CN115301261A - Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method - Google Patents

Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method Download PDF

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CN115301261A
CN115301261A CN202210725440.8A CN202210725440A CN115301261A CN 115301261 A CN115301261 A CN 115301261A CN 202210725440 A CN202210725440 A CN 202210725440A CN 115301261 A CN115301261 A CN 115301261A
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nickel
boron
silicon carbide
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CN115301261B (en
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郭向云
姚丹
焦志锋
赵吉晓
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Changzhou University
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst

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Abstract

The invention relates to the technical field of catalysis, and discloses boron-doped silicon carbide loaded with nickel, a preparation method of the boron-doped silicon carbide and a preparation method of aniline. Boron-doped silicon carbide loaded with nickel and SiC-B x Nickel is loaded on the carrier, the loading capacity of the nickel on the boron-doped silicon carbide loaded with the nickel is 1 to 30 percent, and SiC-B x Wherein X is any value between 0.01 and 0.5. The nickel-loaded boron-doped silicon carbide provided by the invention ensures the catalytic activity and reduces the cost of the nitrobenzene selective hydrogenation catalyst.

Description

Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to boron-doped silicon carbide loaded with nickel, a preparation method of the boron-doped silicon carbide and a preparation method of aniline.
Background
The catalytic reduction of aromatic nitro compounds is an important reaction in chemical industry, and the product aniline is one of the most important amine substances and is mainly used for dyes, medicines and resins. Most anilines are obtained by nitrobenzene reduction. The common methods for reducing nitrobenzene include iron powder reduction, hydrazine hydrate reduction, and sodium sulfide reduction, but the methods are not suitable for mass production and are eliminated due to the huge production equipment and serious three-waste pollution in the production process.
In recent years, siO has been used 2 、TiO 2 、Y-Al 2 O 3 And noble metals such as Pt, pd, and Au supported on a carrier such as a carbon material have been widely studied as nitrobenzene hydrogenation catalysts. The nitrobenzene hydrogenation catalyst loaded with noble metal has high reaction activity, but also has the practical problem of overhigh cost. Therefore, researchers shift their attention to the direction of non-noble metal nitrobenzene hydrogenation catalysts, but because the non-noble metal supported nitrobenzene hydrogenation catalysts have low activity, poor tolerance and high metal loading, the cost of the non-noble metal supported nitrobenzene hydrogenation catalysts is increased, and the wide application of the non-noble metal supported nitrobenzene hydrogenation catalysts in the preparation of aniline is limited. As in one reference, the nitrobenzene hydrogenation catalyst is Co-ZrO2/SBA-15 with Co loadings as high as 2-40wt%.
Therefore, a nickel-loaded boron-doped silicon carbide, a preparation method thereof and a preparation method of aniline are needed, the cost of a nitrobenzene hydrogenation catalyst is reduced, the preparation method of aniline is optimized, pollution generated in the aniline production process is reduced, and the requirement on equipment in the aniline production process is reduced.
Disclosure of Invention
In order to solve the problems, the invention provides the boron-doped silicon carbide loaded with nickel, and a small amount of nickel is loaded on the boron-doped silicon carbide loaded with nickel, so that the cost of the nitrobenzene selective hydrogenation catalyst is reduced while the catalytic activity is ensured.
The nickel-loaded boron-doped silicon carbide is doped with SiC-B x Nickel is loaded on a carrier, the loading amount of the nickel on the nickel-loaded boron-doped silicon carbide is 1-30%, and the SiC-B x Wherein X is any value between 0.01 and 0.5.
The invention also provides a preparation method of the nickel-loaded boron-doped silicon carbide, and the nickel-loaded boron-doped silicon carbide prepared by the method has low cost and is beneficial to optimizing the preparation method of aniline.
The preparation method of the nickel-loaded boron-doped silicon carbide comprises the following steps:
s1: adding SiC-B into a first reaction vessel x Dispersing agent, water and nickel salt to form mixed solution, and filling 2MPa H 2 Reacting for 1-3h at 100-200 ℃ to obtain an intermediate product;
s2: reducing the intermediate product in a tubular furnace at 450-600 ℃ by using mixed gas of hydrogen and nitrogen for 1-3h to obtain the boron-doped silicon carbide loaded with nickel,
wherein the SiC-B x Wherein X is any value between 0.01 and 0.5,
the dispersing agent is selected from one or more of polyvinylpyrrolidone and polyvinylpyrrolidone,
the nickel salt is selected from one or more of nickel nitrate hexahydrate, nickel sulfate, nickel acetate tetrahydrate and nickel chloride hexahydrate.
