A process for the preparation of 3-borneol-2-butanol

Abstract

The application discloses a preparation method of 3-borneol enyl-2-butanol, which comprises the following steps: taking 3-borneol enyl-2-butanone as raw material, reacting under the hydrogen atmosphere and at 60-150 DEG C for 0.2-24h under the heterogeneous gold-based catalyst, and simultaneously reducing the carbonyl and the double bond to obtain 3-borneol enyl-2-butanol. The conversion rate of the raw material 3-borneol enyl-2-butanone is greater than 95%, and the selectivity of 3-borneol enyl-2-butanol is greater than 95%. The preparation system of 3-borneol enyl-2-butanol has the advantages of high catalyst activity, good stability, good product selectivity, simple operation, safety and environmental protection, simple post-treatment, and great industrial application value.

Description

Technical Field

[0001] This invention relates to the field of preparation technology of 3-borneolenyl-2-butanol, specifically to a method for preparing 3-borneolenyl-2-butanol by using 3-borneolenyl-2-butanone as a raw material and simultaneously reducing carbonyl and double bonds under the action of a heterogeneous gold catalyst. Background Technology

[0002] 3-Bornenyl-2-butanol, also known as sandalwood 210, has a strong woody aroma, similar to natural sandalwood, and is widely used in the fragrance formulations of soaps, shampoos, cosmetics, and other daily chemical products. Currently, industrially, 3-bornenyl-2-butanol is prepared by the catalytic hydrogenation of 3-bornenyl-2-butanone, typically using a Cu / Cr catalyst under hydrogen atmosphere. The reaction yields two main results: 1) incomplete reaction, resulting in the formation of products from the reduction of double bonds and carbonyl groups; 2) to increase the degree of reduction, a secondary reduction is performed after reduction with the Cu / Cr catalyst, using reducing agents such as lithium aluminum hydride, aluminum isopropoxide, or sodium borohydride. This complex post-processing and high cost limit its industrial production (CN101125798A). To overcome the shortcomings of the aforementioned technologies, patent CN111298797A invented a copper-aluminum based rare metal catalyst, wherein the rare metal is selected from one or more of manganese oxide, zirconium oxide, and cerium oxide. This catalyst, together with 3-borneolenyl-2-butanone and a solid base, can catalytically hydrogenate to 3-borneolenyl-2-butanol under hydrogen atmosphere, exhibiting high conversion and selectivity. However, this method also has some problems: the reaction process requires the addition of a base for neutralization or washing, increasing the difficulty of post-processing, which is not addressed in this paper; the cyclic stability of the catalyst is also unknown.

[0003] To address the aforementioned challenges, we have invented a novel method for preparing 3-borneolenyl-2-butanol. This method uses 3-borneolenyl-2-butanone as a raw material, reacting it under a heterogeneous gold catalyst and a hydrogen atmosphere at 60-150°C for 0.2-24 h, simultaneously reducing the carbonyl group and double bond to obtain 3-borneolenyl-2-butanol. The conversion rate of the raw material 3-borneolenyl-2-butanone is >95%, and the selectivity of 3-borneolenyl-2-butanol is >95%. This invention's system exhibits high catalyst activity, good stability, and good product selectivity; it is simple to operate, safe, environmentally friendly, and requires minimal post-processing, making it highly valuable for industrial applications. Summary of the Invention

[0004] To address some prominent issues currently faced in the industrial preparation of 3-borneolenyl-2-butanol, we have invented a novel method for its preparation. This method features high catalyst activity, good stability, and excellent product selectivity; it is simple to operate, safe and environmentally friendly, and requires minimal post-processing, making it highly valuable for industrial applications.

[0005] The present invention is achieved through the following technical solution:

[0006] The specific steps of a method for preparing 3-borneolenyl-2-butanol are as follows: 3-borneolenyl-2-butanone is used as a raw material, and the reaction is carried out at 60-250℃ for 0.2-24h in the presence of hydrogen atmosphere and solvent and under the action of heterogeneous gold catalyst, while reducing carbonyl group and double bond to obtain 3-borneolenyl-2-butanol.

[0007]

[0008] The heterogeneous gold-based catalyst described above contains gold with an average particle size of 2-15 nm (particle size distribution range of 1-30 nm); in addition to gold, it also contains metal M, which is selected from one or more of nickel, cobalt, iron, tin and copper, and element N, which is selected from one or more of silicon, boron and aluminum. These metals M and element N form a support in the form of metal solid solution and / or metal oxide (with element N doped therein), and gold is loaded on the support.

