A dehydrogenation catalyst, a method for preparing the same, and use thereof in the preparation of aldehyde or ketone compounds

Abstract

The application discloses a preparation method of aldehyde or ketone compounds and a catalyst thereof. The preparation method comprises the following steps: under the action of a dehydrogenation catalyst, alcohol compounds are subjected to a dehydrogenation reaction to obtain the aldehyde or ketone compounds. The method can catalyze the synthesis of aldehyde and ketone from alcohol compounds under mild reaction conditions by adopting a new dehydrogenation catalyst, can effectively reduce the reaction temperature, reduce the side reactions of the generated products caused by high temperature, reduce the generation of leftovers, and has the characteristics of high safety, high conversion rate, high selectivity, low energy consumption and the like.

Description

Technical Field

[0001] This invention belongs to the field of fine chemicals, specifically relating to a dehydrogenation catalyst, its preparation method, and its application in the preparation of aldehydes or ketones. Background Technology

[0002] Aldehydes / ketone carbonyl compounds are important chemical raw materials, widely used in pharmaceuticals, dyes, food, fragrances, and organic synthesis, possessing broad application value and high economic value. Aldehydes / ketone carbonyl compounds can undergo almost all types of organic transformations, such as oxidation, reduction, condensation, addition, cycloaddition, coupling, and polymerization reactions. Therefore, aldehydes / ketone carbonyl compounds play an irreplaceable role in organic synthesis and industrial applications, making their efficient synthesis of significant theoretical and practical value.

[0003] Patent US3940446 describes a gas-phase dehydrogenation reaction to prepare aldehydes or ketones using copper oxide as a catalyst and a semi-continuous feed of alcohols at a reaction temperature of 200-350°C and a vacuum of 12-20 kPa. To improve selectivity, a large amount of high-boiling-point solvent was added to the reaction system, ultimately achieving a conversion rate of 55.6% and a yield of 88.5%. However, because the products cannot be removed from the reaction system in a timely manner, the heat-sensitive raw materials and their products decompose or polymerize at high temperatures and accumulate within the reaction system, inhibiting or poisoning the catalyst activity and causing a rapid decrease in catalyst lifetime. Furthermore, the addition of a large amount of high-boiling-point solvent not only increases the difficulty of post-processing but also wastes energy.

[0004] Patent US4383124A discloses the use of a Cu / MgO catalyst to dehydrogenate alcohols in the gas phase to obtain the corresponding aldehydes, using monohydric primary alcohols with 2-20 carbon atoms as substrates under a nitrogen atmosphere at a reaction temperature of 225-350°C. However, there is considerable room for improvement in the yield of this method.

[0005] Patent CN111068668A discloses the use of a supported bimetallic catalyst to catalyze the oxidative dehydrogenation reaction of alcohols containing tertiary alcohol structures in an oxygen-containing atmosphere. The reaction is carried out at 80-150°C and a pressure of 0.1-2 MPa in a reactor such as a fixed bed, trickle bed, or reaction vessel, yielding the corresponding carbonyl compounds containing tertiary alcohol structures. The active components of the catalysts used in this method are precious metals such as palladium, gold, platinum, iridium, rhodium, ruthenium, and osmium, which are expensive, leading to high catalyst production costs. During the precious metal catalytic oxidation process, the catalyst is easily deactivated due to oxidation of the metal, loss and leaching of active centers, or blockage by byproducts.

[0006] Aldehydes / ketone carbonyl compounds are typically obtained through the selective oxidation of alcohols, with traditional aldehyde / ketone production processes often employing strong inorganic oxidants such as chromium salts and permanganates. This oxidation process frequently generates large amounts of toxic and hazardous waste, and removing these trace amounts of reagents from the reaction mixture or recycling the waste is extremely costly. In recent years, catalytic reaction systems using molecular oxygen, air, and hydrogen peroxide as inexpensive and clean oxidants have attracted considerable attention. However, aldehydes / ketone compounds are chemically reactive and unstable under oxidation conditions; in particular, aldehydes can be further oxidized to carboxylic acids, making the reaction difficult to control and leading to the formation of byproducts. Furthermore, the presence of oxidants under high temperature and pressure introduces potential safety hazards during operation, such as explosions, limiting the application and scale of this type of reaction.

[0007] The direct dehydrogenation of alcohols to aldehydes and ketones has been industrialized on a large scale, but most of these processes are carried out in the gas phase, resulting in problems such as high reaction temperatures, high energy consumption, and low equilibrium conversion rates due to temperature variations. Furthermore, the selective dehydrogenation of alcohols involves the transformation of various chemical bonds and functional groups, including CO, C=O, CH, and CC bonds, leading to numerous side reactions. The selective dehydrogenation of alcohols to aldehydes and ketones is often conducted at high temperatures, resulting not only in high energy consumption but also in the polymerization of the aldehydes and ketones under high-temperature conditions, leading to high reaction waste rates and low product yields.

