Hydrogenated 3-carene catalyst as well as preparation method and application thereof

Abstract

The molecular formula of the hydrogenated 3-carene catalyst is Ni-Y / TiO2, and Y represents a transition metal ion; the hydrogenated 3-carene catalyst is characterized in that active components nickel ions and transition metal ions are loaded in a nano silicon dioxide carrier, the loading capacity of the nickel ions is 25%-30%, and the loading capacity of the transition metal ions is 12%-16%; the transition metal ions are copper ions or iron ions; the invention further discloses a preparation method and application of the catalyst. According to the method, nanoscale titanium dioxide is adopted as a carrier, the carrier and the active component solution are fully mixed and impregnated by ultrasonic stirring, the process is simple, and long-time mechanical stirring is reduced; the transition metals (nickel, copper and iron) are cheap metals, so that the preparation cost of the catalyst can be greatly reduced in industrial application.

Description

Technical Field

[0001] The invention relates to a terpene catalyst and applications thereof, and in particular to a 3-carene hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] Carane is a synthetic organic compound with the characteristics of a colorless oil. It belongs to the bicyclic monoterpenoid compound with a molecular formula of C 10 H 18 This specific structure makes it play an important role in chemical synthesis. Carane is widely used in coatings, inks, papermaking, electronics, food and other industries, and plays a significant role in improving product performance and production efficiency. Carane can be obtained by chemical synthesis and catalytic hydrogenation.

[0003] In the existing chemical synthesis method, 3-carene is used as a raw material, dissolved in tetrahydrofuran, and reduced by borane dimethyl sulfide complex for 19 hours under argon protection to successfully obtain carene; however, this method has a long reaction time, low yield, and the tetrahydrofuran used is highly toxic and expensive. In the prior art, carene is synthesized by reducing carene with lithium aluminum hydride using carene-4-ol and carene-5-ol as raw materials; this method is cumbersome and expensive. The catalytic hydrogenation method mainly uses a supported catalyst to catalyze the hydrogenation of 3-carene to carene under the action of a catalyst. The reported supported catalysts for hydrogenating 3-carene include Raney Ni and Pd / C; this method uses Raney Ni and Pd / C as catalysts, which are expensive, have harsh reaction conditions, and have a long reaction time; a large amount of organic solvent is required, and the volume ratio of the organic solvent to 3-carene is 3:1, which is expensive.

[0004] In summary, the prior art methods for synthesizing carane generally have many unfavorable factors such as a large number of by-products, a long reaction time, complex reaction steps and a low yield, which affect its industrial application. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a catalyst for hydrogenating 3-carene, a preparation method thereof and an application thereof, aiming to obtain a Ni-Y / TiO2 catalyst which is simple to prepare, low in cost, good in stability and can be used for hydrogenating 3-carene reaction, improve the traditional Raney Ni catalyst preparation technology, and reduce the production cost of catalyzing the hydrogenation of 3-carene to prepare carene.

[0006] To achieve the above purpose, the technical solution provided by the present invention is as follows:

[0007] A 3-carene hydrogenation catalyst has a molecular formula of Ni-Y / TiO2, wherein active components nickel ions (Ni) and transition metal ions (Y) are loaded in a nano silicon dioxide (TiO2) carrier, wherein the nickel ion loading is 25% to 30%, and the transition metal ion loading is 12% to 16%; the transition metal ions (Y) are copper ions or iron ions.

[0008] Preferably, the nickel ion loading is 30%, and the transition metal ion loading is 15.5%.

[0009] The preparation method of the catalyst for hydrogenating 3-carene as described above comprises the following steps: mixing nickel nitrate hexahydrate with a transition metal salt carrier and a solvent, fully dispersing and dissolving them under ultrasonic conditions, directly placing them in an oven for drying after impregnation, taking them out, grinding them, and then roasting them to obtain a Ni-Y / TiO2 catalyst (Y represents a transition metal ion), comprising the following steps:

[0010] (1) Mixing: nickel nitrate hexahydrate and a transition metal salt are respectively dissolved in deionized water (DI) and then ultrasonically dissolved and dispersed. The nickel nitrate solution and the transition metal salt solution obtained after dispersion are mixed, and the pretreated carrier nano-sized titanium dioxide is added and ultrasonicated to obtain a mixed solution.