[0009] In a method for preparing 3-bornenenyl-2-butanol,

[0010] The molar ratio of gold to metal M in the heterogeneous gold-based catalyst, Au / M, is 0.005-0.5, preferably 0.01-0.1; the molar ratio of metal M to element N is 1:(10-200), preferably 1:(30-120), and more preferably 1:(20-80).

[0011] The solvent is selected from one or more of methanol, ethanol, ethylene glycol, sec-butanol, isopropanol, n-butanol, tert-amyl alcohol, tert-butanol, and tetrahydrofuran; the amount of solvent used per gram of 3-pyronorne-2-butanone is 1.0 mL to 50.0 mL, preferably 2.0 mL to 10.0 mL;

[0012] The pressure of the hydrogen atmosphere is 0.1-5.0 MPa, preferably 0.5-2.0 MPa.

[0013] The reaction temperature is 60-150℃, preferably 100-130℃;

[0014] The reaction time is 0.2-24 hours, preferably 2-8 hours.

[0015] The molar ratio of 3-pyronein-2-butanone to gold in the catalyst is 1:0.001 to 5, preferably 1:0.01 to 0.5.

[0016] In a method for preparing 3-borneolenyl-2-butanol, the heterogeneous gold catalyst has an equivalent diameter of less than or equal to 200 μm, preferably 20-200 μm, and the reaction is carried out in a reactor equipped with a stirring device (e.g., a batch stirred tank, a suspension bed, or a slurry bed).

[0017] The preparation of the catalyst includes the following steps:

[0018] Preparation of the support: At -10 to 40°C, 0.001 to 0.05 M of the above-mentioned metal M and 0.05 to 2.0 M of element N (the molar ratio of metal M to element N is 1:(10-200), preferably 1:(30-120), more preferably 1:(20-80) of a soluble salt are mixed in an acidic aqueous solution (the molar concentration of hydrogen ions in the acid is 0.05 to 2.0 M, preferably 0.10 to 1.0 M), and stirred and aged at 40 to 100°C for 2 to 48 hours to obtain a solid solution suspension. After spray drying at 210 to 300°C, the suspension is calcined at 400 to 800°C at a rate of 2 to 15°C / min under nitrogen for 2 to 16 hours to obtain the support.

[0019] Catalyst preparation:

[0020] The support was mixed with a gold precursor and polyvinylpyrrolidone, and then impregnated to obtain a catalyst precursor.

[0021] The catalyst is obtained by reduction with hydrogen. The specific process is as follows: the catalyst precursor is filtered, washed and dried, and then calcined under a hydrogen atmosphere. The calcination temperature is 150–450℃ and the calcination time is 1–8h. Alternatively, the catalyst is obtained by reduction with reducing agent Y. The specific process is as follows: the catalyst precursor is filtered, washed and dried, and then an aqueous solution containing 0.005–0.5M reducing agent is added dropwise. The reaction is stirred for 1–8h, and the solid is filtered, washed and dried.

[0022] The amount of polyvinylpyrrolidone used per millimole of Au is 0.05-3.0 g, preferably 0.10 g-1.5 g;

[0023] The molar ratio of the reducing agent Y to gold Au is Y / Au = (200-2):1, preferably (80-10):1.

[0024] In a method for preparing 3-bornenenyl-2-butanol, the heterogeneous gold catalyst,

[0025] The mixing temperature of the metal M and element N is -10 to 40°C, preferably 0 to 15°C;

[0026] The aging temperature during the preparation of the carrier is 40-100℃, preferably 50-75℃;

[0027] The aging time in the preparation of the carrier is 2-48 hours, preferably 12-24 hours;

[0028] The spray drying temperature of the carrier is 210-300℃, preferably 240-280℃;

[0029] The calcination temperature during the preparation of the carrier is 400-800℃, preferably 500-600℃.

[0030] The hydrogen atmosphere calcination temperature of the catalyst precursor is 150-450℃, preferably 200-300℃;

[0031] The catalyst precursor is calcined in a hydrogen atmosphere for 1-8 hours, preferably 2-4 hours.