[0008] Therefore, developing novel selective dehydrogenation catalysts that are environmentally friendly, economically sound, highly efficient, and easy to use is of great significance. Converting alcohols into corresponding carbonyl compounds such as aldehydes and ketones through simple and convenient methods facilitates the large-scale industrial production of aldehydes, ketones, and their downstream products, and has significant application value. Summary of the Invention

[0009] The technical problem solved by the invention

[0010] This invention provides a dehydrogenation catalyst, its preparation method, and its application in the preparation of aldehydes or ketones. Using this catalyst, under suitable reaction conditions, alcohol dehydrogenation can be efficiently catalyzed to prepare the corresponding aldehydes or ketones, overcoming problems such as high reaction temperature, low feed conversion rate, and difficulty in controlling side reactions in existing technologies. It offers advantages such as high safety, high yield, and low energy consumption. The dehydrogenation catalyst provided by this invention has a stable structure, excellent activity, and a wide range of applicable substrates. It can also be recovered and reused without deactivation.

[0011] Solution for solving the problem

[0012] To solve the above problems, the present invention specifically adopts the following technical solution:

[0013] A method for preparing a dehydrogenation catalyst includes the following steps:

[0014] (1) The pretreated support and active metal salt are mixed and stirred for adsorption, and then dried and calcined to obtain the catalyst intermediate;

[0015] (2) Add a ligand to the catalyst intermediate in step (1) for further modification to obtain the dehydrogenation catalyst.

[0016] In step (1), the carrier is a MOFs material with a macroporous structure, and the metal in the active metal salt is one, two or more of Cu, Bi, Zn and Ce;

[0017] In step (2), the ligand is a bidentate phosphine ligand.

[0018] In step (1), the pretreatment operation of the carrier is to activate it in a vacuum drying oven at 100-150℃ for 3-6 hours.

[0019] In step (1), the carrier is preferably one, two or more of MOF-5, MOF-117, MOF-200, MOF-801, MIL-53, MIL-101, and UiO-66; more preferably one, two or more of UiO-66, MOF-801, and MOF-117.

[0020] In step (1), preferably, the active metal salt includes a first active metal salt and a second active metal salt;

[0021] Wherein, the metal in the first active metal salt is Cu, and the metal in the second active metal salt is Zn, Bi, or Ce, or the metal in the first active metal salt is Zn, and the metal in the second active metal salt is Bi or Ce. Further, the specific type of the active metal salt is selected from nitrates, hydrochlorides, sulfates, acetates, ammonium salts, or their hydrates containing Cu, Bi, Zn, or Ce. Even further, the specific type of the active metal salt is selected from two of CuSO4·5H2O, Cu(OAc)2·H2O, Cu(NO3)2·3H2O, ZnSO4·3H2O, Bi(NO3)2·5H2O, Zn(NO3)2·6H2O, ZnCl2, and Ce(NH4)2(NO3)6.

[0022] In step (1), the adsorption is carried out in a solvent, which is water or other solvents that can dissolve the active metal salt, preferably water.

[0023] In step (2), the ligand is one, two or more of 1,2-bis(diphenylphosphine)ethane (DPPE), 1,3-bis(diphenylphosphine)propane (DPPP), and 1,4-bis(diphenylphosphine)butane (DPPB);

[0024] The organic solvent is a C1-C4 alkyl alcohol, more preferably anhydrous ethanol.

[0025] In step (2), the modification process is carried out in a solvent, preferably a dispersible organic ligand, which can be water or an organic solvent, without limitation.

[0026] In this invention, the mass ratio of the active metal salt to the carrier, based on metal content, is 1.0% to 10.0%:1; preferably 3.0% to 7.0%:1; more preferably 5.0% to 7.0%:1.

[0027] In this invention, the molar ratio of the active metal salt to the ligand is 1:2 to 10.0; preferably 6.0-10.0; more preferably 6.0-8.0.

[0028] Preferably, in step (1), the adsorption temperature is 40-80℃ and the adsorption time is 4-8h;

[0029] The roasting temperature is 300-500℃, and the roasting time is 6-10 hours;

[0030] In step (2), the modification temperature is 60-120℃, and the modification time is 4-8 hours.

[0031] The present invention also provides a dehydrogenation catalyst obtained by the above preparation method.

[0032] The present invention further provides a method for preparing aldehydes or ketones, wherein alcohols undergo a dehydrogenation reaction under the action of a dehydrogenation catalyst to obtain the aldehydes or ketones.

[0033] The reaction formula is as follows:

[0034]

[0035] R1 represents H, C1~C 10 Alkyl, C2-C 10 alkenyl, C6-C 10 Aryl group, R2 is H, C1-C 10 Alkyl, C2-C 10 alkenyl, C6-C 10 Aryl;

[0036] In this invention, the alcohol compounds are aromatic alcohols, fatty alcohols, or enols. Further, the aromatic alcohol is one, two, or more of benzyl alcohol, 4-methoxybenzyl alcohol, cinnamyl alcohol, 3,4-methylenedioxybenzyl alcohol, salicylyl alcohol, and 3,4-dimethoxybenzyl alcohol. The corresponding aldehyde or ketone compounds obtained are one, two, or more of benzaldehyde, 4-methoxybenzaldehyde, cinnamaldehyde, 3,4-methylenedioxybenzaldehyde, salicylaldehyde, and 3,4-dimethoxybenzaldehyde.

