Composite catalyst, preparation method thereof and method for preparing enol compound by reducing alkynol compound

Abstract

The invention provides a composite catalyst and a preparation method thereof, and a method for preparing an enol compound through reduction of an alkynol compound, the composite catalyst comprises an active metal palladium salt, a ligand and a carrier, the active metal palladium salt is the active metal palladium salt, the ligand is a phosphine ligand, and the carrier is an alkynol compound. The method for preparing the enol compound by reducing the alkynol compound comprises the following step: carrying out hydrogenation reaction on the alkynol compound with a structure shown in a formula I in the presence of a composite catalyst to obtain the enol compound shown in a formula II. The composite catalyst is used, the enol compound is prepared through selective hydrogenation of alkynol, generation of saturated alcohol through excessive hydrogenation of enol is inhibited, heating decomposition of a substrate alkynol and a self-polymerization reaction of a substrate product enol are eliminated, and the product yield and the raw material utilization rate are effectively increased.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a composite catalyst, a preparation method thereof, and a method for reducing an alkynol compound to prepare an enol compound. Background Art

[0002] Enols are high-value industrial raw materials and can be used as intermediates for VE, pyrethroid intermediates, to synthesize vitamin A, vitamin K1, carotenoid intermediates, synthetic rubber monomers, and fragrances, and are widely used in various fields such as nutritional products, flavors and fragrances, new materials, and pharmaceuticals and pesticides. The synthesis method is usually to selectively hydrogenate an alkynol to prepare the corresponding enol, and its reaction general formula is:

[0003]

[0004] Among them, R1 and R2 are hydrogen or hydrocarbon groups.

[0005] The selective catalytic hydrogenation of alkynols to prepare the corresponding enols is one of the important processes in fine chemical production. The semi-hydrogenation catalyst for alkynol compounds used in industry is the Lindlar catalyst developed by Roche. This catalyst loads Pd metal on a calcium carbonate or barium sulfate carrier poisoned by lead acetate. At the same time, nitrogen- or sulfur-containing organic compounds such as pyridine or quinoline need to be added as inhibitors in this reaction system. These substances can compete with intermediate products for active sites, thereby reducing the reaction rate of the hydrogenation of enols to saturated alcohols. The outstanding selectivity of this catalyst stems from the synergistic effect of lead copolymers and organic inhibitors. However, the addition of toxic heavy metal lead and organic inhibitors not only easily causes the catalyst to deactivate due to poisoning, but also reduces the quality of the product, significantly increases the complexity of product separation and purification, and limits its application in fine chemical synthesis and pharmaceutical production.

[0006] In Patent CN104394988A, the particle size of the calcium carbonate carrier is controlled above 10 μm to achieve the purpose of reducing the specific surface area. A more general principle is to add sulfur- and nitrogen-containing compounds to reduce the catalyst activity. Common compounds include quinoline, pyridine, thiol, etc. The selection principle is as follows: The coordination ability of alkynes is stronger than that of monoolefins. If an electron-donating reagent with a stronger coordination ability than monoolefins is added in the catalytic hydrogenation reaction, the hydrogenation reaction of monoolefins can be partially or completely inhibited. The inhibitory effect of the electron-donating reagent on the hydrogenation of monoolefins is not only related to the electron-donating reagent but also related to the substrate. The same electron-donating reagent has different inhibitory effects on the selective hydrogenation of different alkynes on the same catalyst, and different electron-donating reagents have different inhibitory effects on the selective hydrogenation of the same alkynes on the same catalyst.

[0007] CN109293472A reported that by using a Lindlar catalyst and adding acetal or ketal in the reaction system, the selective hydrogenation of propargyl alcohol compounds was achieved, claiming that the selectivity of the target product enol was as high as 99%.

[0008] WO2020239721 reported that adding compounds such as triphenylphosphine and triphenylthiophosphine, organic phosphines, organic sulfurs, etc. as additives to the reaction system, the selectivity of the target product enol was above 96%.

[0009] CN101869845A reported that Lindlar catalysts doped with metals such as Mn, Bi, Zn, etc. were used for the selective hydrogenation of dehydroisophytol, and the selectivity of the target product isophytol was above 98%.

[0010] The literature Vernuccio, S.; Goy, R. et al. Hydrogenation of 2-methyl-3-butyn-2-ol over a Pd / ZnO catalyst: kinetic model and selectivity study. Reaction Chemistry Engineering, 2016, 1, 445 - 453 reported that a Pd / ZnO catalyst was used for the catalytic hydrogenation to prepare 2-methyl-3-buten-2-ol, and the catalyst was reused 6 times, and the selectivity of the target product was above 95%.

[0011] CN105175231B discloses that a complex formed by a water-soluble salt of Group VIII metals (Pd, Pt) and a water-soluble phosphine ligand is used as a catalyst for the selective hydrogenation of propargyl alcohol to prepare allyl alcohol. The catalyst is stable and water is used as a solvent without introducing other organic solvents, which is environmentally friendly.

[0012] Noble metal catalysts have the advantages of mild reaction conditions, high activity and good selectivity. However, the active metals in the currently industrially applied Lindlar catalysts are expensive and prone to poisoning and loss. The production process also involves the addition and separation of harmful substances, posing potential environmental risks.

[0013] Non-noble metal catalysts are relatively inexpensive and widely used in industry. However, due to technological monopolies and the easy deactivation of catalysts, the application cost in China is relatively high. Moreover, the reaction needs to be carried out under high temperature and high pressure, which requires high equipment and energy consumption, and is also not conducive to obtaining a high enol yield. Therefore, some effective strategies are currently needed to improve the catalytic activity and atomic utilization rate of non-noble metal catalysts, enabling them to catalyze reactions under mild reaction conditions, reducing equipment investment and production energy consumption.