[0032] The reducing agent is one or both of potassium borohydride and sodium borohydride;

[0033] The soluble salts of metal M are one or more of nitrates, hydrochlorides, acetates, and oxalates;

[0034] The silicon element in element N is selected from one or two of silica sol (20wt%-60wt%) and silica gel (200-300 mesh); the boron element in element N is selected from one or two of boric acid and borate; the aluminum element in element N is selected from one or more of soluble nitrate, hydrochloride, acetate, and sulfate.

[0035] The acid is one or more of nitric acid, hydrochloric acid, acetic acid, oxalic acid, and sulfuric acid;

[0036] The gold precursor is one or more of chloroauric acid, sodium chloroaurate, gold trichloride, potassium gold cyanide, and potassium gold cyanide.

[0037] The conversion rate of the raw material 3-borneolenyl-2-butanone in this invention is >95%, and the selectivity of 3-borneolenyl-2-butanol is >95%. The preparation system of 3-borneolenyl-2-butanol in this invention has high catalyst activity, good stability, and good product selectivity; it is simple to operate, safe and environmentally friendly, and the post-processing is simple, thus having great industrial application value. Attached Figure Description

[0038] Figure 1 This is a particle size distribution diagram of gold in the catalyst prepared in Example 5. Detailed Implementation

[0039] The present invention will be further described in detail below with reference to specific embodiments. The scope of protection of the present invention includes, but is not limited to, the following embodiments. Any modifications to the details and form of the technical solution of the present invention without departing from the meaning and scope of this application shall fall within the scope of protection of the present invention.

[0040] The specific method for preparing the catalyst is as follows:

[0041] Example 1

[0042] Weigh 14.0 g Al(NO3)3·9H2O, 0.1803 g Cu(NO3)2·3H2O, and 2.43 g 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and mix thoroughly under an ice-water bath. Maintain the mixture at 50 °C and age with stirring for 12 h to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 45 μm, and the carrier particle size distribution ranges from 20 to 80 μm. Calcination is then carried out under nitrogen at a rate of 5 °C / min to 600 °C for 5 h.

[0043] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of the above-mentioned support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The mixture was filtered, the solid was washed and dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 45 μm and a particle size distribution range of 20-80 μm. The catalyst was labeled as 0.2 wt% Au / CuO-Al2O3-1, and the average gold particle size in this catalyst was 3.5 nm with a particle size distribution range of 1.2-4.8 nm.

[0044] Example 2

[0045] Weigh 14.0 g of Al(NO3)3·9H2O, 0.1803 g of Cu(NO3)2·3H2O, and 2.43 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and stir until homogeneous. Maintain the mixture at 50 °C and age for 12 h with stirring to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 45 μm, and the carrier particle size distribution ranges from 20 to 80 μm. Calcinate the mixture under nitrogen at a rate of 5 °C / min to 600 °C and maintain the temperature for 5 h.

[0046] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3The mixture of 0.0024 g of polyvinylpyrrolidone (mol / L) and 0.0024 g of sodium borohydride was stirred until homogeneous. Then, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, and dried. An aqueous solution (10 mL) containing 12 mg of sodium borohydride was slowly added dropwise, and the reaction was stirred for 2 h. The solid was filtered, washed with deionized water, and dried under vacuum at 60 °C. The resulting catalyst particles had an average particle size of 45 μm and a particle size distribution range of 20-80 μm. The catalyst was labeled as 0.2 wt% Au / CuO-Al₂O₃⁻², and the average gold particle size in this catalyst was 3.5 nm with a particle size distribution range of 1.2-4.8 nm.

[0047] Example 3

[0048] Weigh 7.5g of 30% silica sol, 14.0g of Al(NO3)3·9H2O, 0.1803g of Cu(NO3)2·3H2O, and 2.43g of 65% HNO3 and place them in a 250mL round-bottom flask. Add 150mL of deionized water and stir until homogeneous. Maintain the mixture at 50℃ and age for 12h with stirring to obtain a solid solution suspension. Spray dry at 270℃. The resulting carrier precursor has an average particle size of 45μm, and the carrier particle size distribution ranges from 20-80μm. Calcinate the mixture under nitrogen at a rate of 5℃ / min to 600℃ and maintain the temperature for 5h.