[0037] Further, the fatty alcohol is one, two, or more of the following: methanol, ethanol, n-pentanol, isopentanol, n-octanol, cyclopentanol, 2,3-butanediol, menthol, L-menthol, and 3,7-dimethyl-1,7-hydroxy-octanediol. The corresponding aldehyde or ketone compounds obtained are one, two, or more of the following: formaldehyde, acetaldehyde, n-pentanol, isopentanol, n-octanol, cyclopentanone, 3-hydroxy-2-butanone, menthone, L-menthone, and 7-hydroxy-3,7-dimethyl-octanol.

[0038] Further, the enol is one, two, or more of 3-methyl-3-buten-1-ol, 3-hexenol, 3-methyl-2-butenol, 3,7-dimethyl-6-octenol, geraniol, nerol, and 4-methyl-3-decen-5-ol. The corresponding aldehyde or ketone compounds obtained are one, two, or more of 3-methyl-3-butenal, 3-hexenal, 3-methyl-2-butenal, 3,7-dimethyl-6-octenal, geraniol, and nerol.

[0039] The mass ratio of the catalyst to the alcohol substrate is 3.0%-9.0%, preferably 3.0%-7.0%; more preferably 5.0%-7.0%.

[0040] The temperature of the dehydrogenation reaction is 120-180℃; preferably 140-180℃; more preferably 140-160℃.

[0041] The dehydrogenation reaction time is 2.0h-8.0h; preferably 4.0h-6.0h.

[0042] The dehydrogenation reaction can be carried out continuously or intermittently; intermittent feeding is preferred here.

[0043] This invention provides a novel supported dehydrogenation catalyst, composed of an active metal component, ligands, and a support. The ligands and metal atoms form stable coordination bonds, precisely constructing the active sites of the catalyst and giving it high activity. These firmly bonded coordination bonds also fix the active metal centers of the catalyst, preventing them from detaching or being lost. The support not only carries the active component but also possesses catalytic activity, synergistically promoting catalysis. The support has a high specific surface area and a well-developed microporous structure, allowing for adjustment of product selectivity by controlling the loading position of the active metal centers on the support. This suppresses side reactions, prevents catalyst poisoning due to adsorption of byproducts, and minimizes catalyst deactivation. Furthermore, this catalyst exhibits outstanding structural stability, enabling multiple uses and reducing production costs.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0045] (1) The synthesis method of aldehydes and ketones provided by the present invention can catalyze the synthesis of aldehydes and ketones from alcohols under mild reaction conditions, effectively reduce the reaction temperature, reduce the side reactions caused by high temperature of the generated products, and reduce the generation of waste materials. It has the characteristics of high safety, high conversion rate, high selectivity and low energy consumption.

[0046] (2) The novel supported catalyst used in this invention is easy to recover, has stable performance, and can be recycled, which not only effectively reduces production costs but also yields high-quality aldehyde and ketone products. Furthermore, the selective dehydrogenation catalyst provided by this invention has a wide range of substrate applicability and strong potential for widespread application. Attached Figure Description

[0047] Figure 1 This is a diagram of the reaction equipment used in the synthesis method of the present invention;

[0048] Figure 2 The gas chromatogram of Example 21;

[0049] Figure 3 This is the gas chromatogram of Example 28. Detailed Implementation

[0050] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0051] Example 1

[0052] Activate UiO-66 in a vacuum drying oven at 120℃ for 5 hours, then cool to room temperature for later use. At room temperature, add 1.965g of CuSO4·5H2O and 1.042g of ZnCl2 to 30mL of deionized water, stir until completely dissolved, then add 10.0g of the activated support UiO-66, heat to 40℃, stir at a constant temperature for 6 hours, then remove moisture by rotary evaporation under reduced pressure. Place the obtained solid in a muffle furnace and calcine at 450℃ for 8 hours, then cool to obtain the catalyst precursor, which is then ready for use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 49.442 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 80 °C and stirred at a constant temperature for 6 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 5% Cu-5% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8).

[0053] Example 2

[0054] Activate UiO-66 in a vacuum drying oven at 120℃ for 5 hours, then cool to room temperature for later use. At room temperature, add 2.750g of CuSO4·5H2O and 1.459g of ZnCl2 to 30mL of deionized water, stir until completely dissolved, then add 10.0g of the activated support UiO-66, heat to 40℃, stir at a constant temperature for 6 hours, then remove moisture by rotary evaporation under reduced pressure. Place the obtained solid in a muffle furnace and calcine at 450℃ for 8 hours, then cool to obtain the catalyst precursor, which is then ready for use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 69.22 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 80 °C and stirred at a constant temperature for 6 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8).

[0055] Example 3

[0056] Activate UiO-66 in a vacuum drying oven at 120℃ for 5 hours, then cool to room temperature for later use. At room temperature, add 2.75g of CuSO4·5H2O and 1.042g of ZnCl2 to 30mL of deionized water, stir until completely dissolved, then add 10.0g of the activated support UiO-66, heat to 40℃, stir at a constant temperature for 6 hours, then remove moisture by rotary evaporation under reduced pressure. Place the obtained solid in a muffle furnace and calcine at 450℃ for 8 hours, then cool to obtain the catalyst precursor, which is then ready for use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 59.47 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 80 °C and stirred at a constant temperature for 6 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Cu-5% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8).

