Preparation method of 3-methyl-2-butene-1-ol and catalyst of 3-methyl-2-butene-1-ol

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a preparation method of 3-methyl-2-butene-1-alcohol and a catalyst thereof, the preparation method comprises the following steps: 2-methyl-3-butene-2-alcohol is subjected to an isomerization reaction under the catalysis of a composite catalyst to generate 3-methyl-2-butene-1-alcohol, the composite catalyst comprises an active component, a modifier and a carrier, the modifier is amino acid; the active component comprises a cobalt element and an auxiliary agent metal; the auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel and bismuth; the carrier is one or more of macroporous silicon dioxide, macroporous calcium phosphate, macroporous aluminum oxide, macroporous carbon, macroporous silicon carbide and macroporous LaFeO3. The isomerization reaction process is simple, hydroisomerization is not needed, the final product selectivity is high, and no hydrogen-passing by-product is generated.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a preparation method of 3-methyl-2-butene-1-ol and a catalyst thereof. Background Art

[0002] 3-Methyl-2-butene-1-ol, also known as isopentenol, is mainly used as an important precursor for the synthesis of vitamin E, vitamin A, spice product citral, high-efficiency and low-toxic pesticide pyrethroid insecticides and other products.

[0003] According to the difference of reaction raw materials, the synthesis routes of 3-methyl-2-butene-1-ol can be mainly divided into the following three categories: (1) Prins method: isobutylene and polyoxymethylene react in the presence of disodium hydrogen phosphate to generate a mixture of 3-methyl-3-butene-1-ol and 3-methyl-2-butene-1-ol, and then the enol is transposed to isopentenol under Pd / C catalyst. (2) Isoprene method: isoprene is used as a raw material to react with hydrogen chloride to generate chloroisopentene, in which 1-chloro-3-methyl-3-butene is transposed to 1-chloro-3-methyl-2-butene, and then reacts with sodium acetate to generate the corresponding acetate, which is then hydrolyzed to obtain 3-methyl-2-butene-1-ol. (3) Methylbutenol isomerization method: Under alkaline conditions, acetone and acetylene undergo acetylation to produce ethynyl isopropanol, which is then hydrogenated over a Pd / C catalyst to produce 2-methyl-3-butene-2-ol, which is then isomerized to produce 3-methyl-2-butene-1-ol. The disadvantage of this method is that the conversion rate is relatively low, and a large amount of unreacted raw materials need to be separated and reused. The specific equation is:

[0004] In US3925485A, linalyl vanadate is used as a catalyst for catalytic isomerization reaction. When the conversion rate is 25.6%, the selectivity of isopentenol is 83%.

[0005] In CN102391073B, 2-methyl-3-butene-2-ol, cyclohexane, and a phosphoric acid aqueous solution with a pH of 1 to 3 are stirred and reacted at 60 to 95° C. for 4 to 15 hours. The conversion rate of 2-methyl-3-butene-2-ol is 19 to 22%, and the selectivity is greater than 99%.

[0006] In patent CN105967978B, aqueous methylbutenol, i.e., 2-methyl-3-butene-2-ol, is used as a raw material, and vanadium oxide or a vanadium-containing metal salt is used as a catalyst to synthesize isopentenol through isomerization.

[0007] In patent CN117417231A, 2-methyl-3-butene-2-ol is used as a raw material, the hydroxyl group in 2-methyl-3-butene-2-ol is substituted by chlorination to generate 3-chloroisopentene, and then a mixture containing 1-chloroisopentene is obtained by isomerization, and the mixture containing 1-chloroisopentene is hydrolyzed to obtain isopentenol.

[0008] Therefore, it is of great significance to design a catalyst with low cost, good catalytic activity, mild reaction conditions and high product purity, and apply it to catalyze the isomerization reaction of 2-methyl-3-butene-2-ol to obtain 3-methyl-2-butene-1-ol. Summary of the invention

[0009] In view of the defects of the above-mentioned prior art, the present invention provides a preparation method of 3-methyl-2-butene-1-ol and a catalyst thereof, which catalyzes the double bond and hydroxyl migration of 2-methyl-3-butene-2-ol to synthesize 3-methyl-2-butene-1-ol. The isomerization reaction process of the present invention is simple, no hydrogen isomerization is required, the final product selectivity is high, and no hydrogen byproduct is generated.