[0049] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 45 μm and a particle size distribution range of 20-80 μm. The catalyst was labeled as 0.2 wt% Au / SiO2-CuO-Al2O3-3, and the average gold particle size in this catalyst was 3.5 nm with a particle size distribution range of 1.2-4.8 nm.

[0050] Example 4

[0051] Weigh 3.74 g of 30% silica sol, 14.0 g of Al(NO3)3·9H2O, 0.1803 g of Cu(NO3)2·3H2O, and 2.43 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and mix thoroughly under an ice-water bath. Maintain the mixture at 50 °C and age with stirring for 12 h to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 60 μm, and the carrier particle size distribution ranges from 32 to 88 μm. Calcinate the mixture under nitrogen at a rate of 5 °C / min to 600 °C for 5 h.

[0052] Add 10 mL of chloroauric acid solution (c = 2.04 × 10⁻⁶) -3 After mixing 0.0050 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 300 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm and a particle size distribution range of 20-80 μm. The catalyst was labeled as 0.4 wt% Au / SiO2-CuO-Al2O3-4, and the average gold particle size in the catalyst was 3.7 nm with a particle size distribution range of 1.0-5.8 nm.

[0053] Example 5

[0054] Weigh 3.74 g of 30% silica sol, 14.0 g of Al(NO3)3·9H2O, 0.1803 g of Cu(NO3)2·3H2O, 1.15 g of H3BO3, and 2.0 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and stir until homogeneous. Maintain the mixture at 50 °C and age for 12 h with stirring to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 60 μm, and the carrier particle size distribution ranges from 32 to 88 μm. Calcinate the mixture under nitrogen at a rate of 5 °C / min to 600 °C and maintain the temperature for 5 h.

[0055] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm and a particle size distribution range of 32-88 μm. The catalyst was labeled as 0.2 wt% Au / SiO2-CuO-Al2O3-B2O3-5, and the average gold particle size in the catalyst was 2.8 nm with a particle size distribution range of 1.3-5.4 nm.

[0056] The particle size distribution of gold in this catalyst Figure 1 As shown.

[0057] Example 6

[0058] 14.0 g of Al(NO3)3·9H2O, 0.25 g of Co(NO3)2·6H2O, and 2.43 g of 65% HNO3 were weighed and placed in a 250 mL round-bottom flask. 150 mL of deionized water was added and the mixture was stirred until homogeneous under an ice-water bath. The mixture was aged at 50 °C with stirring for 18 h to obtain a solid solution suspension. This suspension was spray-dried at 280 °C. The resulting precursor had an average particle size of 60 μm, and the carrier particle size distribution ranged from 32 to 88 μm. The suspension was then calcined under nitrogen at a rate of 5 °C / min to 600 °C for 8 h.

[0059] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L), the mixture was stirred until homogeneous. Then, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm and a particle size distribution range of 32-88 μm. The catalyst was labeled as 0.2 wt% Au / CoOx-Al2O3-6, and the average gold particle size in the catalyst was 3.0 nm with a particle size distribution range of 1.3-5.5 nm.

[0060] Example 7

[0061] Weigh 14.0 g Al(NO3)3·9H2O, 0.50 g Co(NO3)2·6H2O, and 3.0 g 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and mix thoroughly under ice-water bath conditions. Maintain the mixture at 70 °C with stirring and aging for 12 h to obtain a solid solution suspension. Spray dry at 280 °C. The resulting carrier precursor has an average particle size of 40 μm, and the carrier particle size distribution ranges from 22 to 67 μm. Calcinate the carrier under nitrogen at a rate of 5 °C / min to 600 °C for 8 h.

[0062] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -2 After mixing 0.030 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 40 μm and a particle size distribution range of 22-67 μm. The catalyst was labeled as 2.0 wt% Au / CoOx-Al2O3-7, and the average gold particle size in this catalyst was 6.2 nm with a particle size distribution range of 3.4-10.6 nm.

[0063] Example 8

[0064] 14.0 g of Al(NO3)3·9H2O, 0.27 g of Ni(NO3)2·6H2O, and 2.43 g of 65% HNO3 were weighed and placed in a 250 mL round-bottom flask. 150 mL of deionized water was added and stirred until homogeneous under an ice-water bath. The mixture was aged at 70 °C with stirring for 12 h to obtain a solid solution suspension. This suspension was spray-dried at 280 °C. The resulting precursor had an average particle size of 60 μm, and the carrier particle size distribution ranged from 32 to 88 μm. The suspension was then calcined under nitrogen at a rate of 5 °C / min to 600 °C for 8 h.

