at 100 Hz for 30 min to form Hβ molecular sieve suspension. S13. Take 100 mL of the metal salt solution of S11 and 100 mL of the molecular sieve suspension of S12, place them in a three-necked flask, and put the mixture in a water bath, keeping the system temperature within the range of 30℃-50℃. At the same time, while stirring at 400 rpm, add 8% ammonia water dropwise to the system at a rate of 1-2 mL / min. When the pH value of the system is within the range of 9-10, stop adding ammonia water. After the addition is complete, continue stirring for 2 hours, then stop stirring and let it stand for 10 hours. During the aging process, keep the system temperature within the range of 30-60℃. After aging, filter and place the filter cake in an oven to dry for 20 hours within the range of 80℃-100℃. After drying, it is ground into powder and placed in a muffle furnace. The temperature is controlled at 2-5℃ / min and calcined at 500℃-600℃ for 5 hours. After calcination, it is naturally cooled to room temperature and the powder is taken out, which is the MgO-ZrO2-Hβ composite carrier. S2. Preparation of Pd / MgO-ZrO2-Hβ composite catalyst: Take 10 g of the MgO-ZrO2-Hβ composite support obtained in step S1 and add it to 4 mL of chloropalladium acid solution, wherein the content of Pd is 1% (mass concentration). After adding, let it stand for 12 h, and then dry it at 80 °C. The dried powder is then reduced with hydrogen at 300 °C-400 °C for 3 h to obtain the composite catalyst. Second preparation example: Preparation of S1, MgO-ZrO2-Hβ composite support: S11. Preparation of metal salt solution: Weigh 12.8 g of Mg(NO3)2・6H2O and 28.9 g of Zr(NO3)4・5H2O, dissolve them in 200 mL of water, and stir until completely dissolved to form a metal salt solution; S12. Preparation of molecular sieve suspension: Add 8.3 g of Hβ molecular sieve to 200 mL of water and disperse by ultrasonication at 100 Hz for 30 min to form Hβ molecular sieve suspension. S13. Take 100 mL of the metal salt solution of S11 and 100 mL of the molecular sieve suspension of S12, place them in a three-necked flask, and put the mixture in a water bath, keeping the system temperature within the range of 30℃-50℃. At the same time, while stirring at 400 rpm, add 8% ammonia water dropwise to the system at a rate of 1-2 mL / min. When the pH value of the system is within the range of 9-10, stop adding ammonia water. After the addition is complete, continue stirring for 2 hours, then stop stirring and let it stand for 10 hours. During the aging process, keep the system temperature within the range of 30-60℃. After aging, filter and place the filter cake in an oven to dry for 20 hours within the range of 80℃-100℃. After drying, it is ground into powder and placed in a muffle furnace. The temperature is controlled at 2-5℃ / min and calcined at 500℃-600℃ for 5 hours. After calcination, it is naturally cooled to room temperature and the powder is taken out, which is the MgO-ZrO2-Hβ composite carrier. S2. Preparation of Pd / MgO-ZrO2-Hβ composite catalyst: Take 10 g of the MgO-ZrO2-Hβ composite support obtained in step S1 and add it to 4 mL of chloropalladium acid solution, wherein the content of Pd is 1.5% (mass concentration). After adding, let it stand for 12 h, and then dry it at 80 °C. The dried powder is then reduced with hydrogen at 300 °C-400 °C for 3 h to obtain the composite catalyst. Third preparation example: Preparation of S1, MgO-ZrO2-Hβ composite support: S11. Preparation of metal salt solution: Weigh 20.5 g of Mg(NO3)2・6H2O and 38.5 g of Zr(NO3)4・5H2O, dissolve