Process for the preparation of 3-methyl-2-buten-1-ol and catalyst therefor

Abstract

The application belongs to the technical field of organic synthesis, and discloses a preparation method of 3-methyl-2-buten-1-ol and a catalyst thereof. The preparation method comprises the following steps: 2-methyl-3-buten-2-ol is subjected to isomerization under the catalysis of a composite catalyst to generate 3-methyl-2-buten-1-ol; the composite catalyst comprises an active ingredient, a modifier and a carrier; the modifier is an amino acid; the active ingredient comprises cobalt elements and auxiliary metals; the auxiliary metals are one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel and bismuth; and the carrier is one or more of macroporous silica, macroporous calcium phosphate, macroporous aluminum oxide, macroporous carbon, macroporous silicon carbide and macroporous LaFeO3. The isomerization process is simple, no hydrogen is needed for isomerization, the selectivity of the final product is high, and no over-hydrogen by-product is generated.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 3-methyl-2-buten-1-ol and a catalyst thereof. BACKGROUND

[0002] 3-methyl-2-buten-1-ol, namely isopentenol, is mainly used for synthesizing important precursors of products such as vitamin E, vitamin A, a perfume product of citral, and a high-efficiency low-toxicity pesticide of a pyrethroid insecticide.

[0003] According to differences in reaction raw materials, the synthesis route of 3-methyl-2-buten-1-ol can be mainly divided into the following three types: (1) Prins method: isobutene and polyformaldehyde are reacted in the presence of disodium hydrogen phosphate to generate a mixture of 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol, and then the enol is converted into isopentenol under the catalysis of a Pd / C catalyst. (2) Isoprene method: isoprene is used as a raw material to react with hydrogen chloride to generate chloroisoprene, 1-chloro-3-methyl-3-butene in the chloroisoprene is converted into 1-chloro-3-methyl-2-butene, and then sodium acetate is generated to generate a corresponding acetate, and then hydrolysis is performed to obtain 3-methyl-2-buten-1-ol. (3) Methyl butenol isomerization method: under alkaline conditions, aceton and acetylene are subjected to alkyne reaction to generate acetylene isopropyl alcohol, and then 2-methyl-3-buten-2-ol is obtained by hydrogenation under the catalysis of a Pd / C catalyst, and then 3-methyl-2-buten-1-ol is obtained by isomerization. The method has the disadvantage of low conversion rate, and a large amount of unreacted raw material needs to be separated and reused. The specific equation is as follows:

[0004]

[0005] In US3925485A, vanillin vanadate is used as a catalyst to perform catalytic isomerization reaction, when the conversion rate is 25.6%, the selectivity of isopentenol is 83%.

[0006] In CN102391073B, 2-methyl-3-buten-2-ol, cyclohexane, and a phosphoric acid aqueous solution with a pH of 1-3 are stirred and reacted at 60-95℃ for 4-15 hours, the conversion rate of 2-methyl-3-buten-2-ol is 19-22%, and the selectivity is greater than 99%.

[0007] In patent CN105967978B, water-containing methyl butenol, namely 2-methyl-3-buten-2-ol, is used as a raw material, vanadium oxide or a metal salt containing vanadium is used as a catalyst, and isopentenol is synthesized by isomerization.

[0008] In patent CN117417231A, 2-methyl-3-buten-2-ol is used as raw material, the hydroxyl group in 2-methyl-3-buten-2-ol is substituted by chlorination to generate 3-chloroisopentene, and then isomerization is carried out to obtain a mixture containing 1-chloroisopentene, and the mixture containing 1-chloroisopentene is hydrolyzed to obtain isopentenol.

[0009] 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 of 2-methyl-3-buten-2-ol to obtain 3-methyl-2-buten-1-ol. SUMMARY

[0010] In view of the defects of the prior art, the present application provides a preparation method of 3-methyl-2-buten-1-ol and a catalyst thereof, which catalyzes the isomerization of 2-methyl-3-buten-2-ol to synthesize 3-methyl-2-buten-1-ol. The isomerization process of the present application is simple, does not require hydrogenation isomerization, has high selectivity of the final product, and no over-hydrogenation by-product is generated.

