CN113135825B

CN113135825B - Method for preparing aniline by nitrobenzene hydrogenation and hybrid nano-structure nickel catalyst thereof

Info

Publication number: CN113135825B
Application number: CN202110444145.0A
Authority: CN
Inventors: 周继承; 罗文星
Original assignee: Xiangtan University
Current assignee: Xiangtan University
Priority date: 2021-04-23
Filing date: 2021-04-23
Publication date: 2022-04-08
Anticipated expiration: 2041-04-23
Also published as: CN113135825A

Abstract

The invention provides a method for preparing aniline by nitrobenzene hydrogenation and a nickel catalyst with a hybrid nano structure thereof. The method comprises the following steps: under the conditions of specific solvent, catalyst and hydrogenation reaction, the nitrobenzene serving as the raw material undergoes hydrogenation reaction to prepare aniline, wherein the solvent is at least one of isopropanol, methanol and ethanol, and the catalyst is Ni-ZrO₂a/SBA-15 catalyst; the reaction temperature is 80-120 ℃, the hydrogen pressure is 0.8-1.0 MPa, and the reaction time is 10-60 min; wherein the Ni-ZrO₂The preparation method of the SBA-15 catalyst comprises the following steps: preparation of composite carrier ZrO by adopting impregnation method₂SBA-15; ZrO anchoring Ni nanoparticles to composite carrier by gas phase reduction method₂The Ni-ZrO on SBA-15₂The catalyst is SBA-15. The method provided by the invention can obtain 100% of nitrobenzene conversion rate and aniline selectivity under the mild reaction condition.

Description

Method for preparing aniline by nitrobenzene hydrogenation and hybrid nano-structure nickel catalyst thereof

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to a method for preparing aniline by nitrobenzene hydrogenation and a catalyst thereof.

Background

Aniline is widely applied to synthesis of dyes, medicines, pesticides and the like, the traditional aniline production method is nitrobenzene Fe powder reduction, has the characteristics of large environmental pollution, easy corrosion of equipment, difficult continuous production, low efficiency, difficult product separation and the like, and the aniline preparation by adding hydrogen into nitrobenzene liquid phase is an energy-saving and environment-friendly production route and is also the most widely applied aniline production method at present.

Currently, the most commonly used catalysts for this reaction rely primarily on supported noble metals, such as Pd, Pt, Rh, Ru, Au, and the like. However, the limited availability and high price of these rare metals have stimulated catalytic research on non-noble metals, especially Co and Ni metals, but the non-noble metal catalysts must be matched with certain reaction conditions to achieve complete conversion of nitrobenzene to aniline under the existing research forms, because satisfactory product conversion rate is difficult to obtain during catalytic hydrogenation reaction under mild conditions, and meanwhile, the problems of long catalytic time, low selectivity and the like exist, and the production results are difficult to achieve the expected effect.

Therefore, it is especially important to prepare a non-noble metal catalyst which is used for preparing aniline through selective hydrogenation and has excellent activity and selectivity.

Disclosure of Invention

The method adopts an impregnation method to load zirconium oxide on the SBA-15 molecular sieve of the carrier in a single layer form to form a semiconductor film layer, and then anchors nickel nano particles on the semiconductor film layer through a gas phase reduction method, wherein active components of the Ni nano particles and the ZrO nano particles₂The semiconductor film layer generates synergistic effect to prepare Ni-ZrO₂The SBA-15 catalyst has excellent activity and selectivity, and the conversion rate of nitrobenzene and the selectivity of aniline can reach 100% under the mild reaction condition.

In order to achieve the above object, the present invention provides a method for preparing aniline by hydrogenation of nitrobenzene, the method comprising: under the conditions of specific solvent, catalyst and hydrogenation reaction, the nitrobenzene serving as the raw material undergoes hydrogenation reaction to prepare aniline, wherein the solvent is at least one of isopropanol, methanol and ethanol, and the catalyst is Ni-ZrO₂a/SBA-15 catalyst; the hydrogenation reaction conditions include: the reaction temperature is 80-120 ℃, the hydrogen pressure is 0.8-1.0 MPa, and the reaction time is 10-60 min; wherein the Ni-ZrO₂the/SBA-15 catalyst is prepared by the following method comprising:

1) impregnating ZrO₂Loading on SBA-15 molecular sieve in single layer form to form semiconductor film layer to obtain composite carrier ZrO₂/SBA-15；

2) ZrO anchoring Ni nanoparticles to the composite support using gas phase reduction₂The Ni-ZrO on SBA-15₂Catalyst SBA-15, active component Ni nano-particle and ZrO₂The semiconductor film layer has a synergistic effect.