[0010] In order to achieve the above objectives, the first aspect of the present invention provides the following technical solutions: A method for synthesizing 3-methyl-2-butene-1-ol comprises the following steps: 2-methyl-3-butene-2-ol isomerizes under the catalysis of a composite catalyst to generate 3-methyl-2-butene-1-ol; The composite catalyst comprises an active component, a modifier and a carrier; The modifier is an amino acid; The active ingredient comprises cobalt and auxiliary metal; The auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel, and bismuth; The carrier is one or more of macroporous silica, macroporous alumina, macroporous carbon, macroporous silicon carbide, and macroporous LaFeO3.

[0011] The present invention adopts a new composite catalyst to catalyze the isomerization reaction of 2-methyl-3-butene-2-ol. The composite catalyst loads active ingredients and modifiers on a specific macroporous carrier (pore size>50nm), thereby improving the efficiency of isomerization, and the target product can be obtained in high yield without hydrogen isomerization, and less by-products are produced in the reaction.

[0012] The isomerization reaction may be carried out with or without a solvent; if a solvent is used, it may be ethanol, methanol, isopropanol, water, etc., preferably water; if a solvent is used, the mass ratio of the solvent to 2-methyl-3-butene-2-ol is 1.0-2.0:1.

[0013] The mass ratio of the composite catalyst to the 2-methyl-3-butene-2-ol is 0.01-0.09:1, preferably 0.03-0.07:1.

[0014] The isomerization reaction temperature is 80-120°C, preferably 80-100°C.

[0015] The isomerization reaction time is 2 to 6 hours, preferably 2 to 4 hours.

[0016] The reactor suitable for carrying out the isomerization reaction of the present invention is in principle all common containers which allow reaction under the conditions, especially pressure and temperature, and are suitable for isomerization reaction, such as autoclave, fixed bed, tubular reactor, loop reactor, etc., without any particular limitation.

[0017] The process of the present invention can be operated batchwise, semi-continuously or continuously and is particularly suitable for industrial-scale production.

[0018] The second aspect of the present invention provides a composite catalyst for preparing 3-methyl-2-butene-1-ol from 2-methyl-3-butene-2-ol.

[0019] The composite catalyst comprises an active component, a modifier and a carrier.

[0020] The active ingredient comprises cobalt element and auxiliary metal.

[0021] The auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel and bismuth.

[0022] The carrier is one or more of macroporous silica, macroporous alumina, macroporous carbon, macroporous silicon carbide, and macroporous LaFeO3.

[0023] The cobalt element is derived from one or more of cobalt-containing nitrates, sulfates, hydrochlorides, acetates, acetylacetonates or hydrates thereof.

[0024] The auxiliary metal is derived from one or more of nitrates, sulfates, hydrochlorides, acetates, acetylacetonates, chloroplatinates or hydrates thereof containing palladium, ruthenium, iridium, platinum, iron, copper, nickel or bismuth.

[0025] The modifier is selected from one or more of methionine, arginine, glycine and glutamic acid.

[0026] The mass ratio of the modifier to the carrier is 0.5-2.0:1.

[0027] The mass ratio of the cobalt element to the auxiliary metal (based on the mass of the metal element) is 1:0.1-0.7.

[0028] The mass ratio of the cobalt element to the carrier is 0.03-0.09:1.

[0029] The third aspect of the present invention provides a method for preparing the composite catalyst according to the second aspect, comprising: (1) Adding a modifier and a carrier to a solvent, stirring for modification, and obtaining a modified carrier; (2) adding cobalt salt and auxiliary metal salt to the carrier obtained in step (1), stirring for adsorption, and obtaining a catalyst solution; (3) Remove excess solvent and dry to constant weight to obtain the catalyst for later use.

[0030] In step (1), the solvent plays a dispersing role, and the specific type is not limited, and water is the most preferred.

[0031] In step (1), the modification temperature is 40°C to 80°C, and the modification time is 2h to 6h.

[0032] The cobalt salt is selected from one or more of cobalt-containing nitrates, sulfates, hydrochlorides, acetates, acetylacetonates or hydrates thereof, preferably Co(OAc)2·4H2O, CoCl 2、 One or more of CoCl2·6H2O, CoSO4·7H2O and Co(acac)2.

[0033] In step (2), the auxiliary metal salt is selected from one or more of nitrates, sulfates, hydrochlorides, acetates, acetylacetonates, chloroplatinates or hydrates thereof containing palladium, ruthenium, iridium, platinum, iron, copper, nickel or bismuth; preferably one or more of CuSO4·5H2O, Pd(NO3)2·2H2O, RuCl3, IrCl3·3H2O, K2PtCl6, FeCl3·6H2O, NiSO4·6H2O and Bi(NO3)3·6H2O.