[0014] Since the hydrogenation rate of olefins is much faster than that of alkynes, during the preparation of enols by hydrogenation of alkynols, there is a competitive hydrogenation reaction state between the raw material alkynols and the product enols, which causes over-hydrogenation of enols, resulting in over-hydrogenation and affecting the selectivity and yield of the reaction. Therefore, how to solve such technical problems is the research focus in this field. Summary of the Invention

[0015] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a composite catalyst and its preparation method, as well as a method for reducing alkynol compounds to prepare enol compounds.

[0016] To achieve this purpose, the present invention adopts the following technical solutions:

[0017] On the one hand, the present invention provides a composite catalyst, which includes an active metal salt, a ligand, and a carrier. The active metal salt is an active metal palladium salt, and the ligand is a phosphine ligand.

[0018] In the present invention, the composite catalyst contains at least two active metals.

[0019] Preferably, the active metal palladium (Pd) salt is selected from one or a combination of at least two of palladium-containing nitrates, hydrochlorides, sulfates, acetates, acetylacetonates, or their hydrates, but is not limited thereto.

[0020] Preferably, it is one or a combination of at least two of calcium carbonate (CaCO3), barium sulfate (BaSO4), silicon dioxide (SiO2), activated alumina (Al2O3), zinc oxide (ZnO), and zirconium oxide (ZrO2).

[0021] Preferably, the active metal palladium salt is 0.5% - 5.0% of the mass of the carrier, such as 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, or 5.0%, preferably 1.0% - 5.0%, more preferably 1.0% - 3.0%.

[0022] In the present invention, if the proportion of the active metal salt in the combination of the active metal palladium salt and the carrier is too small, the activity and selectivity of the catalyst will decrease due to too low metal content; when the proportion of the active metal salt is too large, the content of the active metal is too high, resulting in too high catalyst activity. Although the conversion rate is appropriately increased, it is not very helpful for improving the selectivity. Instead, it will lead to a decrease in the selectivity of the product due to over-hydrogenation of the product, and also cause waste of raw materials.

[0023] In the present invention, the ligand is selected from phosphine ligands.

[0024] Preferably, the molar ratio of the phosphine ligand to the active palladium metal salt is 2.0 to 10.0:1, such as 2.0:1, 3.0:1, 4.0:1, 5.0:1, 6.0:1, 7.0:1, 8.0:1, 9.0:1 or 10.0:1, preferably 2.0 to 8.0:1, more preferably 4.0 to 8.0:1. In the present invention, if the proportion of the ligand is too small, the ligand content is too low and the selectivity is poor; when the ligand ratio is too high, it is not very helpful for improving the selectivity, and it causes waste of raw materials.

[0025] Preferably, the ligand is selected from one or a combination of at least two of 2-(di-tert-butylphosphino)biphenyl (JohnPhos, MW 298.41), 2-cyclohexylphosphino-2',3',6'-triisopropyl-biphenyl (XPhos, MW 476.72), 2-di-tert-butylphosphino-2-(N,N-dimethylamino)biphenyl (tBuDavePhos, MW 341), 2-(di-tert-butylphosphino)-2'-methylbiphenyl (tBuMePhos, MW 312), 2-dicyclohexylphosphino-2'-(N,N-dimethylamine)-biphenyl (DavePhos, MW 394), 2-(dicyclohexylphosphino)biphenyl (CyJohnPhos, MW 350), 2-diphenylphosphino-2'-(N,N-dimethylamino)biphenyl (PhDavePhos, MW 381), 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl (NsPhos, MW 411) or 2-di-tert-butylphosphino-2',3',6'-triisopropyl-biphenyl (tBuXPhos, MW 424.64).

[0026] The structure of the ligand as described above is shown below:

[0027]

[0028] In the present invention, the catalyst is composed of an active palladium metal salt, a ligand and a support. The aryl steric hindrance in the ligand can prevent the phosphorus atom from being oxidized by air, enhancing the stability of the phosphine ligand; the electron-donating substituents introduced on the aromatic ring can prevent the active metal from being embedded in the cyclization, not only increasing the stability of the catalyst, but also increasing the activity of the catalyst and accelerating the rate of the hydrogenation reaction in the catalytic cycle. The large steric hindrance phosphine ligand of the tert-butyl type not only speeds up the reaction process, but also can regulate the adsorption strength between the active metal and the carbon-carbon triple bond and double bond, achieving high selectivity of the target product olefin, thereby suppressing the over-hydrogenation of the intermediate product and improving the selectivity of the reaction.

[0029] On the other hand, the present invention provides a preparation method of the composite catalyst as described above, and the preparation method includes the following steps:

[0030] (1) Mix the active metal palladium salt, solvent and ligand, and stir to obtain a mixed solution;

[0031] (2) Add a carrier to the above mixed solution, mix and stir to obtain the composite catalyst.

[0032] Preferably, the solvent in step (1) is selected to be capable of dissolving the active metal palladium salt, and is selected from water or ethanol, and no special limitation is made here.

[0033] Preferably, the mixing in step (1) is carried out at room temperature (15 - 30 °C, such as 15 °C, 18 °C, 20 °C, 25 °C, 28 °C or 30 °C), and the mixing time is 2.0 - 4.0 hours, such as 2.0 hours, 2.5 hours, 2.8 hours, 3.0 hours, 3.5 hours, 3.8 hours or 4.0 hours.