[0065] Add 10 mL of chloroauric acid solution (c = 2.04 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L), the mixture was stirred until homogeneous. Then, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 6 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm and a particle size distribution range of 32-88 μm. The catalyst was labeled as 0.4 wt% Au / NiOx-Al2O3-8, and the average gold particle size in the catalyst was 3.3 nm with a particle size distribution range of 1.3-5.5 nm.

[0066] Example 9

[0067] Weigh 3.74 g of 30% silica sol, 14.0 g of Al(NO3)3·9H2O, 0.36 g of Fe(NO3)2·3H2O, 1.15 g of H3BO3, and 2.0 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and stir until homogeneous. Maintain the mixture at 50 °C and age for 24 h with stirring to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 60 μm, and the carrier particle size distribution ranges from 33 to 86 μm. Calcinate at 800 °C under nitrogen at a rate of 5 °C / min for 6 h.

[0068] Add 10 mL of chloroauric acid solution (c = 3.06 × 10⁻⁶). -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 3 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 3 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm and a particle size distribution range of 33-86 μm. The catalyst was labeled as 0.6 wt% Au / SiO2-FeOx-Al2O3-B2O3-9, and the average gold particle size in the catalyst was 3.0 nm with a particle size distribution range of 1.2-5.2 nm.

[0069] Example 10

[0070] Weigh 3.74 g of 30% silica sol, 0.36 g of Fe(NO3)2·3H2O, 7.5 g of H3BO3, and 1.0 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and stir until homogeneous. Maintain the mixture at 50 °C and age for 24 h to obtain a solid solution suspension. Spray dry at 250 °C. The resulting carrier precursor has an average particle size of 160 μm, and the carrier particle size distribution ranges from 135 to 196 μm. Calcinate at 800 °C under nitrogen at a rate of 5 °C / min for 8 h.

[0071] Add 10 mL of chloroauric acid solution (c = 3.06 × 10⁻⁶). -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 3 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 4 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 160 μm and a particle size distribution range of 135-196 μm. The catalyst was labeled as 0.6 wt% Au / SiO2-FeOx-B2O3-10, and the average gold particle size in the catalyst was 2.9 nm with a particle size distribution range of 1.3-5.5 nm.

[0072] Comparative Example 1

[0073] Copper-aluminum catalyst A was prepared according to Example 1 of patent CN111298797A. Experimental results are shown in Example 11. After ten consecutive cycles, the catalyst activity and selectivity significantly decreased. The catalyst was filtered, dried, and weighed; the catalyst mass decreased by 21%, indicating severe mechanical loss and poor catalyst stability, making it unsuitable for long-term cyclic use.

[0074] Comparative Example 2

[0075] Copper-aluminum catalyst B was prepared according to Example 2 of patent CN111298797A. Experimental results are shown in Example 11. After ten consecutive cycles, the catalyst activity and selectivity significantly decreased. The catalyst was filtered, dried, and weighed; the catalyst mass decreased by 19%, indicating severe mechanical loss and poor catalyst stability, making it unsuitable for long-term cyclic use.

[0076] Comparative Example 3

[0077] Weigh 3.74 g of 30% silica sol, 14.0 g of Al(NO3)3·9H2O, and 0.1803 g of Cu(NO3)2·3H2O into a 250 mL round-bottom flask. Add 150 mL of deionized water and mix thoroughly under an ice-water bath. Maintain the mixture at 50 °C with stirring and aging for 12 h to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 60 μm, and the carrier particle size distribution ranges from 33 to 86 μm. Calcination is then carried out under nitrogen at a rate of 5 °C / min to 600 °C for 5 h.

[0078] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm, and the support particle size distribution ranged from 33 to 86 μm. The catalyst was labeled as 0.2 wt% Au / SiO2-CuO-Al2O3-C or catalyst C. The average particle size of gold in this catalyst was 4.8 nm, and the particle size distribution ranged from 1.3 to 8.4 nm.

[0079] Comparative Example 4

[0080] Weigh 3.74 g of 30% silica sol, 14.0 g of Al(NO3)3·9H2O, and 2.0 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and stir until homogeneous. Maintain the mixture at 50 °C and age for 12 h to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 60 μm, and the carrier particle size distribution ranges from 33 to 86 μm. Calcinate the mixture under nitrogen at a rate of 5 °C / min to 600 °C and maintain the temperature for 5 h.