[0034] In step (2), the adsorption temperature is 20°C to 60°C, and the adsorption time is 2h to 6h.

[0035] In step (3), the method for removing excess solvent is common post-treatment operations in chemistry such as rotary evaporation, filtration, and evaporation to dryness, which are not specifically limited here.

[0036] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention provides a method for preparing 3-methyl-2-butene-1-ol by double bond and hydroxyl migration of 2-methyl-3-butene-2-ol under mild non-hydrogen conditions, which inhibits the formation of by-products such as enol hydrogenation and polymerization, obtains high-quality products, and can be applied to the subsequent production of citral, reduces the accumulation of trace impurities in the production process, improves the aroma of the citral product, saves the product aroma optimization process, and reduces production energy consumption.

[0037] (2) The present invention provides a catalyst for preparing 3-methyl-2-butene-1-ol by isomerization reaction of 2-methyl-3-butene-2-ol. The catalyst preparation method is simple, the raw materials are cheap and readily available, and the catalyst activity is high. The active component supported by the macroporous carrier modified by the modifier is not easy to lose, and the catalyst can be recycled without frequent catalyst replacement. The operation is simple, which is conducive to continuous industrial production and significantly improves equipment utilization.

[0038] (3) The reaction of the present invention can be carried out in a solvent-free environment or in water, and has the advantages of being green and environmentally friendly, simple post-treatment, and low production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is an electron microscope photo of catalyst No. 3 magnified 50 times; Figure 2 This is an electron microscope photo of catalyst No. 3 magnified 5000 times; Figure 3 This is the gas phase spectrum of the product obtained in Example 6. DETAILED DESCRIPTION

[0040] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0041] Preparation method of macroporous LaFeO3 carrier: Referring to the synthesis method of macroporous LaFeO3 in the literature "Preparation of three-dimensional ordered macroporous LaFeO3-based nanomaterials and study on their gas-sensing properties, Qin Jian, master's thesis of Tianjin University in 2014", a macroporous LaFeO3 carrier with a pore size of 380 nm was prepared.

[0042] Other macroporous supports are commercially available. Example 1

[0043] At room temperature, 10.0 g of arginine was evenly dispersed in 40 mL of deionized water, and then 10.0 g of a macroporous LaFeO3 carrier (pore size 380 nm, specific surface area 22.862 m 2 / g, pore volume 0.160cm 3 / g), heat to 60°C, keep stirring for 4 hours, cool to 40°C, add 2.959g Co(OAc)2·4H2O and 0.275g CuSO4·5H2O, keep adsorbing for 4 hours, remove excess water by rotary evaporation, and dry the obtained solid in a vacuum drying oven at 80°C to constant weight to obtain catalyst No. 1.

[0044] 7.0 g of the obtained catalyst No. 1, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 97.1% and a selectivity of 98.2%. Example 2

[0045] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.825 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 2.

[0046] 7.0 g of the obtained No. 2 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.5% and a selectivity of 98.8%. Example 3

[0047] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 3.

[0048] 1.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.8% and a selectivity of 99.2%. Example 4

[0049] 3.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.1% and a selectivity of 99.2%. Example 5

[0050] 5.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.2% and a selectivity of 99.5%. Example 6

[0051] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol, and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100°C, and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, and the conversion rate was 99.6% and the selectivity was 99.7%. After the reaction liquid was cooled to room temperature, the catalyst was separated and recovered by filtration. The reaction liquid was separated by vacuum distillation to obtain 85.20 g of 3-methyl-2-butene-1-ol product, and the product purity was >99.5% (gas phase spectrum).

[0052] Electron microscope model: JEOL JSM-6701F Gas phase model: Agilent 8890 Testing conditions: Chromatographic column: (50% phenyl) methyl polysiloxane capillary column, 30m*0.25mm*0.25um Temperature conditions: ① 60℃ for 6 min; ② 10℃ / min rate, rise to 180℃, maintain for 4 min, vaporization chamber 220℃, detector 240℃; Carrier gas: high purity nitrogen; column flow rate: 1.2 ml / min; split ratio: 1 / 100. Example 7

[0053] 9.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.8% and a selectivity of 99.1%. Example 8

[0054] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 80° C., the reaction was carried out for 2 hours, and the reaction was monitored by gas chromatography. The conversion rate was 98.5% and the selectivity was 99.5%. Example 9