them in 200 mL of water, and stir until completely dissolved to form a metal salt solution; S12. Preparation of molecular sieve suspension: Add 6.2 g of Hβ molecular sieve to 200 mL of water and disperse by ultrasonication at 100 Hz for 30 min to form Hβ molecular sieve suspension. S13. Take 100 mL of the metal salt solution of S11 and 100 mL of the molecular sieve suspension of S12, place them in a three-necked flask, and put the mixture in a water bath, keeping the system temperature within the range of 30℃-50℃. At the same time, while stirring at 400 rpm, add 8% ammonia water dropwise to the system at a rate of 1-2 mL / min. When the pH value of the system is within the range of 9-10, stop adding ammonia water. After the addition is complete, continue stirring for 2 hours, then stop stirring and let it stand for 10 hours. During the aging process, keep the system temperature within the range of 30-60℃. After aging, filter and place the filter cake in an oven to dry for 20 hours within the range of 80℃-100℃. After drying, it is ground into powder and placed in a muffle furnace. The temperature is controlled at 2-5℃ / min and calcined at 500℃-600℃ for 5 hours. After calcination, it is naturally cooled to room temperature and the powder is taken out, which is the MgO-ZrO2-Hβ composite carrier. S2. Take 10 g of the MgO-ZrO2-Hβ composite support obtained in step S1 and add it to 4 mL of chloropalladium acid solution, wherein the Pd content is 2% (mass concentration). After adding, let it stand for 12 h, and then dry it at 80℃. Reduce the dried powder with hydrogen at 300℃-400℃ for 3 h to obtain the composite catalyst. Fourth preparation example: Preparation of S1, MgO-ZrO2-Hβ composite support: S11. Preparation of metal salt solution: Weigh 29.3 g of Mg(NO3)2・6H2O and 49.5 g of Zr(NO3)4・5H2O, dissolve them in 200 mL of water, and stir until completely dissolved to form a metal salt solution; S12. Preparation of molecular sieve suspension: Add 3.8 g of Hβ molecular sieve to 200 mL of water and disperse by ultrasonication at 100 Hz for 30 min to form Hβ molecular sieve suspension. S13. Take 100 mL of the metal salt solution of S11 and 100 mL of the molecular sieve suspension of S12, place them in a three-necked flask, and put the mixture in a water bath, keeping the system temperature within the range of 30℃-50℃. At the same time, while stirring at 400 rpm, add 8% ammonia water dropwise to the system at a rate of 1-2 mL / min. When the pH value of the system is within the range of 9-10, stop adding ammonia water. After the addition is complete, continue stirring for 2 hours, then stop stirring and let it stand for 10 hours. During the aging process, keep the system temperature within the range of 30-60℃. After aging, filter and place the filter cake in an oven to dry for 20 hours within the range of 80℃-100℃. After drying, it is ground into powder and placed in a muffle furnace. The temperature is controlled at 2-5℃ / min and calcined at 500℃-600℃ for 5 hours. After calcination, it is naturally cooled to room temperature and the powder is taken out, which is the MgO-ZrO2-Hβ composite carrier. S2. Take 10 g of the MgO-ZrO2-Hβ composite support obtained in step S1 and add it to 4 mL of chloropalladium acid solution, wherein the Pd content is 2.5% (mass concentration). After adding, let it stand for 12 h, then dry it at 80 °C. Reduce the dried powder with hydrogen at 300 °C-400 °C for 3 h to obtain the composite catalyst. Example 2: Application of Composite Catalyst First Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the first preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed that acetone accounted for 37.80%, isobutyraldehyde 0.27%, MIBK and intermediates 1.02%, MIAK content 56.3%, 542K 1.23%, and high-boiling-point compounds 1.97%. The chromatogram is shown below. Figure 1 As shown, acetone was produced at 3.454 min, isobutyraldehyde at 3.712 min, and MIAK at 7.229 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0025] Second Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the first preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 110℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed that acetone accounted for 40.13%, isobutyraldehyde 0.47%, MIBK and intermediates 1.36%, MIAK content 45.2%, 542K 4.13%, and high-boiling-point compounds 8.46%. The chromatogram is shown below. Figure 2 As shown, acetone was produced at 3.525 min, isobutyraldehyde at 3.737 min, and MIAK at 7.238 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0026] Third Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the first preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 3MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 3MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.55% acetone, 0.36% isobutyraldehyde, 1.24% MIBK and intermediates, 45.4% MIAK, 5.89% 542K, and 7.13% high-boiling-point compounds. The chromatogram is shown below. Figure 3 As shown, acetone was produced at 3.525 min, isobutyraldehyde at 3.734 min, and MIAK at 7.231 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0027] Fourth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 5g of Pd / MgO-ZrO2-Hβ from the first preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.80% acetone, 0.31% isobutyraldehyde, 1.12% MIBK and intermediates, 46.4% MIAK, 4.88% 542K, and 6.96% high-boiling-point compounds. The chromatogram is shown below. Figure 4As shown, acetone was produced at 3.533 min, isobutyraldehyde at 3.467 min, and MIAK at 7.296 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0028] Fifth Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the first preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.62% acetone, 1.27% isobutyraldehyde, 2.1% MIBK and intermediates, 42.3% MIAK, 6.21% 542K, and 8.36% high-boiling-point compounds. The chromatogram is shown below. Figure 5 As shown, acetone was produced at 3.549 min, isobutyraldehyde at 3.780 min, and MIAK at 7.213 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0029] Sixth Application Experiment Example In a 1000 mL hydrogenation reactor, 400 g of acetone and 124 g of isobutyraldehyde were added, along with 4 g of the catalyst Pd / MgO-ZrO2-Hβ recovered from five application experiments (from the first to the fifth). The reactor was sealed, purged with hydrogen, and stirred. Hydrogen was added to adjust the pressure inside the reactor to 2 MPa, maintaining the temperature below 95°C and the pressure at approximately 2 MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.62% acetone, 1.27% isobutyraldehyde, 2.1% MIBK and intermediates, 42.3% MIAK, 6.21% 542K, and 8.36% high-boiling-point compounds. The chromatogram is shown below. Figure 5 As shown, the composition includes acetone 38.50%, isobutyraldehyde 0.57%, MIBK and intermediates 1.42%, MIAK 54.1%, 542K 1.23%, and high-boiling-point compounds 1.97%. The chromatogram is shown below. Figure 6 As shown, acetone was present at 3.525 min, isobutyraldehyde at 3.737 min, and MIAK at 7.238 min. This demonstrates that the catalyst maintained good activity even after multiple recovery cycles in this experimental example.