[0011] To achieve the above purpose, the first aspect of the present application provides the following technical scheme:

[0012] A synthesis method of 3-methyl-2-buten-1-ol, comprising the following steps: isomerization of 2-methyl-3-buten-2-ol under catalysis of a composite catalyst to generate 3-methyl-2-buten-1-ol;

[0013] The composite catalyst comprises an active ingredient, a modifier and a carrier;

[0014] The modifier is an amino acid;

[0015] The active ingredient comprises cobalt element and an auxiliary metal;

[0016] The auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel and bismuth;

[0017] The carrier is one or more of macroporous silica, macroporous alumina, macroporous carbon, macroporous silicon carbide and macroporous LaFeO3.

[0018] The present application adopts a new composite catalyst to catalyze the isomerization of 2-methyl-3-buten-2-ol, the composite catalyst loads active ingredients and modifiers on a specific macroporous carrier (pore size > 50 nm), improves the efficiency of isomerization, and can obtain the target product with high yield without hydrogenation isomerization, and the reaction has few by-products.

[0019] The isomerization reaction can be carried out with or without solvent; if a solvent is used, it can be ethanol, methanol, isopropanol, water, etc., and water is preferred; if a solvent is used, the mass ratio of the solvent to 2-methyl-3-buten-2-ol is 1.0-2.0:1.

[0020] The mass ratio of the composite catalyst to 2-methyl-3-buten-2-ol is 0.01-0.09:1, preferably 0.03-0.07:1.

[0021] The isomerization reaction temperature is 80-120°C, preferably 80-100°C.

[0022] The isomerization reaction time is 2-6 hours, preferably 2-4 hours.

[0023] The reactor suitable for the isomerization reaction of the present application is in principle all common vessels that allow the reaction under the conditions, especially pressure and temperature, and are suitable for isomerization reactions, such as autoclaves, fixed beds, tubular reactors, loop reactors, etc., and no particular limitation is made thereto.

[0024] The process of the present application can be operated intermittently, semi-continuously or continuously, and is particularly suitable for industrial scale production.

[0025] The second aspect of the present application provides a composite catalyst for preparing 3-methyl-2-buten-1-ol from 2-methyl-3-buten-2-ol.

[0026] The composite catalyst comprises an active ingredient, a modifier and a carrier.

[0027] The active ingredient comprises a cobalt element and an auxiliary metal.

[0028] The auxiliary metal is one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel, bismuth.

[0029] The carrier is one or more of macroporous silica, macroporous alumina, macroporous carbon, macroporous silicon carbide, macroporous LaFeO3.

[0030] The cobalt element is derived from one or more of cobalt-containing nitrate, sulfate, hydrochloride, acetate, acetylacetone salt or hydrate thereof.

[0031] The auxiliary metal is derived from one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel, bismuth-containing nitrate, sulfate, hydrochloride, acetate, acetylacetone salt, chloroplatinic acid salt or hydrate thereof.

[0032] The modifier is selected from one or more of methionine, arginine, glycine, glutamic acid.

[0033] The mass ratio of the modifier and the carrier is 0.5-2.0:1.

[0034] The mass ratio of the cobalt element and the auxiliary metal (in terms of the mass of metal elements) is 1:0.1-0.7.

[0035] The mass ratio of the cobalt element and the carrier is 0.03-0.09:1.

[0036] The third aspect of the present application provides a preparation method of the composite catalyst of the second aspect, comprising:

[0037] (1) adding a modifier and a carrier in a solvent, stirring to modify, and obtaining a modified carrier;

[0038] (2) adding a cobalt salt and an auxiliary metal salt to the carrier obtained in step (1), stirring to adsorb, and obtaining a catalyst solution;

[0039] (3) removing excess solvent, drying to constant weight, and obtaining a catalyst for standby use.

[0040] In step (1), the solvent plays a dispersing role, and the specific type is not limited, and water is most preferred.

[0041] In step (1), the modification temperature is 40-80°C, and the modification time is 2-6h.