In a specific embodiment, the reaction temperature is preferably 120 ℃ and the reaction time is preferably 30 min.

In a specific embodiment, the Ni-ZrO₂The mol ratio of the nickel in the SBA-15 catalyst to the nitrobenzene is 0.5-1.5%.

In a specific embodiment, the Ni-ZrO₂The mass content of nickel in the SBA-15 catalyst is 3-10%, preferably 5%; the ZrO₂ZrO in/SBA-15 composite carrier₂The content of (b) is 9 to 15% by mass, preferably 10% by mass.

In a specific embodiment, the impregnation method is specifically: ZrOCl is firstly carried out₂Dissolving 8H2O in deionized water, adding molecular sieve SBA-15, uniformly stirring, adding an alkali solution to adjust the pH value to 9, stirring at 80 ℃ for 30-240 min, standing, aging, washing, performing solid-liquid separation, drying and calcining the obtained solution to obtain the composite carrier ZrO, wherein the pH value of the solution is adjusted to 9₂/SBA-15。

In a specific embodiment, in the dipping method, the standing and aging time is 12-24 h; the drying temperature is 70-90 ℃, and the drying time is 8-12 h; the calcination temperature is 450-600 ℃, and the calcination time is 2-4 h.

In a particular embodiment, the gas phase reduction process is in particular: the composite carrier ZrO prepared in the step 1)₂The SBA-15 is dissolved in ethylene glycol, then Ni (NO) is added₃)₂·6H₂O, adding an alkali solution to adjust the pH value to 9 after uniformly stirring, stirring for 4 hours at the temperature of 30 ℃, washing, drying in vacuum and reducing with hydrogen to obtain the Ni-ZrO₂The catalyst is SBA-15.

In a specific embodiment, in the gas-phase reduction method, the temperature of vacuum drying is 70-90 ℃, and the drying time is 8-12 h; the temperature of hydrogen reduction is 600 ℃, and the time of hydrogen reduction is 4 h.

The invention also provides a hybrid nano-structure nickel catalyst for preparing aniline by nitrobenzene hydrogenation, and the expression of the nickel catalyst is Ni-ZrO₂SBA-15 comprises a carrier SBA-15 molecular sieve, ZrO loaded on the carrier SBA-15 molecular sieve in a monolayer form by an impregnation method and forming a semiconductor film layer₂And anchoring to ZrO by gas phase reduction₂Semiconductor filmNi nanoparticles on the layer; wherein the carrier SBA-15 molecular sieve and ZrO loaded on the carrier SBA-15 molecular sieve₂Forming a composite carrier ZrO₂SBA-15, active ingredient Ni nanoparticles and the ZrO₂The semiconductor film layer has a synergistic effect.

In a specific embodiment, the Ni-ZrO₂The mass content of nickel in the SBA-15 catalyst is 3-10%, preferably 5%; the composite carrier ZrO₂ZrO in SBA-15₂The content of (b) is 9 to 15% by mass, preferably 10% by mass.

The beneficial effects of the invention at least comprise:

firstly, because the zirconia is a unique inorganic non-metallic material, the zirconia is a single substance with both an acidic center and a basic center on the surface, and also has excellent ion exchange performance and surface enriched air oxygen sites. And the nano zirconia is an important oxide, and has an irreplaceable position in the field of catalysis due to large specific surface and high activity. And because the nano material has unique properties such as quantum size effect, small size effect, surface effect, macroscopic quantum tunneling effect and the like, the nano zirconia also has various unique physical characteristics and chemical characteristics.

SBA-15 is a molecular sieve with an ordered mesoporous structure, has a unique pore structure, is two-dimensional hexagonal in shape, and has a highly ordered structure. Has the advantages of good hydrothermal stability, strong adsorption capacity, large specific surface area, high microporosity, high pore volume and the like.