[0057] Example 4

[0058] Activate UiO-66 in a vacuum drying oven at 120℃ for 5 hours, then cool to room temperature for later use. At room temperature, add 0.393g of CuSO4·5H2O and 1.875g of ZnCl2 to 30mL of deionized water, stir until completely dissolved, then add 10.0g of the activated support UiO-66, heat to 40℃, stir at a constant temperature for 6 hours, then remove moisture by rotary evaporation under reduced pressure. Place the obtained solid in a muffle furnace and calcine at 450℃ for 8 hours, then cool to obtain the catalyst precursor, which is then ready for use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 48.84 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 80 °C and stirred at a constant temperature for 6 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 1% Cu-9% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8).

[0059] Example 5

[0060] MIL-101 was activated in a vacuum drying oven at 150℃ for 3 hours, then cooled to room temperature for later use. At room temperature, 1.571g of Cu(OAc)2·H2O and 1.624g of Bi(NO3)2·5H2O were added to 30mL of deionized water and stirred until completely dissolved. Then, 10.0g of the activated support MIL-101 was added, the temperature was raised to 80℃, and the mixture was stirred at a constant temperature for 4 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 41.64 g of DPPP. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 60 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 5% Cu-7% Bi / MIL-101-DPPP (metal:ligand molar ratio of 1:9).

[0061] Example 6

[0062] MIL-53 was activated in a vacuum drying oven at 150℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 1.901 g of Cu(NO3)2·3H2O and 3.522 g of Ce(NH4)2(NO3)6 were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support MIL-53 was added, the temperature was raised to 40℃, and the mixture was stirred at a constant temperature for 6 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 300℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 36.57 g of DPPB. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 40 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 5% Cu-9% Ce / MIL-53-DPPB (metal:ligand molar ratio of 1:6).

[0063] Example 7

[0064] MOF-801 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 3.077 g of ZnSO4·7H2O and 1.625 g of Bi(NO3)2·5H2O were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support MOF-801 was added, the temperature was raised to 40℃, and the mixture was stirred at a constant temperature for 6 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 27.99 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 40 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Zn-7% Bi / MOF-801-DPPE (metal:ligand molar ratio of 1:5).

[0065] Example 8

[0066] MOF-801 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 3.077 g of ZnSO4·7H2O and 1.625 g of Bi(NO3)2·5H2O were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support MOF-801 was added, the temperature was raised to 40℃, and the mixture was stirred at a constant temperature for 6 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 55.98 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 50 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Zn-7% Bi / MOF-801-DPPE (metal:ligand molar ratio of 1:10).

[0067] Example 9

[0068] MOF-801 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 3.957 g of ZnSO4·7H2O and 2.089 g of Bi(NO3)2·5H2O were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support MOF-801 was added, the temperature was raised to 40℃, and the mixture was stirred at a constant temperature for 6 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 50 mL of anhydrous ethanol was added, followed by 14.40 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 50 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 9% Zn-9% Bi / MOF-801-DPPE (metal:ligand molar ratio of 1:2).

[0069] Example 10

[0070] MOF-117 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 3.184 g of Zn(NO3)2·6H2O and 3.522 g of Ce(NH4)2(NO3)6 were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support MOF-117 was added, the temperature was raised to 60℃, and the mixture was stirred at a constant temperature for 5 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 56.51 g of DPPP. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 50 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Zn-9% Ce / MOF-117-DPPP (metal:ligand molar ratio of 1:8).

[0071] Example 11

[0072] MOF-5 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 2.274 g of Zn(NO3)2·6H2O and 3.913 g of Ce(NH4)2(NO3)6 were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated MOF-5 support was added, the temperature was raised to 60℃, and the mixture was stirred at a constant temperature for 5 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 300℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 63.04 g of DPPB. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 50 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 5% Zn-10% Ce / MOF-5-DPPB (metal:ligand molar ratio of 1:10).

[0073] Example 12

[0074] MIL-101 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 2.661g of Cu(NO3)2·3H2O and 3.522g of Ce(NH4)2(NO3)6 were added to 30mL of deionized water and stirred until completely dissolved. Then, 10.0g of the activated support MIL-101 was added, the temperature was raised to 60℃, and the mixture was stirred at a constant temperature for 5 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 55.58 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 60 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Cu-10% Ce / MIL-101-DPPE (metal:ligand molar ratio of 1:8).

[0075] Example 13

[0076] MIL-801 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 1.571 g of Cu(OAc)2·H2O and 2.089 g of Bi(NO3)2·5H2O were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support MIL-801 was added, the temperature was raised to 60℃, and the mixture was stirred at a constant temperature for 5 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 350℃ for 10 hours. After cooling, the catalyst precursor was obtained and set aside for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 55.58 g of DPPE. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 60 °C and stirred at a constant temperature for 8 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 5% Cu-9% Bi / MIL-801-DPPE (metal:ligand molar ratio of 1:8).

[0077] Comparative Example 1

[0078] Activate UiO-66 in a vacuum drying oven at 120℃ for 5 hours, then cool to room temperature for later use. At room temperature, add 2.199g of Cu(OAc)2·H2O to 30mL of deionized water, stir until completely dissolved, then add 10.0g of the activated support UiO-66, heat to 40℃, stir at a constant temperature for 6 hours, then remove water by rotary evaporation under reduced pressure. Place the resulting solid in a muffle furnace and calcine at 450℃ for 8 hours, then cool to obtain the catalyst precursor, which is then set aside for later use. In a 250ml three-necked flask, add 80mL of anhydrous ethanol, then add 43.89g of DPPE, stir thoroughly to ensure uniform dispersion, then add the calcined catalyst precursor, heat to 80℃, stir at a constant temperature for 6 hours, remove the solvent by rotary evaporation under reduced pressure to obtain a solid powder, and dry thoroughly to constant weight to obtain the catalyst 7% Cu / UiO-66-DPPE (metal:ligand molar ratio of 1:10).