[0042] The cobalt salt is selected from one or more of cobalt-containing nitrate, sulfate, hydrochloride, acetate, acetylacetone salt or hydrate thereof, and is preferably one or more of Co(OAc)2·4H2O, CoCl 2、 CoCl2·6H2O, CoSO4·7H2O and Co(acac)2.

[0043] In step (2), the auxiliary metal salt is selected from one or more of palladium, ruthenium, iridium, platinum, iron, copper, nickel, bismuth-containing nitrate, sulfate, hydrochloride, acetate, acetylacetone salt, chloroplatinic acid salt or hydrate thereof; and is preferably one or more of CuSO4·5H2O, Pd(NO3)2·2H2O, RuCl3, IrCl3·3H2O, K2PtCl6, FeCl3·6H2O, NiSO4·6H2O, Bi(NO3)3·6H2O.

[0044] In step (2), the adsorption temperature is 20-60°C, and the adsorption time is 2-6h.

[0045] In step (3), the method for removing excess solvent is a common post-treatment operation in chemistry such as rotary evaporation, filtration and evaporation to dryness, which is not specifically limited here.

[0046] Compared with the prior art, the application has the following advantages:

[0047] (1) The application provides a method for preparing 3-methyl-2-buten-1-ol by isomerization of 2-methyl-3-buten-2-ol under mild non-hydrogen conditions, which inhibits the generation of by-products such as enol hydrogenation and polymerization, and high-quality products are obtained.

[0048] (2) The application provides a catalyst for preparing 3-methyl-2-buten-1-ol by isomerization of 2-methyl-3-buten-2-ol, which has the advantages of simple preparation method, low cost and high activity.

[0049] (3) The reaction of the application can be carried out in a solvent-free or aqueous solution, which has the advantages of green environmental protection, simple post-treatment and low production cost. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 It is an electron microscope photo of catalyst No. 3 amplified 50 times;

[0051] Figure 2 It is an electron microscope photo of catalyst No. 3 amplified 5000 times;

[0052] Figure 3 It is a gas chromatogram of the product obtained in Example 6. DETAILED DESCRIPTION

[0053] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the application belongs. The test reagents used in the following examples are conventional biochemical reagents unless otherwise specified, and the experimental methods are conventional methods unless otherwise specified.

[0054] The preparation method of the macroporous LaFeO3 carrier is as follows: refer to the synthesis method of macroporous LaFeO3 in the reference “Preparation of Three-dimensional Ordered Macroporous LaFeO3-based Nanomaterials and Study on Their Gas Sensing Properties, Qin Jian, Master's Thesis of Tianjin University, 2014”, and a macroporous LaFeO3 carrier with a pore size of 380 nm is prepared.

[0055] Other macroporous carriers are commercially available. Example 1

[0056] After 10.0 g of arginine was uniformly dispersed in 40 mL of deionized water at room temperature, 10.0 g of a macroporous LaFeO3 carrier (pore size 380 nm, specific surface area 22.862 m 2 / g, pore volume 0.160 cm 3 / g) was added, and the temperature was raised to 60°C. After stirring for 4 hours, the temperature was lowered to 40°C, 2.959 g of Co(OAc)2·4H2O and 0.275 g of CuSO4·5H2O were added, and adsorption was performed for 4 hours. After the 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, thereby obtaining Catalyst No. 1.

[0057] 7.0 g of Catalyst No. 1, 100 g of 2-methyl-3-buten-2-ol, and 100 g of purified water were added to a high-pressure reaction kettle, the temperature was raised to 100°C, and reaction was performed for 2 hours. The reaction was monitored using gas chromatography, and the conversion rate was 97.1% and the selectivity was 98.2%. Example 2

[0058] After 10.0 g of arginine was uniformly dispersed in 40 mL of deionized water at room temperature, 10.0 g of a macroporous LaFeO3 carrier was added, and the temperature was raised to 60°C. 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 adsorption was performed for 4 hours. After the 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, thereby obtaining Catalyst No. 2.