[0034] Preferably, the mixing in step (2) is carried out with stirring at room temperature (15 - 30 °C, such as 15 °C, 18 °C, 20 °C, 25 °C, 28 °C or 30 °C), and the mixing time is 2.0 - 4.0 hours, such as 2.0 hours, 2.5 hours, 2.8 hours, 3.0 hours, 3.5 hours, 3.8 hours or 4.0 hours.

[0035] On the other hand, the present invention provides a method for reducing an alkynol compound to prepare an enol compound, and the method includes the following steps:

[0036] The alkynol compound having the structure shown in Formula I undergoes a hydrogenation reaction in the presence of a composite catalyst to obtain an enol compound having the structure shown in Formula II;

[0037]

[0038] Wherein, R1 and R2 are each independently hydrogen or a C1 - C20 straight-chain or branched-chain alkyl group, a C2 - C20 alkenyl group, and R1 and R2 are not simultaneously hydrogen;

[0039] The composite catalyst is the composite catalyst as described above.

[0040] In the present invention, by using the composite catalyst, the thermodynamic selectivity of the reaction can be well controlled, that is, in the presence of an olefin, the active metal preferentially adsorbs and activates the alkyne, and by regulating the geometric effect and electronic effect of the active site, the over-hydrogenation of the intermediate product is inhibited, and thus the alkynol compound can undergo a selective hydrogenation reaction to obtain an enol compound.

[0041] Preferably, the alkynol compounds of the structure shown in Formula I include, but are not limited to, propargyl alcohol, 2-methyl-3-butyn-2-ol, 3-methyl-pentyn-3-ol, dehydro linalool, dehydroethyl linalool, dihydrodehydro linalool, furfuryl acetylene alcohol, dehydro nerolidol, dehydro-β-enol, tetrahydrodehydro nerolidol, dehydroisophytol, and dehydroethyl ester. Their structural formulas are respectively:

[0042]

[0043] The corresponding enol compounds obtained from the alkynol compounds described above are: allyl alcohol, 2-methyl-3-buten-2-ol, 3-methyl-penten-3-ol, linalool, ethyl linalool, dihydro linalool, furfuryl vinyl alcohol, nerolidol, tetrahydro nerolidol, and isophytol. Their structural formulas are respectively:

[0044]

[0045] Preferably, the dosage of the composite catalyst is 0.01% to 0.1% of the mass of propargyl alcohol, such as 0.01%, 0.03%, 0.05%, 0.07%, 0.09%, 0.1%. Preferably, it is 0.03% to 0.09%, and more preferably 0.05% to 0.07%.

[0046] Preferably, the temperature of the hydrogenation reaction is 80°C to 160°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or 160°C. Preferably, it is 80°C to 120°C, and more preferably 100°C to 120°C.

[0047] Preferably, the time of the hydrogenation reaction is 30 to 60 min, such as 30 min, 40 min, 50 min, 60 min.

[0048] Preferably, the hydrogen pressure of the selective hydrogenation reaction is 0.3 MPa to 1.0 MPa, such as 0.3 MPa, 0.5 MPa, 0.7 MPa, 1.0 MPa. Preferably, it is 0.5 MPa to 0.7 MPa.

[0049] Preferably, the hydrogenation reaction can be solvent-free or can have a solvent; if there is a solvent, it is selected from any one or a combination of at least two of solvents such as ethanol, methanol, isopropanol, water, etc. Preferably, it is ethanol, including but not limited to this.

[0050] In the present invention, after the hydrogenation reaction, post-treatment is carried out. The post-treatment includes conventional post-treatment operations such as filtration, solvent and raw material recovery, and heavy component removal.

[0051] In the present invention, the hydrogenation reaction can be carried out in a reaction manner well-known in the art, including but not limited to batch autoclave, fixed bed, loop reactor and other processes well-known to those skilled in the art. The present invention preferably conducts the reaction in a loop reactor.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] (1) The present invention uses a composite catalyst to prepare enol compounds by selective hydrogenation of alkynols. It not only inhibits the over-hydrogenation of enols to form saturated alcohols, but also eliminates the thermal decomposition of the substrate alkynols and the self-polymerization reaction of the substrate product enols, effectively improving the product yield and raw material utilization rate.

[0054] (2) The method for preparing enols by selective hydrogenation of alkynols provided by the present invention has a simple reaction system, does not add catalyst inhibitors, can be solvent-free, and the catalyst is easy to recover, which is green and environmentally friendly. It greatly simplifies the post-treatment operation, has high product quality, excellent aroma, and wide applications.

[0055] (3) The non-precious metal catalyst used in the present invention has high activity and conducts the reaction under mild reaction conditions, reducing the requirements for equipment and energy consumption; this catalyst is inexpensive and easy to recover, with stable catalyst performance, realizing the recycling of the catalyst, effectively reducing the production cost, and being beneficial to enhancing the competitiveness of enols and their downstream products. Specific Embodiments

[0056] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0057] The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0058] Example 1

[0059] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 1.344 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of carrier CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 1#, and reserved for use.

[0060] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #1, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 98.2%, and the selectivity of 3-methyl-1-penten-3-ol is 98.6%.

[0061] Example 2

[0062] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O and 2.688 g of ligand XPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, add 5 g of carrier CaCO3, stir at a constant temperature for 4 hours, and then rotary evaporate to remove the excess water to obtain a solid catalyst, denoted as catalyst #2, for standby.

[0063] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #2, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.1%, and the selectivity of 3-methyl-1-penten-3-ol is 98.4%.

[0064] Example 3

[0065] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added. After stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 3#, for standby.

[0066] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst 3# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulation pump was started to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulation pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. The reaction was carried out for 40 min, and then the flow rate of the circulation pump was immediately reduced and the temperature was quickly cooled to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.1%, and the selectivity of 3-methyl-1-penten-3-ol was 99.2%.