[0055] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 120° C., the reaction was carried out for 2 hours, and the reaction was monitored by gas chromatography. The conversion rate was 99.8% and the selectivity was 98.6%. Example 10

[0056] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 4 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.9% and a selectivity of 99.0%. Embodiment 11

[0057] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 6 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.9% and a selectivity of 98.2%. Example 12

[0058] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of methanol were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.6% and a selectivity of 99.7%. Example 13

[0059] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of ethanol were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.4% and a selectivity of 99.7%. Embodiment 14

[0060] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of isopropanol were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.6% and a selectivity of 99.8%. Embodiment 15

[0061] 7.0 g of the obtained No. 3 catalyst and 100 g of 2-methyl-3-butene-2-ol were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 98.6%. Example 16

[0062] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 150 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., the reaction was carried out for 2 hours, and the reaction was monitored by gas chromatography. The conversion rate was 98.6% and the selectivity was 99.5%. Embodiment 17

[0063] 7.0 g of the obtained No. 3 catalyst, 100 g of 2-methyl-3-butene-2-ol and 200 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.2% and a selectivity of 99.6%. Embodiment 18

[0064] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.925 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 4.

[0065] 1.0 g of the obtained No. 4 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.6% and a selectivity of 99.8%. Embodiment 19

[0066] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 1.268 g of Co(OAc)2·4H2O and 0.589 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 5.

[0067] 7.0 g of the obtained No. 5 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.2% and a selectivity of 98.6%. Embodiment 20

[0068] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.113 g of Co(OAc)2·4H2O and 0.982 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 6.

[0069] 7.0 g of the obtained No. 6 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.8% and a selectivity of 99.2%. Embodiment 21

[0070] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 3.804 g of Co(OAc)2·4H2O and 1.768 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 7.

[0071] 7.0 g of the obtained No. 7 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.9% and a selectivity of 99.5%. Embodiment 22

[0072] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous SiO2 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 8.

[0073] 7.0 g of the obtained No. 8 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.1% and a selectivity of 99.2%. Embodiment 23

[0074] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and uniformly dispersed, then 10.0 g of a macroporous Al2O3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 9.

[0075] 7.0 g of the obtained No. 9 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.2% and a selectivity of 99.5%. Embodiment 24

[0076] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous carbon carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 10.

[0077] 7.0 g of the obtained No. 10 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.7% and a selectivity of 98.6%. Embodiment 25

[0078] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and uniformly dispersed, then 10.0 g of a macroporous SiC carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 11.

[0079] 7.0 g of the obtained No. 11 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.0% and a selectivity of 98.4%. Embodiment 26

[0080] At room temperature, 5.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 12.

[0081] 7.0 g of the obtained No. 12 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.2% and a selectivity of 98.6%. Embodiment 27

[0082] At room temperature, 7.0 g of arginine was added to 40 mL of deionized water and uniformly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 13.

[0083] 7.0 g of the obtained No. 13 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.0% and a selectivity of 99.1%. Embodiment 28

[0084] At room temperature, 15.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 14.

[0085] 7.0 g of the obtained No. 14 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.2%. Embodiment 29

[0086] At room temperature, 20.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 15.

[0087] 7.0 g of the obtained No. 15 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.9% and a selectivity of 99.2%. Embodiment 30

[0088] At room temperature, 10.0 g of methionine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 16.

[0089] 7.0 g of the obtained No. 16 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.6%. Embodiment 31

[0090] At room temperature, 10.0 g of glycine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 17.

[0091] 7.0 g of the obtained No. 17 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.4% and a selectivity of 99.6%. Embodiment 32

[0092] At room temperature, 10.0 g of glutamic acid was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 18.

[0093] 7.0 g of the obtained No. 18 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.2% and a selectivity of 99.5%. Embodiment 33

[0094] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 40°C, and after stirring for 4 hours, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 19.

[0095] 7.0 g of the obtained No. 19 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.4% and a selectivity of 99.6%. Embodiment 34

[0096] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 80°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 20.

[0097] 7.0 g of the obtained No. 20 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.2% and a selectivity of 99.3%. Embodiment 35

[0098] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and uniformly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 40°C, and after stirring for 2 hours, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added at 40°C. After adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 21.

[0099] 7.0 g of the obtained catalyst No. 21, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.1% and a selectivity of 99.2%. Embodiment 36

[0100] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 40°C, and the mixture was stirred for 6 hours. Then, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added at 40°C. After adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 22.