[0030] Seventh Application Experiment Example In a 1000mL hydrogenation reactor, 350g of acetone, 50g of 2% NaOH solution (pH > 13), and 4g of Pd / MgO-ZrO2-Hβ from the first preparation example were added. After sealing the reactor, the mixture was purged with hydrogen. The reactor temperature was then set to 90℃ to activate the acetone, and stirring was started. By adding hydrogen, the pressure inside the reactor was adjusted to 2MPa. The liquid phase feed valve was opened, and n-butyraldehyde was continuously fed at a rate of 3ml / min, maintaining the reactor temperature below 95℃. The pressure was maintained at approximately 2 MPa. After continuous feeding for 30 minutes, the feed valve was closed, and feeding was stopped. The reaction was maintained under pressure and temperature conditions for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The results showed that acetone accounted for 38.58%, n-butyraldehyde 0.5%, MIBK and intermediates 3.78%, MAK content 41.62%, MAK intermediates 2.15%, n-butyraldehyde self-polymer 0.38%, and high-boiling-point compounds 9.53%. The chromatogram is shown below. Figure 7 As shown, acetone was present at 3.763 min, butyraldehyde at 4.035 min, and MAK at 11.129 min.

[0031] Eighth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the second preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 36.70% acetone, 0.17% isobutyraldehyde, 1.42% MIBK and intermediates, 58.3% MIAK, 1.34% 542K, and 2.07% high-boiling-point compounds. The chromatogram is shown below. Figure 8 As shown, acetone was produced at 3.580 min, isobutyraldehyde at 3.811 min, and MIAK at 7.283 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0032] Ninth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the second preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 110℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.13% acetone, 0.37% isobutyraldehyde, 1.36% MIBK and intermediates, 46.55% MIAK, 4.13% 542K, and 8.46% high-boiling-point compounds. The chromatogram is shown below. Figure 9 As shown, acetone was produced at 3.556 min, isobutyraldehyde at 3.764 min, and MIAK at 7.218 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0033] Tenth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the second preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 3MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 3MPa. The reaction was maintained at this pressure and temperature for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed that the acetone content was 38.55%, isobutyraldehyde 0.26%, MIBK and intermediates 1.24%, MIAK content 47.4%, 542K 5.89%, and high-boiling-point compounds 6.66%. The chromatogram is shown below. Figure 10 As shown, acetone was produced at 3.613 min, isobutyraldehyde at 3.822 min, and MIAK at 7.261 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0034] Eleventh Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 5g of Pd / MgO-ZrO2-Hβ from the second preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.80% acetone, 0.31% isobutyraldehyde, 1.12% MIBK and intermediates, 46.93% MIAK, 4.88% 542K, and 6.96% high-boiling-point compounds. The chromatogram is shown below. Figure 11As shown, acetone was produced at 3.612 min, isobutyraldehyde at 3.458 min, and MIAK at 7.280 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0035] Twelfth Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the second preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. The pressure inside the reactor was adjusted to 2MPa by adding hydrogen gas, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen gas. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The contents were: acetone 38.21%, isobutyraldehyde 1.17%, MIBK and intermediates 2.2%, MIAK content 43.3%, 542K 6.21%, and high-boiling-point substances 8.91%. The chromatogram is shown below. Figure 12 As shown, acetone was produced at 3.615 min, isobutyraldehyde at 3.853 min, and MIAK at 7.290 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0036] Thirteenth Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of the catalyst Pd / MgO-ZrO2-Hβ recovered from five applications (Examples 8 to 12) were added. The reactor was sealed, purged with hydrogen, and stirred. The pressure inside the reactor was adjusted to 2MPa by adding hydrogen, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 38.12% acetone, 1.17% isobutyraldehyde, 2.1% MIBK and intermediates, 43.74% MIAK, 6.21% 542K, and 8.66% high-boiling-point compounds. The chromatogram is shown below. Figure 5 As shown, the composition includes acetone 38.50%, isobutyraldehyde 0.57%, MIBK and intermediates 1.42%, MIAK 54.1%, 542K 1.23%, and high-boiling-point compounds 1.97%. The chromatogram is shown below. Figure 13 As shown, acetone was present at 3.611 min, isobutyraldehyde at 3.457 min, and MIAK at 7.282 min. This demonstrates that the catalyst maintained good activity even after multiple recovery cycles in this experimental example.