[0081] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 0.0024 g of polyvinylpyrrolidone (mol / L) and stirring until homogeneous, 1.0 g of support powder was added, and the mixture was vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm, and the support particle size distribution ranged from 33 to 86 μm. The catalyst was labeled as 0.2 wt% Au / SiO2-Al2O3-D or Catalyst D, and the average gold particle size in the catalyst was 4.7 nm, with a particle size distribution range of 1.3-8.9 nm.

[0082] Comparative Example 5

[0083] Weigh 3.74 g of 30% silica sol, 14.0 g of Al(NO3)3·9H2O, 0.1803 g of Cu(NO3)2·3H2O, 1.15 g of H3BO3, and 2.0 g of 65% HNO3 and place them in a 250 mL round-bottom flask. Add 150 mL of deionized water and stir until homogeneous. Maintain the mixture at 50 °C and age for 12 h with stirring to obtain a solid solution suspension. Spray dry at 270 °C. The resulting carrier precursor has an average particle size of 60 μm, and the carrier particle size distribution ranges from 33 to 86 μm. Calcinate the suspension under nitrogen at a rate of 5 °C / min to 600 °C for 5 h.

[0084] Add 10 mL of chloroauric acid solution (c = 1.02 × 10⁻⁶) -3 After mixing 1.0 g of gold (mol / L) and 1.0 g of support powder, the mixture was stirred until homogeneous. The mixture was then vigorously stirred at room temperature for 4 h. The precursor was filtered, washed, dried, and then calcined at 200 °C for 2 h under a hydrogen atmosphere. The resulting catalyst particles had an average particle size of 60 μm and a particle size distribution range of 33-86 μm. The catalyst was labeled as 0.2 wt% Au / SiO2-CuO-Al2O3-B2O3--E or Catalyst E. The average gold particle size in this catalyst was 5.5 nm, with a particle size distribution range of 1.0-9.2 nm.

[0085] Example 11

[0086] A heterogeneous gold catalyst (molar ratio of 3-borneolenyl-2-butanone to gold: 1:0.002), 0.32 g of 3-borneolenyl-2-butanone, and 1.5 mL of isopropanol were sequentially added to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 2.0 MPa. The reaction was carried out in a 120 °C water bath for 4 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. The conversion rate of 3-borneolenyl-2-butanone and the selectivity of 3-borneolenyl-2-butanol were analyzed by gas chromatography.

[0087]

[0088]

[0089] After ten cycles of reaction, the catalysts obtained in the table above were filtered, dried, and weighed. The mechanical loss rate was calculated, and it was found that the mechanical loss rate of the catalysts obtained in this invention was relatively small, and the catalyst stability was significantly better than that of the catalyst described in patent CN111298797A. Through comparison of experimental results from the examples, it was found that the addition of elements such as silicon and boron to the catalyst helps the support to form a better solid solution, thereby improving the stability of the catalyst (Examples 3, 4, 5, 9, 10).

[0090] Example 12

[0091] 80 mg of the heterogeneous gold catalyst (0.6 wt% Au / SiO2-FeOx-Al2O3-B2O3-9) obtained in Example 9, 0.32 g of 3-borneolenyl-2-butanone, and 1.5 mL of tetrahydrofuran were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 2.0 MPa. The reaction was carried out in a 120°C water bath for 4 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the gas was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 95.2%, and the selectivity of 3-borneolenyl-2-butanol was 96.2%.

[0092] Example 13

[0093] 120 mg of the heterogeneous gold catalyst (0.6 wt% Au / SiO2-FeOx-Al2O3-B2O3-9) obtained in Example 9, 0.48 g of 3-borneolenyl-2-butanone, and 1.5 mL of tert-amyl alcohol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 2.0 MPa. The reaction was carried out in a 150 °C water bath for 3 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 97.2%, and the selectivity of 3-borneolenyl-2-butanol was 95.1%.

[0094] Example 14

[0095] 120 mg of the heterogeneous gold catalyst (0.6 wt% Au / SiO2-FeOx-Al2O3-B2O3-9) obtained in Example 9, 0.48 g of 3-borneolenyl-2-butanone, and 5.0 mL of methanol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed. Hydrogen gas was introduced at 1.0 MPa, and the reaction was carried out in a 160°C water bath for 2 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the gas was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 99.2%, and the selectivity of 3-borneolenyl-2-butanol was 95.0%.