According to the invention, zirconium oxide is loaded on the carrier SBA-15 molecular sieve in a single-layer form by an impregnation method to form a semiconductor film layer, and then nickel nanoparticles are anchored on the semi-layer film layer, and the area of the formed semi-layer film layer is large due to the large specific surface area of the carrier SBA-15 molecular sieve, so that on one hand, the nickel nanoparticles serving as an active component are loaded on the composite carrier ZrO₂The SBA-15 has high surface dispersity, small particle size and excellent activity; on the other hand, the nickel nano-particles and the semiconductor film layer have strong synergistic effect, so that an interface electronic effect is generated, and the catalytic performance of the catalyst is improved; in this way it is possible to obtain,so that the catalyst Ni-ZrO provided by the invention₂The SBA-15 can obtain higher selectivity and conversion rate by catalyzing nitrobenzene hydrogenation under the mild reaction condition, and 5 percent of Ni and 10 percent of ZrO₂The SBA-15 catalyst can catalyze nitrobenzene hydrogenation under the conditions of reaction temperature of 120 ℃, reaction time of 30 minutes and hydrogen pressure of 1MPa to obtain 100% of selectivity and 100% of conversion rate.

Compared with the catalyst used for nitrobenzene hydrogenation in the prior art, the catalyst of the invention has better activity, shortens the reaction time required when the conversion rate of nitrobenzene and the selectivity of aniline reach 100% from 4 hours and more in the prior art to 30 minutes, and can greatly improve the yield and reduce the production cost.

Drawings

FIG. 1 shows 5% Ni-10% ZrO prepared in example 1₂TEM image of/SBA-15 catalyst;

FIG. 2 shows 5% Ni-10% ZrO prepared in example 1₂A Ni 2P XPS plot of the/SBA-15 catalyst showing the valence state of Ni;

FIG. 3 shows 5% Ni-10% ZrO prepared in example 1₂XPS totipotent spectrum of/SBA-15 catalyst.

Detailed Description

The invention is described in detail below with reference to the figures and examples, but can be implemented in many different ways, which are limited and covered by the claims.

Example 1

Preparing a catalyst:

0.146g of ZrOCl was taken₂·8H₂Dissolving O in 15mL deionized water, and performing ultrasonic treatment for 10min to ensure that ZrOCl₂·8H₂Completely dissolving O, adding 0.5g of carrier SBA-15, heating in water bath at 80 ℃, and stirring for 4h to uniformly mix; then adjusting the pH value to 9 by using 0.1mol/L NaOH solution, continuing heating in water bath for 4h at 80 ℃, stirring, standing and aging for 12h, washing the obtained solution by using deionized water, filtering, drying for 10h at 80 ℃, and calcining for 2h at 600 ℃ to obtain ZrO₂Composite carrier ZrO with mass fraction of 10%₂SBA-15, i.e. 10% ZrO₂and/SBA-15. Taking 0.5g of composite carrier ZrO₂/SBA-15Dissolving in ethylene glycol, and adding 0.1304g of Ni (NO)₃)₂·6H₂O, stirring in a water bath at 30 ℃ for 4 hours to uniformly mix; then adjusting the pH value to 9 by using 0.1mol/L NaOH solution, continuing stirring for 4 hours in water bath at 30 ℃, washing the obtained solution for 3 times by using absolute ethyl alcohol and deionized water respectively, drying for 10 hours in vacuum at 80 ℃, reducing for 4 hours by using hydrogen at 600 ℃ to obtain Ni-ZrO with the mass fraction of 5 percent of Ni₂SBA-15 catalyst, i.e. 5% Ni-10% ZrO₂/SBA-15。

Preparing aniline by nitrobenzene hydrogenation: taking nitrobenzene and 5 percent of Ni-10 percent of ZrO₂SBA-15 catalyst (molar ratio of Ni to nitrobenzene is 0.5 percent) and 15mL of isopropanol are put into a high-pressure reaction kettle, the pressure of hydrogen is set to be 1Mpa, the reaction temperature is 120 ℃, and H is introduced₂After the air in the reaction kettle is replaced, H is closed₂A valve, when the temperature in the kettle reaches the reaction temperature of 120 ℃, H is introduced₂The reaction was started by opening the stirrer for 30min, and after the reaction was completed, the reaction mixture was cooled, and an appropriate amount of the reaction mixture was centrifuged and analyzed by gas chromatography, and the analysis results are shown in table 1.