[0067] Example 4

[0068] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 0.2 g of catalyst 3# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.1 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulation pump was started to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulation pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. The reaction was carried out for 40 min, and then the flow rate of the circulation pump was immediately reduced and the temperature was quickly cooled to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 98.1%, and the selectivity of 3-methyl-1-penten-3-ol was 99.0%.

[0069] Example 5

[0070] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 0.6 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.3 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Start the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 98.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.0%.

[0071] Example 6

[0072] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.0 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.5 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Start the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.0%, and the selectivity of 3-methyl-1-penten-3-ol is 99.2%.

[0073] Example 7

[0074] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.8 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.9 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa and the temperature to be 100 ± 2 °C. React for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.6%, and the selectivity of 3-methyl-1-penten-3-ol is 99.3%.

[0075] Example 8

[0076] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 2.0 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 1.0 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa and the temperature to be 100 ± 2 °C. React for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.6%, and the selectivity of 3-methyl-1-penten-3-ol is 99.5%.

[0077] Example 9

[0078] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 30 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.0%, and the selectivity of 3-methyl-1-penten-3-ol is 99.2%.

[0079] Example 10

[0080] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 50 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.2%.

[0081] Example 11

[0082] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa, and adjust the circulation pump to 60 m / s, which is recorded as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 60 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.6%, and the selectivity of 3-methyl-1-penten-3-ol is 99.3%.

[0083] Example 12

[0084] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 80 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa, and adjust the circulation pump to 60 m / s, which is recorded as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 80 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 98.2%, and the selectivity of 3-methyl-1-penten-3-ol is 98.7%.

[0085] Example 13

[0086] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 120 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 120 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.7%, and the selectivity of 3-methyl-1-penten-3-ol is 98.7%.

[0087] Example 14

[0088] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 3# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 140 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 140 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.6%, and the selectivity of 3-methyl-1-penten-3-ol is 98.2%.

[0089] Example 15

[0090] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.3 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 0.8 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 0.8 MPa and the temperature to be 100 ± 2 °C. React for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 98.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.1%.

[0091] Example 16

[0092] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.7 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.4 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.4 MPa and the temperature to be 100 ± 2 °C. React for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.6%, and the selectivity of 3-methyl-1-penten-3-ol is 99.2%.

[0093] Example 17

[0094] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add 3-methyl-1-pentyn-3-ol (200g, 2.038mol), 100g of ethanol, and 1.4g of catalyst powder No. 3, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100°C (the heating time is about 10min), immediately fill with hydrogen until the reaction pressure reaches 1.0MPa, adjust the circulation pump to 60m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0MPa, the temperature to be 100±2°C, react for 40min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.4%.

[0095] Example 18

[0096] At room temperature, add 0.3756g of Pb(NO3)2·2H2O and 5.377g of ligand XPhos to 20mL of deionized water in sequence. After stirring at a constant temperature of 40°C for 2 hours, then add 5g of carrier CaCO3, stir at a constant temperature for 4 hours, and then evaporate to remove the excess water to obtain a solid catalyst, denoted as catalyst No. 4, for standby.

[0097] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add 3-methyl-1-pentyn-3-ol (200g, 2.038mol), 100g of ethanol, and 1.4g of catalyst powder No. 4, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100°C (the heating time is about 10min), immediately fill with hydrogen until the reaction pressure reaches 1.0MPa, adjust the circulation pump to 60m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0MPa, the temperature to be 100±2°C, react for 40min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.7%, and the selectivity of 3-methyl-1-penten-3-ol is 99.6%.

[0098] Example 19

[0099] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 6.721 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added. After stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 5#, for standby.

[0100] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst 5# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulating pump was turned on to make the liquid in the kettle flow slowly, and then vented. This process was repeated six times to displace the air in the loop reactor. After the temperature was raised to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged until the reaction pressure reached 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was rapidly cooled to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.8%, and the selectivity of 3-methyl-1-penten-3-ol was 99.7%.

[0101] Example 20

[0102] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 3.592 g of ligand tBuXPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added. After stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 6#, for standby.

[0103] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #6. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.4%.

[0104] Example 21

[0105] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O and 2.524 g of the ligand JohnPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier CaCO3 and stir at a constant temperature for 4 hours. Then evaporate the solvent by rotary evaporation to remove the excess water to obtain a solid catalyst, denoted as catalyst #7, for standby.

[0106] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #7. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 98.9%, and the selectivity of 3-methyl-1-penten-3-ol is 96.7%.

[0107] Example 22

[0108] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 2.884 g of the ligand tBuDavePhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the carrier CaCO3 was added. After stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove the excess water to obtain a solid catalyst, denoted as Catalyst 8#, for standby.

[0109] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of Catalyst 8# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the gas inlet until the system pressure reached 0.5 MPa. The circulating pump was started to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately decreased and the temperature was rapidly decreased to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.2%, and the selectivity of 3-methyl-1-penten-3-ol was 98.4%.

[0110] Example 23

[0111] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 2.639 g of the ligand tBuMePhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the carrier CaCO3 was added. After stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove the excess water to obtain a solid catalyst, denoted as Catalyst 9#, for standby.

[0112] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder No. 9. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Start the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 98.6%, and the selectivity of 3-methyl-1-penten-3-ol is 98.2%.

[0113] Example 24

[0114] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O and 3.333 g of the ligand DavePhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier CaCO3, stir at a constant temperature for 4 hours, and then evaporate the solvent by rotary evaporation to remove the excess water to obtain a solid catalyst, denoted as catalyst No. 10, for standby.

[0115] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder No. 10. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Start the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.1%, and the selectivity of 3-methyl-1-penten-3-ol is 98.9%.