[0079] Comparative Example 2

[0080] UiO-66 was activated in a vacuum drying oven at 120℃ for 5 hours, then cooled to room temperature for later use. At room temperature, 2.199 g of Cu(OAc)2·H2O and 1.875 g of ZnCl2 were added to 30 mL of deionized water and stirred until completely dissolved. Then, 10.0 g of the activated support UiO-66 was added, the temperature was raised to 40℃, and the mixture was stirred at a constant temperature for 6 hours. The water was then removed by rotary evaporation under reduced pressure. The resulting solid was placed in a muffle furnace and calcined at 450℃ for 8 hours. After cooling, the catalyst 7% Cu-9% Zn / UiO-66 was obtained.

[0081] Comparative Example 3

[0082] Activate UiO-66 in a vacuum drying oven at 120℃ for 5 hours, then cool to room temperature for later use. At room temperature, add 2.199g of Cu(OAc)2·H2O and 1.875g of ZnCl2 to 30mL of deionized water, stir until completely dissolved, then add 10.0g of the activated support UiO-66, heat to 40℃, stir at a constant temperature for 6 hours, then remove moisture by rotary evaporation under reduced pressure. Place the obtained solid in a muffle furnace and calcine at 450℃ for 8 hours, then cool to obtain the catalyst precursor, which is then taken out for later use. In a 250 ml three-necked flask, 80 mL of anhydrous ethanol was added, followed by 64.98 g of triphenylphosphine. The mixture was stirred thoroughly to ensure uniform dispersion. Then, the calcined catalyst precursor was added, and the mixture was heated to 80 °C and stirred at a constant temperature for 6 hours. The solvent was removed by rotary evaporation under reduced pressure to obtain a solid powder. The powder was dried thoroughly to constant weight to obtain the catalyst 7% Cu-9% Zn / UiO-66-TPP (metal:ligand molar ratio of 1:10).

[0083] Example 14

[0084] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the mixture was purged with nitrogen three times, and then 100g of 3,4-methylenedioxybenzyl alcohol and 5.0g of catalyst 5% Cu-5% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. The mixture was stirred and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 5 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,4-methylenedioxybenzyl alcohol was 97.39%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 98.62%.

[0085] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 94.70 g of 3,4-methylenedioxybenzaldehyde. The yield was calculated to be 95.97%.

[0086] Example 15

[0087] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the mixture was purged with nitrogen three times, and then 100g of 3,4-methylenedioxybenzyl alcohol and 5.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. The mixture was stirred and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 5 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,4-methylenedioxybenzyl alcohol was 99.56%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 98.87%.

[0088] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 97.05 g of 3,4-methylenedioxybenzaldehyde. The yield was calculated to be 98.35%.

[0089] Example 16

[0090] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the mixture was purged with nitrogen three times, and then 100g of 3,4-methylenedioxybenzyl alcohol and 7.0g of catalyst 7% Cu-5% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 7.0%) were added. The mixture was stirred and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 5 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,4-methylenedioxybenzyl alcohol was 99.10%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 98.80%.

[0091] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 96.51 g of 3,4-methylenedioxybenzaldehyde. The yield was calculated to be 97.80%.

[0092] Example 17

[0093] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the mixture was purged with nitrogen three times, and then 100g of 3,4-methylenedioxybenzyl alcohol and 9.0g of catalyst 1% Cu-9% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 9.0%) were added. The mixture was stirred and the reaction temperature was set to 200℃. The reaction was carried out at a constant temperature for 8 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,4-methylenedioxybenzyl alcohol was 92.36%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 89.69%.

[0094] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 80.69 g of 3,4-methylenedioxybenzaldehyde. The yield was calculated to be 81.76%.

[0095] Example 18

[0096] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1As shown in the figure, the mixture was purged with nitrogen three times, and then 100g of 3,4-dimethoxybenzyl alcohol and 5.0g of catalyst 5% Cu-7% Bi / MIL-101-DPPP (metal:ligand molar ratio of 1:9) (catalyst mass concentration of 5.0%) were added. The mixture was stirred and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,4-dimethoxybenzyl alcohol was 98.43%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 99.41%.

[0097] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 96.53 g of 3,4-dimethoxybenzaldehyde. The yield was calculated to be 97.71%.

[0098] Example 19

[0099] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the reaction mixture was purged with nitrogen three times, and then 100g of 4-methoxybenzyl alcohol and 7.0g of catalyst 5% Cu-9% Ce / MIL-53-DPPB (metal:ligand molar ratio of 1:6) (catalyst mass concentration of 7.0%) were added. The mixture was stirred and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 4-methoxybenzyl alcohol was 98.31%, and the selectivity of 4-methoxybenzaldehyde was 98.86%.

[0100] After the reaction liquid was extruded, the catalyst was recovered by filtration and the unreacted raw materials were recovered, yielding 95.64 g of 4-methoxybenzaldehyde. The yield was calculated to be 97.06%.