[0059] 7.0 g of Catalyst No. 2, 100 g of 2-methyl-3-buten-2-ol, and 100 g of purified water were added to a high-pressure reaction kettle, the temperature was raised to 100°C, and reaction was performed for 2 hours. The reaction was monitored using gas chromatography, and the conversion rate was 98.5% and the selectivity was 98.8%. Example 3

[0060] After 10.0 g of arginine was uniformly dispersed in 40 mL of deionized water at room temperature, 10.0 g of a macroporous LaFeO3 carrier was added, and the temperature was raised to 60°C. 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 adsorption was performed for 4 hours. After the 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, thereby obtaining Catalyst No. 3.

[0061] 1.0 g of Catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 100 g of purified water were added to a high-pressure reaction kettle, the temperature was raised to 100°C, and reaction was performed for 2 hours. The reaction was monitored using gas chromatography, and the conversion rate was 98.8% and the selectivity was 99.2%. Example 4

[0062] Take 3.0g of the obtained catalyst No. 3, 100g of 2-methyl-3-buten-2-ol, and 100g of purified water and add them to a high-pressure reactor. Raise the temperature to 100℃ and react for 2 hours. The reaction was monitored by gas chromatography. The conversion rate was 99.1% and the selectivity was 99.2%. Example 5

[0063] Take 5.0g of the obtained catalyst No. 3, 100g of 2-methyl-3-buten-2-ol, and 100g of purified water and add them to a high-pressure reactor. Raise the temperature to 100℃ and react for 2 hours. The reaction was monitored by gas chromatography. The conversion rate was 99.2% and the selectivity was 99.5%. Example 6

[0064] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-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 cooling the reaction solution to room temperature, the catalyst was recovered by filtration. The reaction solution was then separated by vacuum distillation to obtain 85.20 g of 3-methyl-2-buten-1-ol product with a purity >99.5% (gas chromatogram).

[0065] Electron microscope model: JEOL JSM-6701F

[0066] Vapor phase model: Agilent 8890

[0067] Testing conditions:

[0068] Chromatographic column: (50% phenyl)methylpolysiloxane capillary column, 30m*0.25mm*0.25um

[0069] Temperature conditions: ① 60℃ for 6 min; ② 10℃ / min rate, increase to 180℃, hold for 4 min, vaporization chamber 220℃, detector 240℃;

[0070] Carrier gas: high-purity nitrogen; column flow rate: 1.2 ml / min; split ratio: 1 / 100. Example 7

[0071] Take 9.0g of the obtained catalyst No. 3, 100g of 2-methyl-3-buten-2-ol, and 100g of purified water and add them to a high-pressure reactor. Raise the temperature to 100℃ and react for 2 hours. The reaction was monitored by gas chromatography. The conversion rate was 99.8% and the selectivity was 99.1%. Example 8

[0072] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 100 g of purified water were added to a high-pressure reactor. The temperature was raised to 80 °C and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography. The conversion rate was 98.5% and the selectivity was 99.5%. Example 9

[0073] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 100 g of purified water were added to a high-pressure reactor. The temperature was raised to 120 °C and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography. The conversion rate was 99.8% and the selectivity was 98.6%. Example 10

[0074] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.9% and the selectivity was 99.0%. Example 11

[0075] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-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 6 hours. The reaction was monitored by gas chromatography. The conversion rate was 99.9% and the selectivity was 98.2%. Example 12

[0076] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 100 g of methanol 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. The conversion rate was 99.6% and the selectivity was 99.7%. Example 13

[0077] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 100 g of ethanol 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 99.4% and the selectivity was 99.7%. Example 14

[0078] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 100 g of isopropanol were added to a high-pressure reactor, the temperature was raised to 100℃, 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 99.8%. Example 15

[0079] 7.0 g of the obtained catalyst No. 3 and 100 g of 2-methyl-3-buten-2-ol were added to a high-pressure reactor, the temperature was raised to 100℃, and the reaction was carried out for 2 hours. The reaction was monitored by gas chromatography, and the conversion rate was 99.5% and the selectivity was 98.6%. Example 16

[0080] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-2-ol, and 150 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. The conversion rate was 98.6% and the selectivity was 99.5%. Example 17

[0081] 7.0 g of the obtained catalyst No. 3, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.2% and the selectivity was 99.6%. Example 18

[0082] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 1.925 g of CuSO4·5H2O were added. After adsorption for 4 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, which yielded catalyst No. 4.