[0037] Fourteenth Application Experiment Example In a 1000mL hydrogenation reactor, 350g of acetone, 50g of 2% NaOH solution (pH > 13), and 4g of Pd / MgO-ZrO2-Hβ (from the second preparation example) were added. After sealing the reactor, the mixture was purged with hydrogen. The reactor temperature was then set to 90℃ to activate the acetone, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa. The liquid feed valve was opened, and n-butyraldehyde was continuously fed at a rate of 3ml / min, maintaining the reactor temperature below 95℃. The pressure was maintained at approximately 2 MPa. After continuous feeding for 30 minutes, the feed valve was closed, and feeding was stopped. The reaction was maintained under pressure and temperature conditions for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The results showed that acetone accounted for 36.58%, n-butyraldehyde 0.3%, MIBK and intermediates 3.78%, MAK content 46.62%, MAK intermediates 2.65%, n-butyraldehyde self-polymer 0.48%, and high-boiling-point compounds 9.59%. The chromatogram is shown below. Figure 14 As shown, acetone was produced at 3.764 min, butyraldehyde at 4.036 min, and MAK at 11.120 min. This demonstrates that in this experimental example, butyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0038] Fifteenth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the third preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed that the acetone content was 35.70%, isobutyraldehyde 0.17%, MIBK and intermediates 1.4%, MIAK content 59.5%, 542K 1.3%, and high-boiling-point compounds 2.11%. The chromatogram is shown below. Figure 15 As shown, acetone was produced at 3.609 min, isobutyraldehyde at 3.456 min, and MIAK at 7.261 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0039] Sixteenth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the third preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 110℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 38.13% acetone, 0.3% isobutyraldehyde, 1.43% MIBK and intermediates, 47.55% MIAK, 4.19% 542K, and 8.4% high-boiling-point compounds. The chromatogram is shown below. Figure 16 As shown, acetone was produced at 3.608 min, isobutyraldehyde at 3.455 min, and MIAK at 7.266 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0040] Seventeenth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the third preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 3MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 3MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 37.55% acetone, 0.2% isobutyraldehyde, 1.14% MIBK and intermediates, 48.4% MIAK, 542K 5.99%, and 6.66% high-boiling-point compounds. The chromatogram is shown below. Figure 17 As shown, acetone was produced at 3.582 min, isobutyraldehyde at 3.429 min, and MIAK at 7.240 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0041] Eighteenth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 5g of Pd / MgO-ZrO2-Hβ from the third preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 38.80% acetone, 0.21% isobutyraldehyde, 1.12% MIBK and intermediates, 48.03% MIAK, 4.88% 542K, and 6.96% high-boiling-point compounds. The chromatogram is shown below. Figure 18As shown, acetone was produced at 3.614 min, isobutyraldehyde at 3.828 min, and MIAK at 7.284 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0042] Nineteenth Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the third preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 37.21% acetone, 1.07% isobutyraldehyde, 2.2% MIBK and intermediates, 44.4% MIAK, 6.1% 542K, and 9.01% high-boiling-point compounds. The chromatogram is shown below. Figure 19 As shown, acetone was produced at 3.611 min, isobutyraldehyde at 3.457 min, and MIAK at 7.301 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0043] Twentieth Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of the catalyst Pd / MgO-ZrO2-Hβ recovered from five applications (fifteenth to nineteenth examples) were added. The reactor was sealed, purged with hydrogen, and stirred. The pressure inside the reactor was adjusted to 2MPa by adding hydrogen, maintaining the temperature below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 35.12% acetone, 1.0% isobutyraldehyde, 2.1% MIBK and intermediates, 46.81% MIAK, 6.27% 542K, and 8.6% high-boiling-point compounds. The chromatogram is shown below. Figure 20 As shown, acetone was present at 3.611 min, isobutyraldehyde at 3.457 min, and MIAK at 7.280 min. This demonstrates that the catalyst maintained good activity even after multiple recovery cycles in this experimental example.