[0011] (2) Impregnation: placing the mixed solution obtained in step (1) at 80° C. to allow it to be fully impregnated, and then drying;

[0012] (3) calcination: the material obtained after drying in step (2) is crushed, ground, sieved, and calcined;

[0013] (4) Reduction: The material obtained after calcination in step (3) is reduced under a reducing atmosphere to obtain a Ni-Y / TiO2 catalyst (a catalyst in which nickel (Ni) and transition metal ions (Y, where Y is Cu or Fe) are supported on titanium dioxide), which is a catalyst for hydrogenating 3-carene.

[0014] Preferably, the pretreated carrier nano-scale titanium dioxide in step (1) is prepared by dissolving the carrier nano-scale titanium dioxide in deionized water and ultrasonicating for 0.5 hours; the ultrasonic dissolution and dispersion time in step (1) is 0.5 hours; and the pretreated carrier nano-scale titanium dioxide is added and ultrasonicated for 2 hours to obtain a mixed solution.

[0015] Preferably, the solvent in step (1) is deionized water; and the transition metal salt is copper nitrate or iron nitrate.

[0016] Preferably, the impregnation in step (2) is performed at 80° C. for 24 hours; the drying in step (2) is performed in an oven or in a vacuum; the oven drying is performed at 90° C. in an oven for 6 to 8 hours, and the vacuum drying is performed in a vacuum for 5 to 6 hours.

[0017] Preferably, the sieving in step (3) is through a 60-mesh sieve; the calcination temperature in step (3) is 400° C., and the calcination time is 4 hours.

[0018] Preferably, the reducing atmosphere described in step (4) is a mixed gas of hydrogen and nitrogen; specifically, a mixture of hydrogen and nitrogen in a volume ratio of 1:9; the reduction described in step (4) is a reduction at 350-500° C. for 3 hours.

[0019] The hydrogenation 3-carene catalyst prepared as above is used in the preparation of carene.

[0020] As described above, the operation method is to add the Ni-Y / TiO2 catalyst to 3-carene, carry out hydrogenation reaction at 100°C, maintain the hydrogen pressure at 5Mpa, and stir at 600r / min for 3 hours, and cool to room temperature after the reaction to obtain carene. Preferably, 0.075g of Ni-Y / TiO2 catalyst is added per 1mL of 3-carene.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The method of the present invention uses nano-sized titanium dioxide as a carrier, and uses ultrasonic stirring to fully mix and impregnate the carrier and the active component solution. The process is simple and reduces the long-term mechanical stirring. Transition metals (nickel, copper and iron) are all cheap metals, which can greatly reduce the preparation cost of the catalyst in industrial applications.

[0023] (2) The method of the present invention can prepare a large amount of catalysts at the same time, greatly shortening the catalyst preparation time;

[0024] (3) The Ni-YTiO2 catalyst prepared by the present invention is a powdered solid, which is suitable for heterogeneous catalytic 3-carene hydrogenation and has high catalytic efficiency. The 3-carene conversion rate reaches 100%, and the carene selectivity reaches 92.66%. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the infrared spectrum of the Ni-Cu / TiO2 catalyst prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0026] The specific embodiments are described in detail below in conjunction with the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited by the specific embodiments. The raw materials and reagents used in the examples are all commercially available unless otherwise specified. Among them, the specifications of the micro-mechanical stirring reactor are MSC / MSG fast-opening type, and 8860 Agilent gas chromatograph is used for analysis.