[0116] Example 25

[0117] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 2.961 g of the ligand CyJohnPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the carrier CaCO3 was added. After stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove the excess water to obtain a solid catalyst, denoted as Catalyst 11#, and reserved for use.

[0118] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of the powder of Catalyst 11# were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulating pump was started to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After the temperature was raised to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged until the reaction pressure reached 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction process, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was rapidly lowered to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.2%, and the selectivity of 3-methyl-1-penten-3-ol was 97.8%.

[0119] Example 26

[0120] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 3.223 g of the ligand PhDavePhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the carrier CaCO3 was added. After stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove the excess water to obtain a solid catalyst, denoted as Catalyst 12#, and reserved for use.

[0121] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 12# catalyst powder. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.4%, and the selectivity of 3-methyl-1-penten-3-ol is 99.0%.

[0122] Example 27

[0123] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O and 3.477 g of the ligand NsPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier CaCO3, stir at a constant temperature for 4 hours, and then rotary evaporate to remove the excess water to obtain a solid catalyst, denoted as 13# catalyst, for standby.

[0124] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 13# catalyst powder. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.3%, and the selectivity of 3-methyl-1-penten-3-ol is 99.2%.

[0125] Example 28

[0126] At room temperature, 0.0626 g of Pb(NO3)2·2H2O and 0.672 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added, and after stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove the excess water to obtain a solid catalyst, denoted as Catalyst 14#, for standby.

[0127] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of Catalyst 14# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the gas inlet until the system pressure reached 0.5 MPa. The circulating pump was turned on to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After the temperature was raised to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged until the reaction pressure reached 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction process, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was rapidly cooled to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.1%, and the selectivity of 3-methyl-1-penten-3-ol was 98.6%.

[0128] Example 29

[0129] At room temperature, 0.1252 g of Pb(NO3)2·2H2O and 1.344 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added, and after stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove the excess water to obtain a solid catalyst, denoted as Catalyst 15#, for standby.

[0130] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder No. 15. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, use gas chromatography to detect the reaction solution, the conversion rate of 3-methyl-1-pentyn-3-ol is 99.2%, and the selectivity of 3-methyl-1-penten-3-ol is 98.8%.

[0131] Example 30

[0132] At room temperature, add 0.2504 g of Pb(NO3)2·2H2O and 2.688 g of ligand XPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of carrier CaCO3, stir at a constant temperature for 4 hours, and then rotary evaporate to remove the excess water to obtain a solid catalyst, denoted as catalyst No. 16, for standby.

[0133] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder No. 16. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, use gas chromatography to detect the reaction solution, the conversion rate of 3-methyl-1-pentyn-3-ol is 99.2%, and the selectivity of 3-methyl-1-penten-3-ol is 98.9%.

[0134] Example 31

[0135] At room temperature, 0.5009 g of Pb(NO3)2·2H2O, 5.377 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of carrier CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 17#, for standby.

[0136] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst 17# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the gas inlet until the system pressure reached 0.5 MPa. The circulating pump was started to make the liquid in the kettle flow slowly, and then emptied. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction process, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was quickly cooled to room temperature. After emptying, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.4%, and the selectivity of 3-methyl-1-penten-3-ol was 99.5%.

[0137] Example 32

[0138] At room temperature, 0.6261 g of Pb(NO3)2·2H2O, 6.721 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of carrier CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 18#, for standby.

[0139] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 18# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.5%.

[0140] Example 33

[0141] At room temperature, add 0.250 g of PbCl2 and 4.032 g of ligand XPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier CaCO3 and stir at a constant temperature for 4 hours, and then evaporate to remove the excess water to obtain a solid catalyst, denoted as 19# catalyst, for standby.

[0142] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 19# catalyst powder, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.4%.

[0143] Example 34

[0144] At room temperature, 0.4295 g of Pb(acac)2, 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of carrier CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as 20# catalyst, for standby.

[0145] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of 20# catalyst powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulating pump was started to make the liquid in the kettle flow slowly, and then vented. This process was repeated six times to displace the air in the loop reactor. After the temperature was raised to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged until the reaction pressure reached 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction process, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was quickly lowered to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.5%, and the selectivity of 3-methyl-1-penten-3-ol was 99.4%.

[0146] Example 35

[0147] At room temperature, 0.3363 g of Pb(SO4)2·2H2O, 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of carrier CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as 21# catalyst, for standby.

[0148] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #21, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.6%, and the selectivity of 3-methyl-1-penten-3-ol is 99.5%.

[0149] Example 36

[0150] At room temperature, add 0.3815 g of [Pd(NH3)4]SO4 and 4.032 g of ligand XPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier CaCO3, stir at a constant temperature for 4 hours, and then rotary evaporate to remove the excess water to obtain a solid catalyst, denoted as catalyst #22, for standby.

[0151] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #22, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.5%, and the selectivity of 3-methyl-1-penten-3-ol is 99.4%.

[0152] Example 37

[0153] At room temperature, 0.2855 g of PdSO4 and 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 23#, for standby.

[0154] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst 23# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulating pump was started to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was rapidly cooled to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 99.5%, and the selectivity of 3-methyl-1-penten-3-ol was 99.4%.

[0155] Example 38

[0156] At room temperature, 0.3165 g of Pd(OAc)2 and 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support CaCO3 was added, and after stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as catalyst 24#, for standby.

[0157] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #24. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill hydrogen until the reaction pressure reaches 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.4%, and the selectivity of 3-methyl-1-penten-3-ol is 99.4%.