Example 2

Same as example 1 except that Ni-ZrO₂The mass fraction of Ni in SBA-15 is 3%, i.e. 3% Ni-10% ZrO₂/SBA-15。

Example 3

Same as example 1 except that Ni-ZrO₂The mass fraction of Ni in SBA-15 is 10%, i.e. 10% Ni-10% ZrO₂/SBA-15。

Example 4

Same as example 1 except that Ni-ZrO₂ZrO in SBA-15₂Is 15 percent, namely 5 percent of Ni-15 percent of ZrO₂/SBA-15。

Comparative example 1

Same as example 1 except that Ni-ZrO₂ZrO in SBA-15₂Is 5% by mass, i.e. 5% Ni-5% ZrO₂/SBA-15。

Comparative example 2

Same as example 1, except that ZrO was not contained in Ni/SBA-15₂The mass fraction of Ni was 5%, i.e., 5% Ni/SBA-15.

Comparative example 3

Same as example 1 except that Ni/ZrO₂The catalyst does not contain SBA-15 molecular sieve, and the mass fraction of Ni is 5 percent, namely 5 percent of Ni/ZrO₂。

Comparative example 4

Same as example 1 except that ZrO₂ZrO-free from Ni in SBA-15₂Is 10%, i.e. 10% ZrO₂/SBA-15。

Note that ZrO in the above examples₂The mass fraction of (b) means ZrO₂On a composite support ZrO₂(ii)/mass fraction in SBA-15.

The results of the catalytic reactions of the catalysts of examples 1-4 and comparative examples 1-4 in the hydrogenation of nitrobenzene are shown in Table 1.

TABLE 1 results of hydrogenation of nitrobenzene catalyzed by Ni/ZrO2/SBA-15 catalysts with different loadings

	Catalyst and process for preparing same	Nitrobenzene conversion (%)	Aniline selectivity (%)
				Example 1	5％Ni-10％ZrO₂/SBA-15	100	100
Example 2	3％Ni-10％ZrO₂/SBA-15	95.4	100
				Example 3	10％Ni-10％ZrO₂/SBA-15	100	98.12
Example 4	5％Ni-15％ZrO₂/SBA-15	87.5	100
				Comparative example 1	5％Ni-5％ZrO₂/SBA-15	38.82	96.3
Comparative example 2	5％Ni/SBA-15	15.72	87.21
				Comparative example 3	5％Ni/ZrO₂	56.67	97.4
Comparative example 4	10％ZrO₂/SBA-15	6.88	92.97

The reaction conditions of the catalytic nitrobenzene hydrogenation in examples 1 to 4 and comparative examples 1 to 4 are the same, and the difference is mainly that the loading of the nickel nanoparticles as the active component and the loading of the zirconium dioxide which has a synergistic effect with the nickel nanoparticles as the active component are not completely the same. Comparing the result data of the example 1 and the comparative examples 1 to 4, it can be seen that the catalyst activity is low when the active components nickel nanoparticles, the semiconductor film layer zirconium dioxide and the molecular sieve SBA-15 are combined in pairs, and good catalytic activity can be obtained only when the three components are combined according to a certain proportion. Comparing the result data of example 1, example 4, comparative example 1 and comparative example 2, it can be seen from comparative example 2 that the activity of the catalyst is low (the nitrobenzene conversion is 15.72%, and the aniline selectivity is 87.21%) under the mild reaction conditions when nickel is directly loaded on the carrier molecular sieve SBA-15; as can be seen from comparative example 1, the zirconium dioxide supported on the support molecular sieve SBA-15 does not have high catalytic activity at the same time when the amount of zirconium dioxide is small, theoretically, the semiconductor film formed by zirconium dioxide is supported on the support molecular sieve SBA-15 in a single layer, the catalytic activity is high, in this example, the composite support ZrO₂ZrO in SBA-15₂Is preferably 10% by mass, more than 10% by mass, the conversion of nitrobenzene being reduced. Comparing the experimental data of examples 1 to 3, it can be seen that the nickel loading increases from 3% to 5%, the nitrobenzene conversion increases, the nickel loading increases from 5% to 10%, and the aniline selectivity decreases. And 5% Ni-10% ZrO₂the/SBA-15 catalyst has the best catalytic activity.