[0027] Example 1

[0028] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0029] (1) Mixing: dissolving 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain pretreated carrier nano-scale titanium dioxide; dissolving 6.38 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a nickel nitrate solution; dissolving 2.12 g of copper nitrate trihydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a copper nitrate solution; mixing the obtained nickel nitrate solution and copper nitrate solution, adding the pretreated carrier nano-scale titanium dioxide, and continuing ultrasonically dispersing for 2 hours to obtain a mixed solution;

[0030] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0031] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0032] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained brown solid powder is a Ni-Cu / TiO2 catalyst (a catalyst in which nickel (Ni) and copper (Cu) are loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 30% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of copper ions is 15.5% of the mass of the carrier nano-scale titanium dioxide.

[0033] The use of the hydrogenation 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Cu / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 3 hours, and cool to room temperature after the reaction to obtain carene. After filtering the sample through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 100%, and the selectivity of carene is 93.21%.

[0034] Example 2

[0035] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0036] (1) Mixing: Dissolve 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonicate for 0.5 hours to obtain pretreated carrier nano-scale titanium dioxide; Dissolve 6.38 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonicate for 0.5 hours to obtain a nickel nitrate solution; Dissolve 3.54 g of iron (III) nitrate nonahydrate in 10 mL of deionized water, and ultrasonicate for 0.5 hours to obtain an iron nitrate solution; Mix the obtained nickel nitrate solution and iron nitrate solution, and then add the pretreated carrier nano-scale titanium dioxide and continue ultrasonicate for 2 hours to obtain a mixed solution;

[0037] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0038] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0039] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained brown solid powder is a Ni-Fe / TiO2 catalyst (a catalyst of nickel (Ni) and iron (Fe) supported on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 30% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of iron ions is 14.1% of the mass of the carrier nano-scale titanium dioxide.

[0040] The use of the hydrogenation 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Fe / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 3 hours, and cool to room temperature after the reaction to obtain carene. After filtering the sample through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 100%, and the selectivity of carene is 92.50%.

[0041] Example 3

[0042] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0043] (1) Mixing: dissolving 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain pretreated carrier nano-scale titanium dioxide; dissolving 4.96 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a nickel nitrate solution; dissolving 1.65 g of copper nitrate trihydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a copper nitrate solution; mixing the obtained nickel nitrate solution and copper nitrate solution, and then adding the pretreated carrier nano-scale titanium dioxide and continuing ultrasonically dispersing for 2 hours to obtain a mixed solution;

[0044] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0045] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0046] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained brown solid powder is a Ni-Cu / TiO2 catalyst (a catalyst of nickel (Ni) and copper (Cu) loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 25% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of copper ions is 12.6% of the mass of the carrier nano-scale titanium dioxide.

[0047] The use of the hydrogenation 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Fe / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 3 hours, and cool to room temperature after the reaction to obtain carene. After filtering the sample through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 92.70%, and the selectivity of carene is 91.60%.

[0048] Comparative Example 1

[0049] A method for preparing a catalyst, the operating steps are as follows:

[0050] (1) Mixing: 3 g of carrier nano-scale titanium dioxide was dissolved in 20 mL of deionized water, and ultrasonicated for 0.5 hours to obtain a pretreated carrier nano-scale titanium dioxide; 6.38 g of nickel nitrate hexahydrate was dissolved in 10 mL of deionized water, and ultrasonicated for 0.5 hours to obtain a nickel nitrate solution, and then the pretreated carrier nano-scale titanium dioxide was added and ultrasonicated for 2 hours to obtain a mixed solution;

[0051] The remaining operating steps are the same as those in Example 1; a Ni / TiO2 catalyst (a catalyst of nickel (Ni) loaded on titanium dioxide) is obtained; the loading amount of nickel (Ni) in the obtained catalyst is 30% of the mass of the carrier nano-sized titanium dioxide.

[0052] The catalyst prepared above is used in the preparation of carane. The preparation method is as follows: 20 mL of 3-carene is weighed and placed in a 50 mL micro-mechanical stirring reactor, and then 1.5 g of the prepared Ni / TiO2 catalyst is added, hydrogen is introduced and ventilation treatment is performed three times to completely replace the original air in the reactor, and then a hydrogenation reaction is performed at a temperature of 100° C., a hydrogen pressure of 5 MPa, and a stirring speed of 600 r / min. The reaction is performed for 3 hours, and the reaction is cooled to room temperature after the reaction to obtain carane. After the sample is filtered through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 100%, and the selectivity of carane is 73.10%.