[0158] Example 39

[0159] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O and 4.032 g of ligand XPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, add 5 g of carrier BaSO4, stir at a constant temperature for 4 hours, and then perform rotary evaporation to remove the excess water to obtain a solid catalyst, denoted as catalyst #25, for standby.

[0160] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #25. That is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill hydrogen until the reaction pressure reaches 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.2%, and the selectivity of 3-methyl-1-penten-3-ol is 99.0%.

[0161] Example 40

[0162] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the carrier SiO2 was added. After stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as Catalyst 26#, for standby.

[0163] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of Catalyst 26# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the gas inlet until the system pressure reached 0.5 MPa. The circulating pump was started to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After the temperature was raised to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged until the reaction pressure reached 1.0 MPa. The circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction process, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulating pump was immediately reduced and the temperature was rapidly cooled to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 98.9%, and the selectivity of 3-methyl-1-penten-3-ol was 99.2%.

[0164] Example 41

[0165] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the carrier Al2O3 was added. After stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as Catalyst 27#, for standby.

[0166] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder of No. 27, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.1%, and the selectivity of 3-methyl-1-penten-3-ol is 99.0%.

[0167] Example 42

[0168] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O and 4.032 g of ligand XPhos to 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier ZnO, stir at a constant temperature for 4 hours, and then rotary evaporate to remove the excess water to obtain a solid catalyst, denoted as catalyst No. 28, for standby.

[0169] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder of No. 28, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-1-pentyn-3-ol is 99.2%, and the selectivity of 3-methyl-1-penten-3-ol is 99.5%.

[0170] Example 43

[0171] At room temperature, 0.3756 g of Pb(NO3)2·2H2O and 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of support ZrO2 was added. After stirring at a constant temperature for 4 hours, the mixture was rotary evaporated to remove excess water to obtain a solid catalyst, denoted as Catalyst 29#, for standby.

[0172] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of Catalyst 29# powder were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulation pump was started to make the liquid in the kettle flow slowly, and then the reactor was emptied. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulation pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulation pump was immediately reduced and the temperature was quickly lowered to room temperature. After emptying, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 98.5%, and the selectivity of 3-methyl-1-penten-3-ol was 98.9%.

[0173] Example 44

[0174] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), propargyl alcohol (200 g, 3.568 mol), 100 g of ethanol, and 1.4 g of Catalyst 3# powder were added, that is, the relative ratio of the catalyst to the reactant propargyl alcohol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulation pump was started to make the liquid in the kettle flow slowly, and then the reactor was emptied. This process was repeated six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulation pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. After reacting for 40 min, the flow rate of the circulation pump was immediately reduced and the temperature was quickly lowered to room temperature. After emptying, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of propargyl alcohol was 99.7%, and the selectivity of allyl alcohol was 99.4%.

[0175] Example 45

[0176] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add 2-methyl-3-butyn-2-ol (200 g, 2.378 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant 2-methyl-3-butyn-2-ol is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 2-methyl-3-butyn-2-ol is 99.5%, and the selectivity of 2-methyl-3-buten-2-ol is 99.6%.

[0177] Example 46

[0178] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add dehydro linalool (200 g, 1.314 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydro linalool is 0.7 wt%. Pass hydrogen into the reactor through the gas inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydro linalool is 99.5%, and the selectivity of linalool is 99.1%.

[0179] Example 47

[0180] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add dehydroethyl linalool (200 g, 1.203 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydroethyl linalool is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydroethyl linalool is 99.4%, and the selectivity of ethyl linalool is 98.9%.

[0181] Example 48

[0182] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add dihydrodehydro linalool (200 g, 1.297 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dihydrodehydro linalool is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dihydrodehydro linalool is 99.4%, and the selectivity of tetrahydrolinalool is 98.9%.

[0183] Example 49

[0184] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add furfuryl ethynol (200 g, 1.638 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant furfuryl ethynol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, use gas chromatography to detect the reaction solution, the conversion rate of furfuryl ethynol is 99.2%, and the selectivity of furfuryl vinyl alcohol is 99.1%.

[0185] Example 50

[0186] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add dehydronerolidol (200 g, 0.908 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydronerolidol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to the reaction pressure of 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, use gas chromatography to detect the reaction solution, the conversion rate of dehydronerolidol is 99.3%, and the selectivity of nerolidol is 99.0%.

[0187] Example 51

[0188] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add tetrahydro nerolidol (200 g, 0.891 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant tetrahydro nerolidol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of tetrahydro nerolidol is 99.4%, and the selectivity of tetrahydro nerol is 99.1%.

[0189] Example 52

[0190] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add dehydroisophytol (200 g, 0.679 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydroisophytol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen until the reaction pressure reaches 1.0 MPa. Adjust the circulation pump to 60 m / s and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, and react for 40 min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydroisophytol is 99.2%, and the selectivity of isophytol is 98.7%.

[0191] Example 53

[0192] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add dehydroethyl arylate (200 g, 1.029 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydroethyl arylate is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydroethyl arylate is 99.3%, and the selectivity of ethyl arylate is 98.7%.

[0193] Example 54

[0194] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), add dehydro-β-enol (200 g, 1.297 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydro-β-enol is 0.7 wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5 MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately charge hydrogen until the reaction pressure reaches 1.0 MPa, adjust the circulation pump to 60 m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0 MPa, the temperature to be 100 ± 2 °C, react for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydro-β-enol is 99.4%, and the selectivity of β-enol is 99.5%.