[0101] Example 20

[0102] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the reaction mixture was purged with nitrogen three times, and then 100g of 3,7-dimethyl-1,7-hydroxy-octanediol and 7.0g of catalyst 7% Zn-7% Bi / MOF-801-DPPE (metal:ligand molar ratio of 1:5) (catalyst mass concentration of 7.0%) were added. The mixture was stirred and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,7-dimethyl-1,7-hydroxy-octanediol was 96.35%, and the selectivity of 7-hydroxy-3,7-dimethyl-octanal was 97.45%.

[0103] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered to obtain 92.59 g of 7-hydroxy-3,7-dimethyl-octanal. The yield was calculated to be 93.68%.

[0104] Example 21

[0105] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the mixture was purged with nitrogen three times, and then 100g of 3,7-dimethyl-6-octenol and 7.0g of catalyst 7% Zn-7% Bi / MOF-801-DPPE (metal:ligand molar ratio of 1:10) (catalyst mass concentration of 7.0%) were added. Stirring was started, the reaction temperature was set to 160℃, and the reaction was maintained at this temperature for 6 hours until no more bubbles escaped from the glass-sealed container. The reaction was then stopped. Gas chromatography analysis of the reaction solution showed a 3,7-dimethyl-6-octenol conversion of 99.46% and a 3,7-dimethyl-6-octenal selectivity of 97.69%. Figure 2 As shown.

[0106] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 95.76 g of 3,7-dimethyl-6-octenal. The yield was calculated to be 97.01%.

[0107] Test conditions: Fuli gas chromatograph, OV-1701 column, 30m*0.25mm*0.25μm;

[0108] The vaporization chamber temperature is 240℃; the detector temperature is 230℃.

[0109] Column temperature: 140℃ for 18 minutes.

[0110] Example 22

[0111] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of cinnamyl alcohol and 7.0g of catalyst 9% Zn-9% Bi / MOF-801-DPPE (metal:ligand molar ratio of 1:2) (catalyst mass concentration of 7.0%) were added. Stirring was started, and the reaction temperature was set to 180℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of cinnamyl alcohol was 95.56%, and the selectivity of cinnamaldehyde was 97.38%.

[0112] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 91.55g of cinnamaldehyde. The yield was calculated to be 92.95%.

[0113] Example 23

[0114] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of benzyl alcohol and 5.0g of catalyst 7% Zn-9% Ce / MOF-117-DPPP (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of benzyl alcohol was 98.11%, and the selectivity of benzaldehyde was 98.37%.

[0115] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 94.61g of benzaldehyde. The yield was calculated to be 96.42%.

[0116] Example 24

[0117] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the reaction mixture was purged with nitrogen three times, and 100g of salicylol and 7.0g of catalyst 5% Zn-10% Ce / MOF-5-DPPB (metal:ligand molar ratio of 1:10) (catalyst mass concentration of 7.0%) were added. The mixture was stirred and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 5 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of salicylol was 98.39%, and the selectivity of salicylaldehyde was 96.21%.

[0118] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 92.97g of salicylaldehyde. The yield was calculated to be 94.51%.

[0119] Example 25

[0120] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of cyclopentanol and 5.0g of catalyst 7% Cu-9% Ce / MIL-101-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of cyclopentanol was 99.14%, and the selectivity of cyclopentanaldehyde was 98.42%.

[0121] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 95.18 g of cyclopentanaldehyde. The yield was calculated to be 97.46%.

[0122] Example 26

[0123] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of n-pentanol and 5.0g of catalyst 7% Cu-9% Ce / MIL-101-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of n-pentanol was 98.95%, and the selectivity of n-pentanaldehyde was 98.31%.

[0124] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 94.92 g of n-pentanal. The yield was calculated to be 97.15%.

[0125] Example 27

[0126] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the mixture was purged with nitrogen three times, and then 100g of isoamyl alcohol and 3.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 3.0%) were added. The mixture was stirred, and the reaction temperature was set to 100℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the isoamyl alcohol conversion rate was 97.68%, and the isopentaldehyde selectivity was 99.49%.

[0127] After the reaction liquid was extruded, the catalyst was recovered by filtration and the unreacted raw materials were recovered, yielding 94.83 g of isovaleraldehyde. The yield was calculated to be 97.06%.

[0128] Example 28

[0129] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the reaction mixture was purged with nitrogen three times, then 100g of menthol and 5.0g of catalyst (7% Cu-9% Ce / MIL-101-DPPE, metal:ligand molar ratio 1:8, catalyst mass concentration 5.0%) were added. Stirring was started, the reaction temperature was set to 160℃, and the reaction was maintained at this temperature for 6 hours until no more bubbles escaped from the glass-sealed container. The reaction was then stopped. Gas chromatography analysis of the reaction solution showed a menthol conversion of 100% and a menthone selectivity of 99.97%. Figure 3 As shown.

[0130] After the reaction liquid was extruded, the catalyst was recovered by filtration and the unreacted raw materials were recovered, yielding 98.56g of menthone. The yield was calculated to be 99.85%.

[0131] Test conditions for the reaction solution: Fuli gas chromatograph, DB-17 capillary column; model: 30m×0.25mm×0.25μm;

[0132] Vaporization chamber: 250℃, detector: 300℃;

[0133] Column temperature: Hold at 60℃ for 1 min, then increase the temperature to 180℃ / min at a rate of 20℃ / min.