[0044] Twenty-first Application Experiment Example In a 1000mL hydrogenation reactor, 350g of acetone, 50g of 2% NaOH solution (pH > 13), and 4g of Pd / MgO-ZrO2-Hβ (from the third preparation example) were added. After sealing the reactor, the mixture was purged with hydrogen. The reactor temperature was then set to 90℃ to activate the acetone, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa. The liquid feed valve was opened, and n-butyraldehyde was continuously fed at a rate of 3ml / min, maintaining the reactor temperature below 95℃. The pressure was maintained at approximately 2 MPa. After continuous feeding for 30 minutes, the feed valve was closed, and feeding was stopped. The reaction was maintained under pressure and temperature conditions for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The results showed that acetone accounted for 36.0%, n-butyraldehyde 0.28%, MIBK and intermediates 3.78%, MAK content 47.22%, MAK intermediates 2.65%, n-butyraldehyde self-polymer 0.48%, and high-boiling-point compounds 9.59%. The chromatogram is shown below. Figure 21 As shown, acetone was produced at 3.769 min, butyraldehyde at 4.042 min, and MAK at 11.112 min. This demonstrates that in this experimental example, butyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0045] Twenty-two Application Experiment Examples In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ (from the fourth preparation example) were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes. The pressure was maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 38.52% acetone, 0.16% isobutyraldehyde, 4.4% MIBK and intermediates, 53.6% MIAK, 1.4% 542K, and 1.92% high-boiling-point compounds. The chromatogram is shown below. Figure 22 As shown, acetone was produced at 3.615 min, isobutyraldehyde at 3.833 min, and MIAK at 7.307 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0046] Twenty-three Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the fourth preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 110℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.23% acetone, 0.3% isobutyraldehyde, 1.33% MIBK and intermediates, 46.55% MIAK, 4.19% 542K, and 8.4% high-boiling-point compounds. The chromatogram is shown below. Figure 23 As shown, acetone was produced at 3.608 min, isobutyraldehyde at 3.455 min, and MIAK at 7.270 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0047] Twenty-fourth Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the fourth preparation example were added. After sealing the reactor, hydrogen gas was used to purge the mixture, and stirring was started. Hydrogen gas was added to adjust the pressure inside the reactor to 3MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 3MPa. The reaction was maintained at this pressure and temperature for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed that the acetone content was 36.35%, isobutyraldehyde 0.23%, MIBK and intermediates 1.15%, MIAK content 49.4%, 542K 6.1%, and high-boiling-point compounds 6.86%. The chromatogram is shown below. Figure 24 As shown, acetone was produced at 3.612 min, isobutyraldehyde at 3.458 min, and MIAK at 7.285 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0048] Twenty-Five Application Experiment Example In a 1000mL hydrogenation reactor, 300g of acetone, 124g of isobutyraldehyde, and 5g of Pd / MgO-ZrO2-Hβ (from the fourth preparation example) were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction, the temperature was lowered, and samples were taken for analysis. The results showed 39.70% acetone, 0.29% isobutyraldehyde, 1.22% MIBK and intermediates, 47.75% MIAK, 4.68% 542K, and 6.36% high-boiling-point compounds. The chromatogram is shown below. Figure 25As shown, acetone was produced at 3.611 min, isobutyraldehyde at 3.458 min, and MIAK at 7.290 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0049] Twenty-sixth Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of Pd / MgO-ZrO2-Hβ from the fourth preparation example were added. After sealing the reactor, hydrogen was used to purge the mixture, and stirring was started. The pressure inside the reactor was adjusted to 2MPa by adding hydrogen, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The results showed 34.61% acetone, 1.01% isobutyraldehyde, 2.25% MIBK and intermediates, 46.5% MIAK, 6.6% 542K, and 9.03% high-boiling-point compounds. The chromatogram is shown below. Figure 26 As shown, acetone was produced at 3.610 min, isobutyraldehyde at 3.457 min, and MIAK at 7.297 min. This demonstrates that in this experimental example, isobutyraldehyde exhibits high conversion rate, few byproducts, and high product selectivity.