[0195] Example 55

[0196] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add dehydro-β-enol (200g, 1.297mol), 100g of deionized water, and 1.4g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydro-β-enol is 0.7wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5MPa. Start the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100°C (the heating time is about 10min), immediately charge hydrogen until the reaction pressure reaches 1.0MPa, and adjust the circulation pump to 60m / s, which is recorded as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0MPa, the temperature to be 100±2°C, and react for 40min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydro-β-enol is 98.2%, and the selectivity of β-enol is 97.3%.

[0197] Example 56

[0198] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add dehydro-β-enol (200g, 1.297mol) and 1.4g of catalyst powder #3, that is, the relative ratio of the catalyst to the reactant dehydro-β-enol is 0.7wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5MPa. Start the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating up to the preset reaction temperature of 100°C (the heating time is about 10min), immediately charge hydrogen until the reaction pressure reaches 1.0MPa, and adjust the circulation pump to 60m / s, which is recorded as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0MPa, the temperature to be 100±2°C, and react for 40min. Immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of dehydro-β-enol is 99.3%, and the selectivity of β-enol is 95.1%.

[0199] Example 57

[0200] Use a batch high-pressure reaction kettle for hydrogenation operation.

[0201] Add 3-methyl-pent-3-yn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of catalyst powder #3 into a 1 L high-pressure reactor, i.e., the relative ratio of the catalyst to the reactant 3-methyl-pent-3-yn-3-ol is 0.7 wt%. Close the reactor, displace with nitrogen three times first, then displace with hydrogen three times, and then pressurize with hydrogen to 1.0 MPa. Control the hydrogen pressure connected to the reactor to be constantly 1.0 MPa. Turn on the heating and stirring of the reactor. After the internal temperature of the reactor rises to 100 °C, keep the reaction for 2 hours. Use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-pent-3-yn-3-ol is 98.4%, and the selectivity of 3-methyl-pent-3-en-3-ol is 99.1%.

[0202] Comparative Example 1: Traditional Lindlar catalyst

[0203] The traditional Lindlar catalyst (5% Pd / CaCO3) is denoted as Comparative Catalyst #1.

[0204] Add 3-methyl-pent-3-yn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of Comparative Catalyst #1 into a 1 L loop reactor (the volume of the reactor is 1 L), i.e., the relative ratio of the catalyst to the reactant 3-methyl-pent-3-yn-3-ol is 0.7 wt%. Pass hydrogen into the reactor through the inlet to a system pressure of 0.5 MPa. Turn on the circulation pump to make the liquid in the reactor flow slowly, and vent. Repeat six times to displace the air in the loop reactor. After the temperature rises to the preset reaction temperature of 100 °C (the heating time is about 10 min), immediately fill with hydrogen to a reaction pressure of 1.0 MPa, and adjust the circulation pump to 60 m / s, which is recorded as the start time of the reaction. During the reaction, control the hydrogen pressure connected to the reactor to be constantly 1.0 MPa, and the temperature to be 100 ± 2 °C. React for 40 min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product, sample and analyze it using gas chromatography. The conversion rate of 3-methyl-pent-3-yn-3-ol is 97.6%, and the selectivity of 3-methyl-pent-3-en-3-ol is 90.3%.

[0205] Comparative Example 2

[0206] At room temperature, add 0.3756 g of Pb(NO3)2·2H2O into 20 mL of deionized water in sequence. After stirring at a constant temperature of 40 °C for 2 hours, then add 5 g of the carrier CaCO3, stir at a constant temperature for 4 hours, and then rotary evaporate to remove the excess water to obtain a solid catalyst, which is denoted as Comparative Catalyst #2 and reserved.

[0207] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add 3-methyl-pent-3-yn-3-ol (200g, 2.038mol), 100g of ethanol, and 1.4g of comparative catalyst 2#. That is, the relative ratio of the catalyst to the reactant 3-methyl-pent-3-yn-3-ol is 0.7wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100°C (the heating time is about 10min), immediately fill with hydrogen to the reaction pressure of 1.0MPa, adjust the circulation pump to 60m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0MPa, the temperature to be 100±2°C, react for 40min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-pent-3-yn-3-ol is 80.6%, and the selectivity of 3-methyl-pent-3-en-3-ol is 56.3%.

[0208] Comparative Example 3

[0209] At room temperature, add 0.3756g of Pb(NO3)2·2H2O and 4.032g of ligand XPhos to 20mL of deionized water in sequence. Stir at a constant temperature of 40°C for 6 hours, then remove the excess water to obtain comparative catalyst 3#, which is reserved for use.

[0210] Into a 1L loop reactor (the volume of the reaction kettle is 1L), add 3-methyl-pent-3-yn-3-ol (200g, 2.038mol), 100g of ethanol, and 1.4g of comparative catalyst 3#. That is, the relative ratio of the catalyst to the reactant 3-methyl-pent-3-yn-3-ol is 0.7wt%. Pass hydrogen into the reactor through the inlet until the system pressure reaches 0.5MPa. Turn on the circulation pump to make the liquid in the kettle flow slowly, vent, and repeat six times to displace the air in the loop reactor. After heating to the preset reaction temperature of 100°C (the heating time is about 10min), immediately fill with hydrogen to the reaction pressure of 1.0MPa, adjust the circulation pump to 60m / s, and record it as the start time of the reaction. During the reaction process, control the hydrogen pressure connected to the reaction kettle to be constant at 1.0MPa, the temperature to be 100±2°C, react for 40min, immediately reduce the flow rate of the circulation pump and quickly cool down to room temperature. After venting, take the liquid product and use gas chromatography to detect the reaction solution. The conversion rate of 3-methyl-pent-3-yn-3-ol is 83.5%, and the selectivity of 3-methyl-pent-3-en-3-ol is 64.1%.