[0083] 1.0 g of the obtained catalyst No. 4, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.6% and the selectivity was 99.8%. Example 19

[0084] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 1.268 g of Co(OAc)2·4H2O and 0.589 g of CuSO4·5H2O were added. After adsorption for 4 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 5.

[0085] 7.0 g of the obtained catalyst No. 5, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.2% and the selectivity was 98.6%. Example 20

[0086] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 2.113 g of Co(OAc)2·4H2O and 0.982 g of CuSO4·5H2O were added. After adsorption for 4 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, which yielded catalyst No. 6.

[0087] 7.0 g of the obtained catalyst No. 6, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.8% and the selectivity was 99.2%. Example 21

[0088] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 3.804 g of Co(OAc)2·4H2O and 1.768 g of CuSO4·5H2O were added. After adsorption for 4 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, which yielded catalyst No. 7.

[0089] 7.0 g of the obtained catalyst No. 7, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.9% and the selectivity was 99.5%. Example 22

[0090] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous SiO2 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 8.

[0091] 7.0 g of the obtained catalyst No. 8, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.1% and the selectivity was 99.2%. Example 23

[0092] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous Al2O3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, which yielded catalyst No. 9.

[0093] 7.0 g of the obtained catalyst No. 9, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.2% and the selectivity was 99.5%. Example 24

[0094] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous carbon support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 10.

[0095] 7.0 g of the obtained catalyst No. 10, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.7% and the selectivity was 98.6%. Example 25

[0096] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous SiC support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 11.

[0097] 7.0 g of the obtained catalyst No. 11, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.0% and the selectivity was 98.4%. Example 26

[0098] At room temperature, 5.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 12.

[0099] 7.0 g of the obtained catalyst No. 12, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.2% and the selectivity was 98.6%. Example 27

[0100] At room temperature, 7.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 13.

[0101] 7.0 g of the obtained catalyst No. 13, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.0% and the selectivity was 99.1%. Example 28

[0102] At room temperature, 15.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 14.

[0103] 7.0 g of the obtained catalyst No. 14, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.2%. Example 29

[0104] At room temperature, 20.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 15.

[0105] 7.0 g of the obtained catalyst No. 15, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.9% and the selectivity was 99.2%. Example 30

[0106] At room temperature, 10.0 g of methionine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 16.

[0107] 7.0 g of the obtained catalyst No. 16, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.6%. Example 31

[0108] At room temperature, 10.0 g of glycine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 17.

[0109] 7.0 g of the obtained catalyst No. 17, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.4% and the selectivity was 99.6%. Example 32

[0110] At room temperature, 10.0 g of glutamic acid was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 18.

[0111] 7.0 g of the obtained catalyst No. 18, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.2% and the selectivity was 99.5%. Example 33

[0112] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 40 °C and stirred for 4 hours. Then, 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 19.

[0113] 7.0 g of the obtained catalyst No. 19, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.4% and the selectivity was 99.6%. Example 34

[0114] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 80 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 20.

[0115] 7.0 g of the obtained catalyst No. 20, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.2% and the selectivity was 99.3%. Example 35

[0116] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 40 °C and stirred for 2 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 21.

[0117] 7.0 g of the obtained catalyst No. 21, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.1% and the selectivity was 99.2%. Example 36

[0118] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 40 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 22.

[0119] 7.0 g of the obtained catalyst No. 22, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.8% and the selectivity was 99.5%. Example 37

[0120] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 20 °C and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 23.

[0121] 7.0 g of the obtained catalyst No. 23, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.9% and the selectivity was 99.1%. Example 38

[0122] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. Then, 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 24.

[0123] 7.0 g of the obtained catalyst No. 24, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.9% and the selectivity was 99.1%. Example 39

[0124] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 2 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 25.