Optionally, the preparation method of the nickel-loaded boron-doped silicon carbide includes post-treatment after step S2: and passivating the nickel-loaded boron-doped silicon carbide for 1 hour under the protection of inert gas at room temperature.
Alternatively, in step S1, the reaction temperature is 150 ℃ and the reaction time is 2h.
Optionally, the preparation method of the nickel-loaded boron-doped silicon carbide includes intermediate treatment after step S1 and before step S2: and cooling, filtering, drying in vacuum and grinding the intermediate product. In the step S2, the reduction reaction temperature is 450 ℃, and the reduction reaction time is 1h.
Optionally, the SiC-B x The preparation method comprises the following steps:
s01: dissolving a carbon source in a first solvent, adding a silicon source, a metal salt and a boride to obtain a mixed solution, reacting the mixed solution at 150-200 ℃ for 2-7h to obtain a first product, standing, and removing a supernatant of the first product to obtain a precipitate;
s02: placing the precipitate in an inert atmosphere, and carrying out carbothermic reduction reaction for 3-30h at 1000-1500 ℃ to obtain a second product;
s03: placing the second product in air, and calcining for 2-8h at 500-900 ℃ to obtain a third product;
s04: soaking the third product for 12-48h by using a mixture of hydrochloric acid and hydrofluoric acid in a volume ratio of 1-5 to obtain the SiC-B x ，
Wherein the molar ratio of the carbon source to the silicon source in the mixed solution of S01 is 0.1 to 20, and the molar ratio of the silicon source to the metal salt is 0.5:1-5, the molar ratio of the silicon source to the boride is 0.01.
Optionally, the carbon source is selected from one or more of sucrose, biomass polystyrene sulfonic acid resin and graphite, the silicon source is selected from one or more of silica sol, water glass and polycarbosilane, the metal salt is selected from one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the boride is selected from one or more of boric acid, borax, sodium borohydride, 3-aminobenzeneboronic acid, trialkylborane, boron trifluoride-methanol and ammonia borane.
The invention also provides a preparation method of the aniline, and the aniline preparation method can reduce pollution generated in the aniline production process and reduce the requirements on equipment in the aniline production process.
The preparation method of the aniline comprises the following steps:
a, preparing boron-doped silicon carbide loaded with nickel;
b, adding nitrobenzene, a second solvent and the boron-doped silicon carbide loaded with nickel into a second reaction vessel, introducing a reducing agent hydrogen, heating, carrying out reduction reaction to obtain the aniline,
wherein the volume ratio of the nitrobenzene to the solvent is 0.1-1 to 5-20, the molar ratio of the nitrobenzene to the nickel-loaded boron-doped silicon carbide is 1-10,
after the hydrogen is filled, the pressure value of the second container is 0.5-6MPa, the reduction reaction temperature is 20-100 ℃, and the reduction reaction time is 2-8h.
Alternatively, the reduction reaction temperature is 90 ℃ and the reduction reaction time is 5h.
Optionally, the second solvent is one or more of methanol, ethanol, acetonitrile, or N, N-dimethylformamide.
The supported nickel on the nickel-loaded boron-doped silicon carbide has low content and high activity, reduces the cost of the non-noble metal nitrobenzene hydrogenation catalyst, is beneficial to wide application in the production of aniline, reduces pollution generated in the production process of aniline, and reduces the requirement on equipment in the production process of aniline.
Drawings
FIG. 1 is a flow chart of a method for preparing nickel-loaded boron-doped silicon carbide according to the present invention;
FIG. 2 is a flow chart of a process for preparing aniline according to the present invention;
FIG. 3 shows SiC/B doped with different boron amounts according to the present invention x XRD pattern of (X =0.01, 0.05, 0.1, 0.5);
FIG. 4 shows SiC/B x EDS plot of (X =0.01, 0.05, 0.1, 0.5).
Detailed Description
In order to make the above objects, features and advantages of the present invention more comprehensible, specific embodiments accompanied with figures are described in detail below, but the scope of the present invention is not to be construed as limited thereto.