[0211] Comparative Example 4

[0212] At room temperature, 0.3756 g of Pb(NO3)2·2H2O, 4.032 g of ligand XPhos were successively added to 20 mL of deionized water. After stirring at a constant temperature of 40 °C for 2 hours, 5 g of the support activated carbon (AC) was added. After stirring at a constant temperature for 4 hours, rotary evaporation was carried out to remove the excess water to obtain a solid catalyst, denoted as Comparative Catalyst 4#, for standby.

[0213] Into a 1 L loop reactor (the volume of the reaction kettle is 1 L), 3-methyl-1-pentyn-3-ol (200 g, 2.038 mol), 100 g of ethanol, and 1.4 g of Comparative Catalyst 4# were added, that is, the relative ratio of the catalyst to the reactant 3-methyl-1-pentyn-3-ol was 0.7 wt%. Hydrogen was introduced into the reactor through the inlet until the system pressure reached 0.5 MPa. The circulating pump was turned on to make the liquid in the kettle flow slowly, and then the air was vented. This process was repeated six times to displace the air in the loop reactor. After the temperature was raised to the preset reaction temperature of 100 °C (the heating time was about 10 min), hydrogen was immediately charged to the reaction pressure of 1.0 MPa, and the circulating pump was adjusted to 60 m / s, which was recorded as the start time of the reaction. During the reaction, the hydrogen pressure connected to the reaction kettle was controlled to be constant at 1.0 MPa, and the temperature was 100 ± 2 °C. The reaction was carried out for 40 min, and then the flow rate of the circulating pump was immediately reduced and the temperature was rapidly lowered to room temperature. After venting, the liquid product was taken, and the reaction solution was detected by gas chromatography. The conversion rate of 3-methyl-1-pentyn-3-ol was 91.5%, and the selectivity of 3-methyl-1-penten-3-ol was 92.4%.

[0214] The applicant declares that the present invention uses the above embodiments to illustrate the composite catalyst of the present invention, its preparation method, and the method for reducing alkynol compounds to prepare enol compounds. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A composite catalyst, characterized in that: The composite catalyst comprises an active metal salt, a ligand and a carrier. The active metal salt is an active metal palladium salt, and the ligand is a phosphine ligand.

2. The composite catalyst according to claim 1, characterized in that The active metal palladium salt is selected from one or a combination of at least two of palladium-containing nitrates, hydrochlorides, sulfates, acetates, ammonium salts or hydrates thereof; Preferably, the ligand is selected from 2-(di-tert-butylphosphino)biphenyl, 2-cyclohexylphosphino-2',3',6'-triisopropyl-biphenyl, 2-di-tert-butylphosphino-2-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)-2'-methylbiphenyl, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)-biphenyl, 2-(dicyclohexylphosphino)biphenyl, 2-diphenylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl or 2-di-tert-butylphosphino-2',3',6'-triisopropyl-biphenyl or a combination of at least two thereof; Preferably, the molar ratio of the ligand to the active metal palladium salt is 2.0 to 10.0:1, preferably 2.0 to 8.0:1, and more preferably 4.0 to 8.0:

1.

3. The composite catalyst according to claim 1, characterized in that The carrier is a metal oxide carrier; Preferably, the carrier is one or a combination of at least two of calcium carbonate, barium sulfate, silicon dioxide, activated alumina, zinc oxide or zirconium oxide; Preferably, the active metal palladium salt accounts for 0.5% to 5.0% of the mass of the carrier, preferably 1.0% to 5.0%, more preferably 1.0% to 3.0%.

4. The method for preparing the composite catalyst according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: (1) mixing an active metal palladium salt with a solvent and a ligand, and stirring to obtain a mixed solution; (2) Adding the carrier to the mixed solution, mixing and stirring to obtain the composite catalyst.

5. The preparation method according to claim 4, characterized in that: The amount of the solvent added in step (1) is sufficient to dissolve the active metal palladium salt; Preferably, the solvent in step (1) is selected from water or ethanol. Preferably, the mixing in step (1) is carried out at room temperature, and the mixing time is 2.0 to 4.0 hours.

6. The method according to claim 4, characterized in that The mixing in step (2) is carried out under stirring at room temperature, and the mixing time is 2.0 to 4.0 hours.

7. A method for preparing an enol compound by reducing an alkynol compound, characterized in that: The method comprises the following steps: The alkynol compound of the structure shown in formula I is subjected to a hydrogenation reaction in the presence of a composite catalyst to obtain an enol compound of formula II; Wherein, R1 and R2 are independently hydrogen or C1-C20 straight or branched alkyl, C2-C20 alkenyl, and R1 and R2 are not hydrogen at the same time; The composite catalyst is the composite catalyst according to any one of claims 1 to 3.

8. The method according to claim 7, characterized in that The alkynol compound of the structure shown in formula I includes propargyl alcohol, 2-methyl-3-butyn-2-ol, 3-methyl-pentyn-3-ol, dehydrolinalool, dehydroethyllinalool, dihydrodehydrolinalool, furfuryl acetylene alcohol, dehydronerolidol, dehydroβ-enol, tetrahydrodehydronerolidol, dehydroisophytol or dehydroethyl aryl ester.

9. The method according to claim 7, characterized in that: The amount of the composite catalyst is 0.01% to 0.1% of the mass of propargyl alcohol; Preferably, the temperature of the hydrogenation reaction is 80°C to 160°C, preferably 80°C to 120°C, more preferably 100°C to 120°C. Preferably, the hydrogenation reaction time is 30 to 60 minutes.

10. The method according to any one of claims 7 to 9, characterized in that: The hydrogen pressure of the hydrogenation reaction is 0.3 MPa to 1.0 MPa, preferably 0.5 MPa to 0.7 MPa.

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