FIG. 1 shows 5% Ni-10% ZrO prepared in example 1₂TEM image of/SBA-15 catalyst; FIG. 2 shows 5% Ni-10% ZrO prepared in example 1₂A Ni 2P XPS plot of the/SBA-15 catalyst showing the valence state of Ni; FIG. 3 shows 5% Ni-10% ZrO prepared in example 1₂XPS totipotent spectrum of/SBA-15 catalyst. As can be seen from fig. 1 to 3, the mass fraction of nickel atoms in the catalyst reaches 31.10%, and the particle size of the nickel nanoparticles is small; meanwhile, because of strong synergistic action of nickel and the semiconductor film layer, an interface electron effect is generated, thereby being beneficial to improving the activity of the catalyst.

Examples 5 to 10

Examples 5 to 10 all of the 5% Ni-10% ZrO prepared in example 1 was used₂The catalyst SBA-15 is different in hydrogenation reaction conditions, and specifically, the hydrogenation reaction conditions of the example 1 are as follows: hydrogen pressure is 1Mpa, reaction temperature is 120 ℃, and reaction time is 30 min; the hydrogenation conditions for example 5 were: hydrogen pressure 1Mpa, reaction temperature 80 deg.C, reaction time 30 min; the hydrogenation conditions for example 6 were: the hydrogen pressure is 1Mpa, the reaction temperature is 100 ℃, and the reaction time is 30 min; the hydrogenation conditions for example 7 were: hydrogen pressure 1Mpa, reaction temperature 120 deg.C, reaction time 20 min; the hydrogenation conditions for example 8 were: hydrogen pressure 1Mpa, reaction temperature 120 deg.C, reaction time 10 min; the hydrogenation conditions for example 9 were: the hydrogen pressure is 0.9Mpa, the reaction temperature is 120 ℃, and the reaction time is 30 min; the hydrogenation conditions for example 10 were: the hydrogen pressure is 0.8Mpa, the reaction temperature is 120 ℃, and the reaction time is 30 min. The results of the catalytic reactions in examples 1 and 5 to 10 in the hydrogenation of nitrobenzene are shown in Table 2.

TABLE 2 results of nitrobenzene hydrogenation under different hydrogenation conditions

Comparing the result data of example 1, example 5 and example 6, it can be seen that, under the same reaction time and hydrogen pressure, the nitrobenzene conversion and aniline selectivity both increase with the increase of reaction temperature, and reach 100% at a reaction temperature of 120 ℃; comparing the data of the results of example 1, example 7 and example 8, it can be seen that the nitrobenzene conversion increases and the aniline selectivity is maintained at 100% with the reaction time under the same reaction temperature and hydrogen pressure; comparing the result data of example 1, example 9 and example 10, it can be seen that the nitrobenzene conversion rate increases and the aniline selectivity is maintained at 100% with the increase of the hydrogen pressure under the same reaction temperature and reaction time. It should be noted that, in the catalytic hydrogenation reaction process of nitrobenzene of the present invention, when the reaction temperature is less than 120 ℃ or the hydrogen pressure is less than 1Mpa, the reaction time can be prolonged to increase the conversion rate of nitrobenzene.

Examples 11 to 12

Examples 11 to 12 all used the 5% Ni-10% ZrO prepared in example 1₂The catalyst/SBA-15 is different from the solvent for preparing aniline by hydrogenation of nitrobenzene, and specifically, the solvent in the embodiment 1 is isopropanol, the solvent in the embodiment 11 is absolute methanol, and the solvent in the embodiment 12 is absolute ethanol. The results of the catalytic reactions in examples 1 and 11 to 12 in the hydrogenation of nitrobenzene are shown in Table 3.

TABLE 3 results of hydrogenation of p-nitrobenzene in different solvents

	Solvent(s)	Nitrobenzene conversion (%)	Aniline selectivity (%)
				Example 1	Isopropanol (I-propanol)	100	100
Examples11	Anhydrous methanol	100	93.11
				Example 12	Anhydrous ethanol	100	98.64

As can be seen from Table 3, when the solvents were absolute methanol and absolute ethanol, nitrobenzene was completely converted at 120 deg.C, 1MPa and 30min, but the selectivity to aniline was slightly decreased.

From the above examples, it can be seen that the catalysts with different mass fractions provided by the present invention have activity for nitrobenzene selective hydrogenation, and most of the catalysts can achieve excellent catalytic activity under the premise of adjusting and changing the catalytic reaction temperature, hydrogen pressure and reaction time. The scope of the present invention is not limited to the above examples, and good effect can be achieved for nitrobenzene hydrogenation reaction as long as the mass fraction of the active components of the catalyst and the reaction conditions are controlled.