Doping of non-metal elements, such as boron (B), fluorine (F), sulfur (S), and nitrogen (N), has been attracting attention as a method capable of affecting the reactivity, having the effect of adjusting the electronic structure, morphology, and physicochemical properties of the carrier. 1. In the literature, nitrogen (N) -doped mesoporous carbon materials supporting palladium (Pd) are prepared, achieving a high dispersion of Pd nanoparticles (Journal of the American Chemical Society,2012,134 (41): 16987-16990). In another document B-doped graphene energyThe charge transfer efficiency can be remarkably improved, and the electrocatalytic reaction can be favorably carried out (Journal of Materials Chemistry A,2018, 6. In view of the advantages of non-metallic element doping, in order to solve the problems of low catalyst reaction activity and high catalyst cost caused by large metal loading in the research of the catalyst for preparing aniline and the problems of high equipment requirement and large amount of three wastes generated in the reaction of preparing aniline, the invention dopes silicon carbide (SiC-B) in boron x ) A small amount of nickel is loaded on the catalyst, so that the activity of the nickel-loaded boron-doped silicon carbide serving as the catalyst in the reaction of preparing aniline by selective hydrogenation of nitrobenzene is improved, and the cost of the catalyst is reduced, thereby being beneficial to the optimization of an aniline preparation method, reducing the pollution generated in the preparation method and lowering the requirements of the preparation method on equipment.
The boron-doped silicon carbide loaded with nickel is formed by loading transition metal nickel as an active component on boron-doped silicon carbide, and the raw materials used in the preparation process of the boron-doped silicon carbide loaded with nickel are easy to obtain and low in price, so that the cost of the catalyst can be reduced.
A nickel-loaded boron-doped silicon carbide, which is SiC-B x Nickel is loaded as a carrier, the loading amount of the nickel on the boron-doped silicon carbide loaded with the nickel is 1-30 percent, and SiC-B x Wherein X is any value between 0.01 and 0.5. The nickel-loaded boron-doped silicon carbide provided by the invention has the loaded nickel content of 1-30%, and compared with the existing nitrobenzene hydrogenation catalyst which is 2-40wt% of the cobalt loading of Co-ZrO2/SBA-15, the nickel loading is reduced by 25-50%, and the price of nickel is lower than that of cobalt, so that the cost of the catalyst is reduced while the catalytic hydrogenation activity is ensured, the wide application in the aniline preparation process is facilitated, and the aniline preparation method is optimized.
Referring to fig. 1, a method for preparing boron-doped silicon carbide loaded with nickel includes the following steps:
s1: adding SiC-B into a first reaction vessel x Mixing with dispersant, water and nickel salt to form mixed solution, sealing the first reaction container, washing with gas and filling 2MPa H 2 Reacting for 1-3h at 100-200 ℃ to obtain an intermediate product;
s2: reducing the intermediate product in a tubular furnace at 450-600 ℃ for 1-3h by using hydrogen-nitrogen mixed gas to obtain boron-doped silicon carbide loaded with nickel,
wherein, siC-B x Wherein X is any value between 0.01 and 0.5,
the dispersant is selected from one or more of polyvinylpyrrolidone and polyvinylpyrrolidone,
the nickel salt is selected from one or more of nickel nitrate hexahydrate, nickel sulfate, nickel acetate tetrahydrate and nickel chloride hexahydrate,
the polyvinylpyrrolidone and the polyacrylamide are water-soluble polymers and are mainly used for dispersing metals in the preparation process of the catalyst. PVP belongs to a non-ionic solvent, and PAM belongs to an ionic solvent.
First to H 2 The gas washing is carried out, so that the impurities in the gas can be reduced, and the occurrence of side reactions is reduced.
In step S2, the intermediate product NiO/SiC-B x Reducing to form nickel-loaded boron-doped silicon carbide Ni/SiC-B x 。
The content of nickel loaded on the nickel-loaded boron-doped silicon carbide prepared by the method is 1-30%, compared with the content of Co-ZrO in the prior art 2 The Co loading amount on the SBA-15 is 2-40wt%, the metal loading amount is reduced by 25-50%, the price of nickel is lower than that of cobalt, and the cost of the nitrobenzene selective hydrogenation catalyst is remarkably reduced while the catalytic activity of the nitrobenzene selective hydrogenation catalyst is ensured.
Content of nickel salt participating in reaction and SiC-B participating in reaction x When the mass ratio of the substances is 1.56, the nickel loading amount in the prepared nickel-loaded boron-doped silicon carbide reaches 30 percent.
Content of nickel salt participating in reaction and SiC-B participating in reaction x When the mass ratio of the substances is 0.1, the nickel loading amount in the prepared nickel-loaded boron-doped silicon carbide reaches 2%.
In one embodiment, the preparation method of the nickel-loaded boron-doped silicon carbide comprises the post-treatment after the step S2: and passivating the nickel-loaded boron-doped silicon carbide for 1 hour under the protection of inert gas at room temperature.