[0096] Example 15

[0097] 120 mg of the heterogeneous gold catalyst (0.6 wt% Au / SiO2-FeOx-Al2O3-B2O3-9) obtained in Example 9, 0.88 g of 3-borneolenyl-2-butanone, and 5.0 mL of methanol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 0.5 MPa. The reaction was carried out in a 160°C water bath for 5 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 99.2%, and the selectivity of 3-borneolenyl-2-butanol was 96.1%.

[0098] Example 16

[0099] 120 mg of the heterogeneous gold catalyst (0.6 wt% Au / SiO2-FeOx-Al2O3-B2O3-9) obtained in Example 9, 0.88 g of 3-borneolenyl-2-butanone, and 3.0 mL of methanol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 0.5 MPa. The reaction was carried out in a water bath at 130 °C for 8 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the pressure was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 99.2%, and the selectivity of 3-borneolenyl-2-butanol was 98.1%.

[0100] Example 17

[0101] 120 mg of the heterogeneous gold catalyst (0.2 wt% Au / SiO2-CuO-Al2O3-B2O3-5) obtained in Example 5, 0.48 g of 3-borneolenyl-2-butanone, and 3.0 mL of ethylene glycol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 0.5 MPa. The reaction was carried out in a water bath at 130 °C for 8 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the gas was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 97.2%, and the selectivity of 3-borneolenyl-2-butanol was 95.6%.

[0102] Example 18

[0103] 120 mg of the heterogeneous gold catalyst (0.2 wt% Au / SiO2-CuO-Al2O3-B2O3-5) obtained in Example 5, 0.48 g of 3-borneolenyl-2-butanone, and 2.0 mL of tert-butanol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 2.0 MPa. The reaction was carried out in a 150 °C water bath for 5 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the gas was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 96.2%, and the selectivity of 3-borneolenyl-2-butanol was 95.7%.

[0104] Example 19

[0105] 120 mg of the heterogeneous gold catalyst (0.2 wt% Au / SiO2-CuO-Al2O3-B2O3-5) obtained in Example 5, 0.48 g of 3-borneolenyl-2-butanone, and 4.0 mL of tert-butanol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 1.0 MPa. The reaction was carried out in a 160°C water bath for 3 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the gas was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 95.5%, and the selectivity of 3-borneolenyl-2-butanol was 97.7%.

[0106] Example 20

[0107] 150 mg of the heterogeneous gold catalyst (0.2 wt% Au / SiO2-CuO-Al2O3-B2O3-5) obtained in Example 5, 0.64 g of 3-borneolenyl-2-butanone, and 3.0 mL of isopropanol were weighed and added sequentially to a 10 mL glass reaction tube. The tube was placed in a stainless steel reactor, which was then sealed and purged with hydrogen gas at 2.0 MPa. The reaction was carried out in a 120°C water bath for 8 h to generate 3-borneolenyl-2-butanol. After the reaction was completed, the reactor was cooled to room temperature using an ice-water bath, and the gas was slowly released to atmospheric pressure. The reactor was then opened, and 150 mg of naphthalene was added to the reaction solution as an internal standard. Gas chromatography analysis showed that the conversion rate of 3-borneolenyl-2-butanone was 97.2%, and the selectivity of 3-borneolenyl-2-butanol was 95.2%.