[0134] Example 29

[0135] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the mixture was purged with nitrogen three times, and then 100g of 2,3-butanediol and 5.0g of catalyst 5% Cu-7% Bi / MIL-101-DPPP (metal:ligand molar ratio of 1:9) (catalyst mass concentration of 5.0%) were added. The mixture was stirred, and the reaction temperature was set to 120℃. The reaction was carried out at a constant temperature for 4 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3-hydroxy-2-butanol was 99.72%, and the selectivity of 3-hydroxy-2-butanone was 98.11%.

[0136] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 95.57 g of 3-hydroxy-2-butanone. The yield was calculated to be 97.76%.

[0137] Example 30

[0138] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. 100g of 3-hexenol and 5.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 120℃. The reaction was carried out at a constant temperature for 5 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of 3-hexenol was 99.43%, and the selectivity of 3-hexenal was 98.76%.

[0139] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 96.11 g of 3-hexenal. The yield was calculated to be 98.09%.

[0140] Example 31

[0141] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1As shown in the figure, the mixture was purged with nitrogen three times, and 100g of 3-methyl-3-buten-1-ol and 5.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. The mixture was stirred and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 4 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3-methyl-3-buten-1-ol was 99.62%, and the selectivity of 3-methyl-3-butenal was 98.46%.

[0142] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 95.67 g of 3-methyl-3-butenal. The yield was calculated to be 97.96%.

[0143] Example 32

[0144] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the mixture was purged with nitrogen three times, and 100g of 3-methyl-2-butenol and 5.0g of catalyst 5% Cu-7% Bi / MIL-101-DPPP (metal:ligand molar ratio of 1:9) (catalyst mass concentration of 5.0%) were added. Stirring was started, the reaction temperature was set to 160℃, and the reaction was carried out at a constant temperature for 5 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution, and the conversion rate of 3-methyl-2-butenol was 99.31%, and the selectivity of 3-methyl-2-butenol was 98.25%.

[0145] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 95.15 g of 3-methyl-3-butenal. The yield was calculated to be 97.43%.

[0146] Example 33

[0147] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of geraniol and 5.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of geraniol was 99.48%, and the selectivity of geranialdehyde was 99.23%.

[0148] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 97.31g of geranialdehyde. The yield was calculated to be 98.61%.

[0149] Example 34

[0150] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of nerol and 5.0g of catalyst 7% Cu-9% Ce / MIL-101-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of nerol was 99.05%, and the selectivity of neraldehyde was 98.86%.

[0151] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 96.52g of neraldehyde. The yield was calculated to be 97.81%.

[0152] Example 35

[0153] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the reaction mixture was purged with nitrogen three times, and then 100g of n-octanol and 7.0g of catalyst 5% Cu-7% Bi / MIL-101-DPPP (metal:ligand molar ratio of 1:9) (catalyst mass concentration of 7.0%) were added. The mixture was stirred, and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of n-octanol was 99.64%, and the selectivity of n-octanal was 98.73%.

[0154] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 96.73 g of n-octanal. The yield was calculated to be 98.26%.

[0155] Example 36

[0156] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. Then, 100g of methanol and 5.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 120℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to detect the reaction solution. The methanol conversion rate was 99.24%, and the formaldehyde selectivity was 95.47%.

[0157] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 88.67g of formaldehyde. The yield was calculated to be 94.61%.

[0158] Example 37

[0159] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), nitrogen was used to purge the mixture three times. 100g of ethanol and 5.0g of catalyst 7% Cu-9% Ce / MIL-101-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. Stirring was started, and the reaction temperature was set to 120℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The ethanol conversion rate was 99.02%, and the acetaldehyde selectivity was 96.09%.

[0160] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 90.89 g of acetaldehyde. The yield was calculated to be 95.06%.

[0161] Example 38

[0162] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the mixture was purged with nitrogen three times, and 100g of L-menthol and 5.0g of catalyst 7% Cu-7% Zn / UiO-66-DPPE (metal:ligand molar ratio of 1:8) (catalyst mass concentration of 5.0%) were added. The mixture was stirred, and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of L-menthol was 99.35%, and the selectivity of L-menthone was 98.79%.

[0163] After the reaction liquid was extruded, the catalyst was recovered by filtration and the unreacted raw materials were recovered, yielding 96.71g of L-menthol. The calculated yield was 97.98%.

[0164] Example 39

[0165] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown), the mixture was purged with nitrogen three times, and 100g of 4-methyl-3-decen-5-ol and 7.0g of catalyst 5% Cu-7% Bi / MIL-101-DPPP (metal:ligand molar ratio of 1:9) (catalyst mass concentration of 7.0%) were added. The mixture was stirred, and the reaction temperature was set to 140℃. The reaction was carried out at a constant temperature for 8 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 4-methyl-3-decen-5-ol was 99.48%, and the selectivity of 4-methyl-3-decen-5-one was 96.57%.

[0166] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 94.79 g of 4-methyl-3-decen-5-one, with a calculated yield of 95.91%.