[0101] 7.0 g of the obtained No. 22 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.8% and a selectivity of 99.5%. Embodiment 37

[0102] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 20°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 23.

[0103] 7.0 g of the obtained catalyst No. 23, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.9% and a selectivity of 99.1%. Embodiment 38

[0104] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 24.

[0105] 7.0 g of the obtained No. 24 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.9% and a selectivity of 99.1%. Embodiment 39

[0106] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 2 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 25.

[0107] 7.0 g of the obtained No. 25 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 98.6% and a selectivity of 99.1%. Embodiment 40

[0108] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 26.

[0109] 7.0 g of the obtained catalyst No. 26, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.8% and a selectivity of 99.4%. Embodiment 41

[0110] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.826 g of CoCl2·6H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 27.

[0111] 7.0 g of the obtained No. 27 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.6%. Embodiment 42

[0112] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 3.339 g of CoSO4·7H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 28.

[0113] 7.0 g of the obtained No. 28 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.4% and a selectivity of 99.6%. Embodiment 43

[0114] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and uniformly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 4.232 g of Co(acac)2 and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 29.

[0115] 7.0 g of the obtained catalyst No. 29, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.7%. Embodiment 44

[0116] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 3.457 g of Co(NO3)2·6H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, the excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 30.

[0117] 7.0 g of the obtained No. 30 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.6%. Embodiment 45

[0118] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and uniformly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 1.542 g of CoCl2 and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight, thereby obtaining catalyst No. 31.

[0119] 7.0 g of the obtained No. 31 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.5%. Embodiment 46

[0120] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.876 g of Pd(NO3)2·2H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 32.

[0121] 7.0 g of the obtained No. 32 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.9% and a selectivity of 99.8%. Embodiment 47

[0122] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.718 g of RuCl3 were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 33.

[0123] 7.0 g of the obtained catalyst No. 33, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.9% and a selectivity of 99.8%. Embodiment 48

[0124] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.642 g of IrCl3·3H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 34.

[0125] 7.0 g of the obtained No. 34 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was increased to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.4% and a selectivity of 99.8%. Embodiment 49

[0126] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.872 g of K2PtCl6 were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 35.

[0127] 7.0 g of the obtained No. 35 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.5% and a selectivity of 99.6%. Embodiment 50

[0128] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.694 g of FeCl3·6H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 36.

[0129] 7.0 g of the obtained No. 36 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.2% and a selectivity of 99.1%. Embodiment 51

[0130] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.568 g of NiSO4·6H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 37.

[0131] 7.0 g of the obtained No. 37 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.1% and a selectivity of 99.3%. Embodiment 52

[0132] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of macroporous LaFeO3 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.812 g of Bi(NO3)3·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain catalyst No. 38.

[0133] 7.0 g of the obtained No. 38 catalyst, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 99.2% and a selectivity of 99.5%.

[0134] Catalyst Application Example The catalyst recovered in Example 6 was subjected to an application experiment. The reaction conditions and operation were the same as in Example 6. The experimental results are shown in Table 1.

[0135] Table 1

[0136] Table 1 shows that after the composite catalyst provided by the present invention was used for 10 times continuously, the conversion rate decreased by 0.5% and the selectivity decreased by 1.1%. It can be seen that the catalyst has good stability and activity and has good prospects for industrial application.

[0137] Comparative Example 1 At room temperature, 10.0 g of a macroporous LaFeO3 carrier was added to 40 mL of deionized water, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 6 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain the catalyst of Comparative Example 1.

[0138] 7.0 g of the catalyst obtained in Comparative Example 1, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 69.3% and a selectivity of 73.6%.

[0139] Comparative Example 2 At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, and 10.0 g of a macroporous LaFeO3 carrier was added. The temperature was raised to 60°C, stirred for 4 hours, and then cooled to 40°C. 2.959 g of Co(OAc)2·4H2O was added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain the catalyst of Comparative Example 2.

[0140] 7.0 g of the catalyst obtained in Comparative Example 2, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 56.3% and a selectivity of 70.1%.

[0141] Comparative Example 3 At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, and 10.0 g of a macroporous LaFeO3 carrier was heated to 60°C, stirred for 4 hours, cooled to 40°C, 1.375 g of CuSO4·5H2O was added, and adsorbed for 6 hours. Excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain the catalyst of Comparative Example 3.

[0142] 7.0 g of the catalyst obtained in Comparative Example 3, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 52.1% and a selectivity of 65.4%.