[0125] 7.0 g of the obtained catalyst No. 25, 100 g of 2-methyl-3-buten-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. The conversion rate was 98.6% and the selectivity was 99.1%. Example 40

[0126] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 26.

[0127] 7.0 g of the obtained catalyst No. 26, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.8% and the selectivity was 99.4%. Example 41

[0128] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 2.826 g of CoCl2·6H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 27.

[0129] 7.0 g of the obtained catalyst No. 27, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.6%. Example 42

[0130] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 3.339 g of CoSO4·7H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 28.

[0131] 7.0 g of the obtained catalyst No. 28, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.4% and the selectivity was 99.6%. Example 43

[0132] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 4.232 g of Co(acac)2 and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 29.

[0133] 7.0 g of the obtained catalyst No. 29, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.7%. Example 44

[0134] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 3.457 g of Co(NO3)2·6H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 30.

[0135] 7.0 g of the obtained catalyst No. 30, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.6%. Example 45

[0136] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 1.542 g of CoCl2 and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 31.

[0137] 7.0 g of the obtained catalyst No. 31, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.5%. Example 46

[0138] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 0.876 g of Pd(NO3)2·2H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 32.

[0139] 7.0 g of the obtained catalyst No. 32, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.9% and the selectivity was 99.8%. Example 47

[0140] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 0.718 g of RuCl3 were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 33.

[0141] 7.0 g of the obtained catalyst No. 33, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.9% and the selectivity was 99.8%. Example 48

[0142] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 0.642 g of IrCl3·3H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 34.

[0143] 7.0 g of the obtained catalyst No. 34, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.4% and the selectivity was 99.8%. Example 49

[0144] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 2.959 g of Co(OAc)2·4H2O and 0.872 g of K2PtCl6 were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 35.

[0145] 7.0 g of the obtained catalyst No. 35, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.5% and the selectivity was 99.6%. Example 50

[0146] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 2.959 g of Co(OAc)2·4H2O and 1.694 g of FeCl3·6H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 36.

[0147] 7.0 g of the obtained catalyst No. 36, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.2% and the selectivity was 99.1%. Example 51

[0148] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 1.568 g of NiSO4·6H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 37.

[0149] 7.0 g of the obtained catalyst No. 37, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.1% and the selectivity was 99.3%. Example 52

[0150] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of macroporous LaFeO3 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 2.959 g of Co(OAc)2·4H2O and 0.812 g of Bi(NO3)3·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining catalyst No. 38.

[0151] 7.0 g of the obtained catalyst No. 38, 100 g of 2-methyl-3-buten-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. The conversion rate was 99.2% and the selectivity was 99.5%.

[0152] Catalyst Application Examples

[0153] The catalyst recovered in Example 6 was used in a re-experiment, with the same reaction conditions and operation as in Example 6. The experimental results are shown in Table 1.

[0154] Table 1

[0155]

[0156] Table 1 shows that after 10 consecutive applications, the conversion rate of the composite catalyst provided by this invention decreased by 0.5% and the selectivity decreased by 1.1%, indicating that the catalyst has good stability and activity and has good prospects for industrial application.

[0157] Comparative Example 1

[0158] At room temperature, 10.0 g of macroporous LaFeO3 support was added to 40 mL of deionized water, the temperature was raised to 60 °C, and stirred for 4 hours. Then the temperature was lowered to 40 °C, and 2.959 g of Co(OAc)2·4H2O and 1.375 g of CuSO4·5H2O were added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining the catalyst of Comparative Example 1.

[0159] 7.0 g of the catalyst obtained in Comparative Example 1, 100 g of 2-methyl-3-buten-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. The conversion rate was 69.3% and the selectivity was 73.6%.

[0160] Comparative Example 2

[0161] 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 support was added, heated to 60 °C, and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 2.959 g of Co(OAc)2·4H2O was added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining the catalyst of Comparative Example 2.

[0162] Take 7.0 g of the catalyst obtained in Comparative Example 2, 100 g of 2-methyl-3-buten-2-ol, and 100 g of purified water and add them to a high-pressure reactor. Raise the temperature to 100 °C and react for 2 hours. The reaction was monitored by gas chromatography. The conversion rate was 56.3% and the selectivity was 70.1%.