[0167] Comparative Example 4

[0168] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, the mixture was purged with nitrogen three times, and then 100g of 3,4-methylenedioxybenzyl alcohol and 7.0g of catalyst 7% Cu / UiO-66-DPPE (metal:ligand molar ratio of 1:10) (catalyst mass concentration of 7.0%) were added. The mixture was stirred and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 8 hours until no bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. The reaction solution was analyzed by gas chromatography, and the conversion rate of 3,4-methylenedioxybenzyl alcohol was 90.47%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 60.58%.

[0169] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 51.62 g of 3,4-methylenedioxybenzaldehyde. The calculated yield was 52.31%.

[0170] Comparative Example 5

[0171] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1 As shown in the figure, nitrogen was used to purge the mixture three times. 100g of 3,4-methylenedioxybenzyl alcohol and 7.0g of catalyst 7% Cu-9% Zn / UiO-66 (catalyst mass concentration was 7.0%) were added. Stirring was started, and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 8 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of 3,4-methylenedioxybenzyl alcohol was 91.26%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 54.43%.

[0172] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 49.90 g of 3,4-methylenedioxybenzaldehyde. The calculated yield was 49.55%.

[0173] Comparative Example 6

[0174] The autoclave is connected to a tail gas pipe, which passes through a buffer tank and is then immersed in a glass melt seal tank (e.g., Figure 1As shown in the figure, nitrogen was used to purge the mixture three times. 100g of 3,4-methylenedioxybenzyl alcohol and 7.0g of catalyst 7% Cu-9% Zn / UiO-66-TPP (catalyst mass concentration was 7.0%) were added. Stirring was started, and the reaction temperature was set to 160℃. The reaction was carried out at a constant temperature for 6 hours until no more bubbles escaped from the glass liquid-sealed container. The reaction was then stopped. Gas chromatography was used to analyze the reaction solution. The conversion rate of 3,4-methylenedioxybenzyl alcohol was 94.31%, and the selectivity of 3,4-methylenedioxybenzaldehyde was 82.69%.

[0175] After the reaction liquid was extruded, the catalyst was recovered by filtration, and the unreacted raw materials were recovered, yielding 76.50 g of 3,4-methylenedioxybenzaldehyde. The calculated yield was 77.52%.

[0176] Example 40 Catalyst Application Experiment

[0177] The catalyst recovered in Example 18 was directly used in a catalyst reuse experiment, with the same reaction conditions and procedures as in Example 18. The experimental results are shown in the table below.

[0178] Table 1

[0179]

[0180] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0181] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing an aldehyde or ketone compound, characterized in that, include: Under the action of a dehydrogenation catalyst, alcohols undergo a dehydrogenation reaction to yield the aldehydes or ketones described above. The reaction formula is as follows: ； R1 represents H, C1~C 10 Alkyl, C2~C 10 alkenyl or C6~C 10 Aryl group, R2 is H, C1~C 10 Alkyl, C2~C 10 alkenyl or C6~C 10 Aryl; The method for preparing the dehydrogenation catalyst includes the following steps: (1) The pretreated support and active metal salt are mixed and adsorbed, and then dried and calcined to obtain the catalyst intermediate; (2) Add a ligand to the catalyst intermediate in step (1) for further modification to obtain the dehydrogenation catalyst; In step (1), the pretreatment operation of the carrier is to activate it in a vacuum drying oven at 100-150℃ for 3-6 h; In step (1), the carrier is one or more of MOF-5, MOF-801, MIL-53, MIL-101, and UiO-66, and the metal in the active metal salt is two or more of Cu, Bi, Zn, and Ce. In step (1), the roasting temperature is 300-500℃ and the roasting time is 6-10 h; In step (2), the modification temperature is 60-120℃, and the modification time is 4-8 hours. In step (2), the ligand is a bidentate phosphine ligand; The dehydrogenation reaction is carried out at a temperature of 120-180℃ and for a time of 2.0 h-8.0 h.

2. The method for preparing aldehydes or ketones according to claim 1, characterized in that, In step (1), the mass ratio of the active metal salt to the carrier is (1.0%~10.0%):1, based on metal content.

3. The method for preparing aldehydes or ketones according to claim 2, characterized in that, In step (1), the mass ratio of the active metal salt to the carrier is (3.0%~7.0%):1, based on metal content.

4. The method for preparing aldehydes or ketones according to claim 1, characterized in that, In step (2), the ligand is one or more of 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, and 1,4-bis(diphenylphosphine)butane; The molar ratio of the active metal salt to the ligand is 1:(2~10.0).

5. The method for preparing aldehydes or ketones according to claim 4, characterized in that, In step (2), the molar ratio of the active metal salt to the ligand is 1:(6.0-10.0).

6. The method for preparing aldehydes or ketones according to claim 1, characterized in that, In step (1), the adsorption temperature is 40-80℃ and the adsorption time is 4-8 h.

7. The method for preparing aldehydes or ketones according to any one of claims 1 to 6, characterized in that, The mass ratio of the dehydrogenation catalyst to the alcohol compound is (3.0%-9.0%):

1.

8. The method for preparing aldehydes or ketones according to claim 7, characterized in that, The mass ratio of the dehydrogenation catalyst to the alcohol compound is (3.0%-7.0%):

1.

9. The method for preparing aldehydes or ketones according to claim 1, characterized in that, The dehydrogenation reaction is carried out at a temperature of 140-180℃ and for a time of 4.0 h-6.0 h.

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