[0053] Comparative Example 2

[0054] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0055] (1) Mixing: 3 g of carrier nano-scale titanium dioxide was dissolved in 20 mL of deionized water, and ultrasonicated for 0.5 hours to obtain the pretreated carrier nano-scale titanium dioxide; 6.38 g of nickel nitrate hexahydrate was dissolved in 10 mL of deionized water, and ultrasonicated for 0.5 hours to obtain a nickel nitrate solution; 1.73 g of manganese chloride tetrahydrate was dissolved in 10 mL of deionized water, and ultrasonicated for 0.5 hours to obtain a manganese chloride solution; the obtained nickel nitrate solution and manganese chloride solution were mixed, and the pretreated carrier nano-scale titanium dioxide was added and ultrasonicated for 2 hours to obtain a mixed solution;

[0056] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0057] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0058] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained off-white solid powder is a Ni-Mn / TiO2 catalyst (a catalyst in which nickel (Ni) and manganese (Mn) are loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 30% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of manganese ions is 13.8% of the mass of the carrier nano-scale titanium dioxide.

[0059] The use of the hydrogenation 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Mn / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 3 hours, and cool to room temperature after the reaction to obtain carene. After filtering the sample through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 53.80% and the selectivity of carene is 99%.

[0060] Comparative Example 3

[0061] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0062] (1) Mixing: dissolving 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a pretreated carrier nano-scale titanium dioxide; dissolving 6.38 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a nickel nitrate solution; dissolving 3.97 g of lanthanum nitrate hexahydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a lanthanum nitrate solution; mixing the obtained nickel nitrate solution and lanthanum nitrate solution, adding the pretreated carrier nano-scale titanium dioxide, and continuing ultrasonically dispersing for 2 hours to obtain a mixed solution;

[0063] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0064] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0065] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The resulting black solid powder is a Ni-La / TiO2 catalyst (a catalyst of nickel (Ni) and lanthanum (La) loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 30% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of lanthanum ions is 14.3% of the mass of the carrier nano-scale titanium dioxide.

[0066] The use of the hydrogenated 3-carene catalyst prepared above in the preparation of carene is as follows: 20 mL of 3-carene is weighed and placed in a 50 mL micro-mechanical stirring reactor, then 1.5 g of the prepared Ni-La / TiO2 catalyst is added, hydrogen is introduced and ventilation treatment is performed three times, and after completely replacing the original air in the reactor, a hydrogenation reaction is performed at a temperature of 100° C., a hydrogen pressure of 5 MPa, and a stirring speed of 600 r / min, and the reaction is performed for 3 hours, and then cooled to room temperature after the reaction to obtain carene. After filtering the sample through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 100%, and the selectivity of carene is 86.84%.

[0067] Comparative Example 4

[0068] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0069] (1) Mixing: Dissolve 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonicate for 0.5 hours to obtain pretreated carrier nano-scale titanium dioxide; Dissolve 3.72 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonicate for 0.5 hours to obtain a nickel nitrate solution; Dissolve 1.24 g of copper nitrate trihydrate in 10 mL of deionized water, and ultrasonicate for 0.5 hours to obtain a copper nitrate solution; Mix the obtained nickel nitrate solution and copper nitrate solution, and then add the pretreated carrier nano-scale titanium dioxide and continue ultrasonicate for 2 hours to obtain a mixed solution;

[0070] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0071] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0072] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained brown solid powder is a Ni-Cu / TiO2 catalyst (a catalyst of nickel (Ni) and copper (Cu) loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 20% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of copper ions is 9.8% of the mass of the carrier nano-scale titanium dioxide.

[0073] The use of the hydrogenated 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Fe / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 3 hours, cool to room temperature after the reaction, and obtain carene. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the conversion rate of 3-carene is 78.60%, and the selectivity of carene is 87.10%.