The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments, and it is not intended that the practice of the invention be limited to these descriptions. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, which should be construed as belonging to the scope of the invention.

Claims

1. A method for preparing aniline by nitrobenzene hydrogenation is characterized by comprising the following steps: under the conditions of specific solvent, catalyst and hydrogenation reaction, the raw material nitrobenzene is subjected to hydrogenation reaction to prepare aniline, wherein the solvent is isopropanol, methanol,At least one of ethanol, and Ni-ZrO as catalyst₂a/SBA-15 catalyst; the hydrogenation reaction conditions include: the reaction temperature is 80-120 ℃, the hydrogen pressure is 0.8-1.0 MPa, and the reaction time is 10-60 min; wherein the Ni-ZrO₂the/SBA-15 catalyst is prepared by the following method comprising:

2. The method for preparing aniline by nitrobenzene hydrogenation according to claim 1, wherein the reaction temperature is 120 ℃ and the reaction time is 30 min.

3. The method for preparing aniline by hydrogenation of nitrobenzene according to claim 1, wherein the Ni-ZrO₂The mol ratio of the nickel in the SBA-15 catalyst to the nitrobenzene is 0.5-1.5%.

4. The method for preparing aniline by hydrogenation of nitrobenzene according to claim 1, wherein the Ni-ZrO₂The mass content of nickel in the SBA-15 catalyst is 3-10%; the composite carrier ZrO₂ZrO in SBA-15₂The mass content of (A) is 9-15%.

5. The process for the hydrogenation of nitrobenzene to aniline according to any one of claims 1 to 4 wherein the impregnation process is in particular: ZrOCl is firstly carried out₂Dissolving 8H2O in deionized water, adding molecular sieve SBA-15, stirring uniformly, adding an alkali solution to adjust the pH value to 9, stirring at 80 ℃ for 30-240 min, standing the obtained solution for aging, washing, performing solid-liquid separation, drying and calcining to obtain the composite materialZrO combined with carrier₂/SBA-15。

6. The method for preparing aniline by nitrobenzene hydrogenation according to claim 5, wherein in the dipping method, the standing and aging time is 12-24 h; the drying temperature is 70-90 ℃, and the drying time is 8-12 h; the calcination temperature is 450-600 ℃, and the calcination time is 2-4 h.

7. The method for preparing aniline by nitrobenzene hydrogenation according to any one of claims 1 to 4, characterized in that the gas phase reduction process is in particular: the composite carrier ZrO prepared in the step 1)₂The SBA-15 is dissolved in ethylene glycol, then Ni (NO) is added₃)₂·6H₂O, adding an alkali solution to adjust the pH value to 9 after uniformly stirring, stirring for 4 hours at the temperature of 30 ℃, washing, drying in vacuum and reducing with hydrogen to obtain the Ni-ZrO₂The catalyst is SBA-15.

8. The method for preparing aniline by nitrobenzene hydrogenation according to claim 7, wherein in the gas phase reduction method, the temperature of vacuum drying is 70-90 ℃, and the drying time is 8-12 h; the temperature of hydrogen reduction is 600 ℃, and the time of hydrogen reduction is 4 h.

9. A hybridized nano-structure nickel catalyst for preparing aniline by nitrobenzene hydrogenation is characterized in that the expression of the nickel catalyst is Ni-ZrO₂SBA-15 comprises a carrier SBA-15 molecular sieve, ZrO loaded on the carrier SBA-15 molecular sieve in a monolayer form by an impregnation method and forming a semiconductor film layer₂And anchoring to ZrO by gas phase reduction₂Ni nanoparticles on the semiconductor film layer; wherein the carrier SBA-15 molecular sieve and ZrO loaded on the carrier SBA-15 molecular sieve₂Forming a composite carrier ZrO₂SBA-15, active ingredient Ni nanoparticles and the ZrO₂The semiconductor film layer has a synergistic effect.

10. According toThe hybrid nanostructured nickel catalyst according to claim 9, characterized in that the Ni-ZrO₂The mass content of nickel in the SBA-15 catalyst is 3-10%; the composite carrier ZrO₂ZrO in SBA-15₂The mass content of (A) is 9-15%.