Claims

1. A method for preparing 3-borneolenyl-2-butanol, characterized in that, Using 3-borneolenyl-2-butanone as a raw material, under the presence of hydrogen atmosphere and solvent, and with the action of a heterogeneous gold catalyst, the reaction was carried out at 60-250℃ for 0.2-24 h, while simultaneously reducing the carbonyl group and double bond to obtain 3-borneolenyl-2-butanol. The heterogeneous gold-based catalyst described above contains gold with an average particle size of 2-15 nm and a particle size distribution range of 1-30 nm; in addition to gold, it also contains metal M, which is selected from one or more of nickel, cobalt, iron, and copper, and element N, which is selected from one or more of silicon, boron, and aluminum. These metals M and element N form a support in the form of a metal solid solution and / or metal oxide, with gold loaded on the support; the preparation of the catalyst includes the following steps: Preparation of the support: At -10 to 40°C, 0.001 to 0.05 M of the above-mentioned metal M and 0.05 to 2.0 M of element N, with a molar ratio of metal M to element N of 1:(10 to 200), a soluble salt is mixed in an acidic aqueous solution with a hydrogen ion concentration of 0.05 to 2.0 M in the acid. The mixture is stirred and aged at 40 to 100°C for 2 to 48 h to obtain a solid solution suspension. After spray drying at 210 to 300°C, the suspension is calcined at 400 to 800°C under nitrogen at a rate of 2 to 15°C / min for 2 to 16 h to obtain the support. Catalyst preparation: The support was mixed with a gold precursor and polyvinylpyrrolidone, and then impregnated to obtain a catalyst precursor. The catalyst is obtained by hydrogen reduction. The specific process is as follows: the catalyst precursor is filtered, washed and dried, and then calcined under a hydrogen atmosphere. The calcination temperature is 150–450°C, and the calcination time is 1–8 h. Alternatively, the catalyst is obtained by reduction with a reducing agent. The specific process is as follows: the catalyst precursor is filtered, washed and dried, and then an aqueous solution containing 0.005–0.5 M of reducing agent is added dropwise. The reaction is stirred for 1–8 h, and the solid is filtered, washed, and dried. The amount of polyvinylpyrrolidone used per millimole of Au is 0.05-3.0 g.

2. The preparation method according to claim 1, characterized in that, In the heterogeneous gold-based catalyst, the molar ratio of gold to metal M (Au / M) is 0.005-0.5; the molar ratio of metal M to element N is 1:(10-200).

3. The preparation method according to claim 2, characterized in that, The molar ratio of gold to metal M in the heterogeneous gold-based catalyst is Au / M, which is 0.01-0.1; the molar ratio of metal M to element N is 1:(30-120).

4. The preparation method according to claim 1, characterized in that, The solvent is selected from one or more of methanol, ethanol, ethylene glycol, sec-butanol, isopropanol, n-butanol, tert-amyl alcohol, tert-butanol, and tetrahydrofuran; the amount of solvent used per gram of 3-pyronorne-2-butanone is 1.0 mL to 50.0 mL. The pressure of the hydrogen atmosphere is 0.1-5.0 MPa; The reaction temperature is 60-150 ℃; The reaction time is 0.2-24 h.

5. The preparation method according to claim 4, characterized in that, The solvent is selected from one or more of methanol, ethanol, ethylene glycol, sec-butanol, isopropanol, n-butanol, tert-amyl alcohol, tert-butanol, and tetrahydrofuran; the amount of solvent used per gram of 3-pyronorne-2-butanone is 2.0 mL to 10.0 mL. The pressure of the hydrogen atmosphere is 0.5-2.0 MPa; The reaction temperature is 100-130 ℃; The reaction time is 2-8 h.

6. The preparation method according to claim 1, characterized in that, The molar ratio of 3-pyronein-2-butanone to gold in the catalyst is 1:0.001~5.

7. The preparation method according to claim 6, characterized in that, The molar ratio of 3-pyronein-2-butanone to gold in the catalyst is 1:0.01~0.

5.

8. The method of claim 1, wherein, The equivalent diameter of the catalyst particles is less than or equal to 200µm, and the reaction is carried out in a reactor equipped with a stirring device.

9. The preparation method according to any one of claims 1-5, characterized in that, The amount of polyvinylpyrrolidone used per millimole of Au is 0.10 g to 1.5 g; The molar ratio of the reducing agent to gold (Au) is reducing agent / Au = (200-2):

1.

10. The preparation method according to claim 9, characterized in that, The mixing temperature of the metal M and element N is -10 to 40°C; The aging temperature during the preparation of the carrier is 40-100℃; The aging time during the preparation of the carrier is 2-48 h; The spray drying temperature of the carrier is 210-300℃; The calcination temperature during the preparation of the carrier is 400-800℃.

11. The preparation method according to claim 10, characterized in that, The mixing temperature of the metal M and element N is 0-15℃; The aging temperature during the preparation of the carrier is 50-75℃; The aging time during the preparation of the carrier is 12-24 h; The spray drying temperature of the carrier is 240-280℃; The calcination temperature during the preparation of the carrier is 500-600℃.

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