[0074] Comparative Example 5

[0075] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0076] (1) Mixing: dissolving 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain pretreated carrier nano-scale titanium dioxide; dissolving 8.03 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a nickel nitrate solution; dissolving 2.66 g of copper nitrate trihydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a copper nitrate solution; mixing the obtained nickel nitrate solution and copper nitrate solution, adding the pretreated carrier nano-scale titanium dioxide, and continuing ultrasonically dispersing for 2 hours to obtain a mixed solution;

[0077] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0078] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 400° C. for 4 hours;

[0079] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained brown solid powder is a Ni-Cu / TiO2 catalyst (a catalyst in which nickel (Ni) and copper (Cu) are loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 35% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of copper ions is 20% of the mass of the carrier nano-scale titanium dioxide.

[0080] The use of the hydrogenation 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Fe / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments, after completely replacing the original air in the reactor, at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa and a stirring speed of 600r / min for hydrogenation reaction, react for 3 hours, cool to room temperature after the reaction, and obtain carene. After filtering the sample through a filter membrane, take the filtrate for gas chromatography analysis, and calculate that the conversion rate of 3-carene is 67.40% and the selectivity of carene is 78.60%.

[0081] Comparative Example 6

[0082] A method for preparing a catalyst for hydrogenating 3-carene, the operating steps are as follows:

[0083] (1) Mixing: dissolving 3 g of carrier nano-scale titanium dioxide in 20 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain pretreated carrier nano-scale titanium dioxide; dissolving 6.38 g of nickel nitrate hexahydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a nickel nitrate solution; dissolving 2.12 g of copper nitrate trihydrate in 10 mL of deionized water, and ultrasonically dissolving and dispersing for 0.5 hours to obtain a copper nitrate solution; mixing the obtained nickel nitrate solution and copper nitrate solution, adding the pretreated carrier nano-scale titanium dioxide, and continuing ultrasonically dispersing for 2 hours to obtain a mixed solution;

[0084] (2) Impregnation: The mixed solution obtained in step (1) is impregnated at 80° C. for 24 hours, and then placed in an oven and dried at 90° C. for 8 hours;

[0085] (3) Calcination: The dried material obtained in step (2) was fully crushed and ground to pass through a 60-mesh sieve, and the sieved material was placed in a muffle furnace and calcined at 450° C. for 4 hours;

[0086] (4) Reduction: The material obtained after calcination in step (3) is reduced at 450° C. for 3 hours in a mixed gas of hydrogen and nitrogen (hydrogen and nitrogen are mixed in a volume ratio of 1:9). The obtained brown solid powder is a Ni-Cu / TiO2 catalyst (a catalyst of nickel (Ni) and copper (Cu) loaded on titanium dioxide), i.e., a catalyst for hydrogenating 3-carene; the loading amount of nickel (Ni) in the obtained catalyst is 30% of the mass of the carrier nano-scale titanium dioxide, and the loading amount of copper ions is 15.5% of the mass of the carrier nano-scale titanium dioxide.

[0087] The use of the hydrogenation 3-carene catalyst prepared above in the preparation of carene, the preparation method is as follows: weigh 20mL 3-carene and put it into a 50mL micro-mechanical stirring reactor, then add 1.5g of the prepared Ni-Fe / TiO2 catalyst, introduce hydrogen and perform three ventilation treatments to completely replace the original air in the reactor, and then carry out hydrogenation reaction at a temperature of 100°C, maintain a hydrogen pressure of 5Mpa, and a stirring speed of 600r / min for 3 hours, and cool to room temperature after the reaction to obtain carene. After filtering the sample through a filter membrane, the filtrate is taken for gas chromatography analysis, and the conversion rate of 3-carene is calculated to be 100%, and the selectivity of carene is 89.73%.