[0143] Comparative Example 4 At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and evenly dispersed, then 10.0 g of a microporous ZSM-5 carrier was added, the temperature was raised to 60°C, and after stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added, and after adsorption for 4 hours, excess water was removed by rotary evaporation, and the obtained solid was placed in a vacuum drying oven at 80°C and dried to constant weight to obtain the catalyst of Comparative Example 4.

[0144] 7.0 g of the catalyst obtained in Comparative Example 4, 100 g of 2-methyl-3-butene-2-ol and 100 g of purified water were added to a high-pressure reactor, the temperature was raised to 100° C., and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, with a conversion rate of 92.3% and a selectivity of 85.9%.

[0145] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A method for synthesizing 3-methyl-2-butene-1-ol, characterized in that: The following steps are involved: 2-methyl-3-butene-2-ol undergoes isomerization reaction under the catalysis of the composite catalyst to generate 3-methyl-2-butene-1-ol; The composite catalyst comprises an active component, a modifier and a carrier; The modifier is an amino acid; The active ingredient comprises cobalt and auxiliary metal; The auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel, and bismuth; The carrier is one or more of macroporous silica, macroporous alumina, macroporous carbon, macroporous silicon carbide, and macroporous LaFeO3.

2. The method for synthesizing 3-methyl-2-butene-1-ol according to claim 1, characterized in that: The isomerization reaction is carried out in the presence of a solvent or in the absence of a solvent; The solvent is one or more of ethanol, methanol, isopropanol and water, and the mass ratio of the solvent to 2-methyl-3-butene-2-ol is 1.0-2.0:

1.

3. The method for synthesizing 3-methyl-2-butene-1-ol according to claim 1, characterized in that: The mass ratio of the composite catalyst to the 2-methyl-3-butene-2-ol is 0.01-0.09:1; The isomerization reaction temperature is 80-120° C., and the isomerization reaction time is 2-6 hours.

4. The method for synthesizing 3-methyl-2-butene-1-ol according to any one of claims 1 to 3, characterized in that: The cobalt element is derived from one or more of cobalt-containing nitrates, sulfates, hydrochlorides, acetates, acetylacetonates or hydrates thereof.

5. The method for synthesizing 3-methyl-2-butene-1-ol according to any one of claims 1 to 3, characterized in that: The auxiliary metal is derived from one or more of nitrates, sulfates, hydrochlorides, acetates, acetylacetonates, chloroplatinates or hydrates thereof containing palladium, ruthenium, iridium, platinum, iron, copper, nickel or bismuth.

6. The method for synthesizing 3-methyl-2-butene-1-ol according to any one of claims 1 to 3, characterized in that: The modifier is selected from one or more of methionine, arginine, glycine and glutamic acid.

7. The method for synthesizing 3-methyl-2-butene-1-ol according to any one of claims 1 to 3, characterized in that: The mass ratio of the modifier to the carrier is 0.5-2.0:1; The mass ratio of the cobalt element to the auxiliary metal is 1:0.1-0.7; The mass ratio of the cobalt element to the carrier is 0.03-0.09:

1.

8. A composite catalyst, characterized in that Includes active ingredients, modifiers and carriers; The modifier is an amino acid; The active ingredient comprises cobalt and auxiliary metal; The auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel, and bismuth; The carrier is one or more of macroporous silica, macroporous alumina, macroporous carbon, macroporous silicon carbide, and macroporous LaFeO3.

9. A method for preparing a composite catalyst as claimed in claim 8, characterized in that: The following steps are involved: (1) Adding a modifier and a carrier to a solvent, stirring for modification, and obtaining a modified carrier; (2) adding cobalt salt and auxiliary metal salt to the carrier obtained in step (1), stirring for adsorption, and obtaining a catalyst solution; (3) removing excess solvent and drying to constant weight to obtain the composite catalyst.

10. The method for preparing the composite catalyst according to claim 9, characterized in that: In step (1), the modification temperature is 40°C to 80°C, and the modification time is 2h to 6h; In step (2), the adsorption temperature is 20°C to 60°C, and the adsorption time is 2h to 6h; In step (1), the solvent is water; In step (2), the cobalt salt is one or more of cobalt-containing nitrates, sulfates, hydrochlorides, acetates, acetylacetonates or hydrates thereof; The auxiliary metal salt is one or more of nitrates, sulfates, hydrochlorides, acetates, acetylacetonates, chloroplatinates or hydrates thereof containing palladium, ruthenium, iridium, platinum, iron, copper, nickel or bismuth.

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