[0050] Twenty-seventh Application Experiment Example In a 1000mL hydrogenation reactor, 400g of acetone, 124g of isobutyraldehyde, and 4g of the catalyst Pd / MgO-ZrO2-Hβ recovered from the 22nd to 26th reactions were added. After sealing the reactor, hydrogen was used to purge the reaction mixture, and stirring was started. The pressure inside the reactor was adjusted to 2MPa by adding hydrogen, maintaining the temperature inside the reactor below 95℃ and the pressure at approximately 2MPa. The reaction was maintained at this pressure and temperature for 40 minutes, with the pressure maintained by introducing hydrogen. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The results showed 38.12% acetone, 1.1% isobutyraldehyde, 2.0% MIBK and intermediates, 44.41% MIAK, 6.37% 542K, and 8.0% high-boiling-point compounds. The chromatogram is shown below. Figure 27 As shown, acetone was present at 3.609 min, isobutyraldehyde at 3.456 min, and MIAK at 7.275 min. This demonstrates that the catalyst maintained good activity even after multiple recovery cycles in this experimental example.

[0051] Twenty-eighth Application Experiment Example In a 1000mL hydrogenation reactor, 350g of acetone, 50g of 2% NaOH solution (pH > 13), and 4g of Pd / MgO-ZrO2-Hβ (from the fourth preparation example) were added. After sealing the reactor, the mixture was purged with hydrogen. The reactor temperature was then set to 90℃ to activate the acetone, and stirring was started. Hydrogen was added to adjust the pressure inside the reactor to 2MPa. The liquid phase feed valve was opened, and n-butyraldehyde was continuously fed at a rate of 3ml / min, maintaining the reactor temperature below 95℃. The pressure was maintained at approximately 2 MPa. After continuous feeding for 30 minutes, the feed valve was closed, and feeding was stopped. The reaction was maintained under pressure and temperature conditions for 40 minutes. The pressure was maintained by introducing hydrogen gas. After the reaction was completed, the temperature was lowered, and samples were taken for analysis. The results showed that acetone accounted for 37.8%, n-butyraldehyde 0.35%, MIBK and intermediates 3.28%, MAK content 48.32%, MAK intermediates 2.38%, n-butyraldehyde self-polymer 0.41%, and high-boiling-point substances 7.46%. The chromatogram is shown below. Figure 28 As shown, acetone was produced at 3.765 min, butyraldehyde at 4.037 min, and MAK at 11.137 min. This demonstrates that in this experimental example, butyraldehyde exhibited high conversion rate, few byproducts, and high product selectivity.

[0052] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A composite catalyst, characterized in that, The composite catalyst is Pd / MgO-ZrO2-Hβ, obtained by the following method: S1. An alkaline solution is added to a system containing Hβ molecular sieve, magnesium ions and zirconium ions to obtain a precipitate. The precipitate is filtered, dried, ground and calcined to obtain a MgO-ZrO2-Hβ composite carrier. S2. The MgO-ZrO2-Hβ composite support obtained in S1 is mixed with a palladium-containing solution and allowed to stand. After drying and reduction with a reducing agent, the Pd / MgO-ZrO2-Hβ composite catalyst is obtained.

2. The composite catalyst as described in claim 1, characterized in that, In S1, the system containing Hβ molecular sieve, magnesium ions and zirconium ions is obtained by mixing a suspension containing Hβ molecular sieve with a metal salt solution containing magnesium ions and zirconium ions, wherein the volume ratio of the suspension containing Hβ molecular sieve to the metal salt solution is 1:0.5-1.

5.

3. The composite catalyst as described in claim 2, characterized in that, The mass concentration of Hβ molecular sieve in the suspension containing Hβ molecular sieve is 1%-10%; In the metal salt solution, the molar concentration of magnesium ions is 0.08-0.8 mol / L, and the concentration of zirconium ions is 0.08-0.8 mol / L.

4. The composite catalyst as described in claim 1, characterized in that, The alkaline solution in S1 is added dropwise at a rate of 1-2 mL / min. During the dropwise addition, the temperature of the system is maintained between 30-50℃. When the pH of the system reaches 9-10, the addition of the alkaline solution is stopped.

5. The composite catalyst as described in claim 1, characterized in that, The alkaline solution in S1 is ammonia water with a mass concentration of 5%-10%.

6. The composite catalyst as described in claim 1, characterized in that, In S1, after the alkaline solution is added, the solution is allowed to stand at 30-60℃ for 6-12 hours. The calcination temperature is 500℃-600℃, and the time is 4-6 hours.

7. The composite catalyst as described in claim 1, characterized in that, In S2, the palladium-containing solution includes chloropalladic acid solution, palladium chloride, and tetraamminepalladium chloride, wherein the mass concentration of palladium ions is 0.5-2.5%.

8. The composite catalyst as described in claim 1, characterized in that, The settling time in S2 is 6-15 hours; The reducing agent is hydrogen gas, and the reduction process involves introducing hydrogen gas at 300℃-400℃ for 2-5 hours.

9. The use of a composite catalyst as described in any one of claims 1-8 in a reaction that simultaneously involves aldol condensation and catalytic hydrogenation.

10. The application as described in claim 9, characterized in that, Simultaneous aldol condensation and catalytic hydrogenation reactions include one or more of the following reactions: MIAK was synthesized in one step using acetone and isobutyraldehyde as raw materials. MIBK is synthesized in one step using acetone as a raw material; MAK was synthesized in one step from acetone and n-butyraldehyde. MIPK was synthesized in one step using butanone and formaldehyde aqueous solution as raw materials.

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