[0088] Figure 1 The infrared spectrum of the Ni-Cu / TiO2 catalyst prepared by the method of the present invention is as follows: Figure 1 It can be seen that the infrared curve is located at 1200-1600cm -1 The peaks in the region and 2842 cm -1 The peaks near 490-750cm correspond to the stretching vibration bands of CN and NH bonds. -1 The peak at 1042 cm-1 belongs to the stretching vibration of the Cu-O bond. -1 The weak peak at 625 cm-1 can be well attributed to the CO-Cu bond, and the broad peak at around 625 cm-1 belongs to the Ti-O bond. This shows that nickel ions and copper ions have successfully entered the titanium dioxide lattice and are effectively loaded on the nano-TiO2 carrier.

[0089] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A catalyst for hydrogenating 3-carene, characterized in that: The molecular formula of the hydrogenation 3-carene catalyst is Ni-Y / TiO2, where Y represents a transition metal ion. The hydrogenation 3-carene catalyst is an active component of nickel ions and transition metal ions loaded in a nano-silicon dioxide carrier, wherein the nickel ion loading is 25% to 30%, and the transition metal ion loading is 12% to 16%. The transition metal ions are copper ions or iron ions.

2. The catalyst for hydrogenating 3-carene according to claim 1, characterized in that: The nickel ion loading is 30%, and the transition metal ion loading is 15.5%.

3. A method for preparing the catalyst for hydrogenating 3-carene as claimed in claim 1, characterized in that: The following steps are included: (1) Mixing: nickel nitrate and transition metal salt are dissolved in water and then dispersed by ultrasonication. The nickel nitrate solution and transition metal salt solution obtained after dispersion are mixed. The pretreated carrier titanium dioxide is added and ultrasonication is continued to obtain a mixed solution. (2) impregnation: impregnating the mixed solution obtained in step (1), and then drying; (3) calcination: the material obtained after drying in step (2) is crushed, ground, sieved, and calcined; (4) Reduction: The material obtained after calcination in step (3) is reduced under a reducing atmosphere to obtain a Ni-Y / TiO2 catalyst, which is a catalyst for hydrogenating 3-carene.

4. The method for preparing the catalyst for hydrogenating 3-carene according to claim 3, characterized in that: The pretreated carrier titanium dioxide described in step (1) is prepared by dissolving carrier nano-scale titanium dioxide in water and ultrasonicating for 0.5 hours; the ultrasonic dispersion time described in step (1) is 0.5 hours; the pretreated carrier titanium dioxide is added and ultrasonicated for 2 hours to obtain a mixed solution; the solvent described in step (1) is water; the transition metal salt described in step (1) is copper nitrate or iron nitrate.

5. The method for preparing the catalyst for hydrogenating 3-carene according to claim 3, characterized in that: The impregnation described in step (2) is impregnation at 80° C. for 24 hours; the drying described in step (2) is one of oven drying and vacuum drying; the oven drying is drying in an oven at 90° C. for 6 to 8 hours, and the vacuum drying is vacuum drying for 5 to 6 hours.

6. The method for preparing the catalyst for hydrogenating 3-carene according to claim 3, characterized in that: The sieving in step (3) is through a 60-mesh sieve; the calcination temperature in step (3) is 400° C., and the calcination time is 4 hours.

7. The method for preparing the catalyst for hydrogenating 3-carene according to claim 3, characterized in that: The reducing atmosphere in step (4) is a mixture of hydrogen and nitrogen in a volume ratio of 1:9; the reduction in step (4) is a reduction at 350-500° C. for 3 hours.

8. Use of the catalyst for hydrogenating 3-carene as claimed in any one of claims 1 to 7 in the preparation of carene.

9. Use of the catalyst for hydrogenating 3-carene according to claim 8 in preparing carene, characterized in that: The operation method is to add the Ni-Y / TiO2 catalyst to 3-carene, carry out hydrogenation reaction at 100°C, maintain the hydrogen pressure at 5Mpa and the stirring speed at 600r / min, react for 3 hours, and cool to room temperature after the reaction to obtain carene.

10. Use of the catalyst for hydrogenating 3-carene according to claim 9 in preparing carene, characterized in that: 0.075 g of Ni-Y / TiO2 catalyst was added per 1 mL of 3-carene.

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