[0163] Comparative Example 3

[0164] 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 support was added. The mixture was heated to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C and 1.375 g of CuSO4·5H2O was added. After adsorption for 6 hours, excess water was removed by rotary evaporation. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, thus obtaining the catalyst of Comparative Example 3.

[0165] 7.0 g of the catalyst obtained in Comparative Example 3, 100 g of 2-methyl-3-buten-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. The conversion rate was 52.1% and the selectivity was 65.4%.

[0166] Comparative Example 4

[0167] At room temperature, 10.0 g of arginine was added to 40 mL of deionized water and dispersed evenly. Then, 10.0 g of microporous ZSM-5 support was added. The temperature was raised to 60 °C and stirred for 4 hours. After that, the temperature was lowered to 40 °C, and 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. The resulting solid was dried in a vacuum drying oven at 80 °C until constant weight, which yielded the catalyst of Comparative Example 4.

[0168] 7.0 g of the catalyst obtained in Comparative Example 4, 100 g of 2-methyl-3-buten-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. The conversion rate was 92.3% and the selectivity was 85.9%.

[0169] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A method for synthesizing 3-methyl-2-buten-1-ol, characterized in that, Includes the following steps: 2-Methyl-3-buten-2-ol undergoes an isomerization reaction under the catalysis of a composite catalyst to produce 3-methyl-2-buten-1-ol; The composite catalyst includes an active ingredient, a modifier, and a support; The active ingredient contains cobalt and auxiliary metals; 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; The modifier is selected from one or more of methionine, arginine, glycine, and glutamic acid; 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 cobalt to the carrier is 0.03~0.09:1; 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-buten-2-ol is 1.0~2.0:1; The mass ratio of the composite catalyst to the 2-methyl-3-buten-2-ol is 0.01~0.09:1; The isomerization reaction temperature is 80~120℃, and the isomerization reaction time is 2~6 hours.

2. The method for synthesizing 3-methyl-2-buten-1-ol according to claim 1, characterized in that, The cobalt element is derived from one or more of cobalt-containing nitrates, sulfates, hydrochlorides, acetates, acetylacetone salts, or their hydrates.

3. The method for synthesizing 3-methyl-2-buten-1-ol according to claim 1, characterized in that, The auxiliary metal is derived from one or more of the following: nitrates, sulfates, hydrochlorides, acetates, acetylacetone salts, chloroplatinates, or hydrates of palladium, ruthenium, iridium, platinum, iron, copper, nickel, and bismuth.

4. A composite catalyst, characterized in that, Includes active ingredients, modifiers, and carriers; The modifier is an amino acid; The active ingredient contains cobalt and auxiliary metals; 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; The modifier is selected from one or more of methionine, arginine, glycine, and glutamic acid; 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 cobalt to the carrier is 0.03~0.09:

1.

5. A method for preparing the composite catalyst as described in claim 4, characterized in that, Includes the following steps: (1) Add the modifier and the carrier to the solvent, stir to carry out the modification, and obtain the modified carrier; (2) Add cobalt salt and auxiliary metal salt to the carrier obtained in step (1), stir to carry out adsorption, and obtain catalyst solution; (3) Remove excess solvent and dry to constant weight to obtain the composite catalyst.

6. The method for preparing the composite catalyst according to claim 5, characterized in that, In step (1), the modification temperature is 40℃~80℃, and the modification time is 2h~6h; In step (2), the adsorption temperature is 20℃~60℃, and the adsorption time is 2h~6h; In step (1), the solvent is water; In step (2), the cobalt salt is one or more of the following: cobalt-containing nitrates, sulfates, hydrochlorides, acetates, acetylacetone salts, or their hydrates; The auxiliary metal salt is one or more of the following: nitrates, sulfates, hydrochlorides, acetates, acetylacetone salts, chloroplatinates, or hydrates of palladium, ruthenium, iridium, platinum, iron, copper, nickel, and bismuth.

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