Due to reduced Ni/SiC-B x The catalyst is unstable and can be exposed to air in the process of transferring to a reaction kettle, so that the Ni/SiC-B x The surface of the catalyst is oxidized; in addition, due to reduced Ni/SiC-B x The metallic nickel loaded on the catalyst has high activity and high surface hydrogen concentration, and is easy to generate sparks when exposed in air. Therefore, passivation by an inert gas at room temperature forms a protective layer on the catalyst surface, preventing the above from occurring.
In one embodiment, in S1, the reaction temperature is 150 ℃ and the reaction time is 2h.
In one embodiment, the method comprises intermediate processing after step S1 and before step S2: and cooling, filtering, vacuum drying and grinding the intermediate product.
The reduction temperature of the intermediate product in S2 is 450 ℃, and the reduction time is 1h.
The tubular furnace has fast heat transfer, high heat efficiency and short reaction period, and the reduction reaction time may be prolonged based on the heat transfer efficiency of the reaction container in other cases.
The intermediate product comprises the processes of cooling, suction filtration, vacuum drying and grinding of the intermediate product before entering the tube furnace, preferably cooling to room temperature naturally, and drying in a vacuum drying oven overnight. The suction filtration process is to remove the dispersant and unreacted nickel from the intermediate product. The grinding process is to make the reaction fully contact with each other, increase the reaction efficiency and shorten the reaction time.
In one embodiment, siC-B x The preparation method comprises the following steps:
s01: dissolving a carbon source in a first solvent, adding a silicon source, a metal salt and a boride to obtain a mixed solution, reacting the mixed solution at 150-200 ℃ for 2-7h to obtain a first product, standing, and removing a supernatant of the first product to obtain a precipitate;
s02: placing the precipitate in an inert atmosphere, and carrying out carbothermic reduction reaction for 3-30h at 1000-1500 ℃ to obtain a second product;
s03: placing the second product in air, and calcining for 2-8h at 500-900 ℃ to obtain a third product;
s04: soaking the third product in a mixture of hydrochloric acid and hydrofluoric acid with the volume ratio of 1-5 for 12-48h to obtain SiC-B x ，
Wherein the molar ratio of the carbon source to the silicon source in the mixed solution in the step S01 is 0.1: 1-5, the molar ratio of the silicon source to the boride is 0.01.
The chemical property of the silicon carbide is very stable, and boron doping is difficult to realize by an impregnation method or a coprecipitation method, so that the silicon carbide is doped in the process of preparing the silicon carbide by an in-situ doping method.
Optionally, soaking the third product for 12-48h by using a mixture of hydrochloric acid and hydrofluoric acid in a volume ratio of 1.
Alternatively, the carbon source is selected from one or more of sucrose, biomass, polystyrene sulfonate resin and graphite, and different carbon sources affect SiC-B x Specific surface area of support, pore distribution and yield. The silicon source is selected from one or more of silica sol, water glass and polycarbosilane, and different silicon sources can influence the specific surface area and the pore distribution of SiC. The metal salt is selected from one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the boride is selected from one or more of boric acid, sodium borax borohydride, 3-aminophenylboronic acid, trialkylborane, boron trifluoride-methanol and ammonia borane. The first solvent is an aqueous solvent, preferably water.
The invention also provides a preparation method of aniline, referring to fig. 2, the preparation method of aniline comprises:
a, preparing boron-doped silicon carbide loaded with nickel;
b, adding nitrobenzene, a second solvent and nickel-loaded boron-doped silicon carbide into a second reaction vessel, introducing a reducing agent hydrogen, heating, carrying out reduction reaction to obtain the aniline,
wherein the volume ratio of nitrobenzene to the second solvent is 0.1-1 to 5-20, the molar ratio of nitrobenzene to nickel-loaded boron-doped silicon carbide is 1-10,
after the hydrogen is filled, the pressure in the second container is 0.5-6MPa, the reduction reaction temperature is 20-100 ℃, and the reduction reaction time is 2-8h.
The reaction route for preparing the aniline by selectively hydrogenating nitrobenzene in the preparation method of the aniline is as follows:
Figure BDA0003713087740000061
and (3) selectively hydrogenating nitrobenzene to generate aniline and water, carrying out solid-liquid separation on a reaction product in the second reaction vessel after the reaction is finished, separating out a solid phase as a catalyst, and drying the catalyst for recycling.
Alternatively, the reduction reaction temperature is 90 ℃ and the reduction reaction time is 5h. Under the conditions of the reaction temperature and the reaction duration, the conversion rate of nitrobenzene and the selectivity of directional hydrogenation are the best in the process of preparing aniline by catalytic hydrogenation of nitrobenzene.
Optionally, the second solvent is a polar solvent, and may be selected from a polar protic solvent, such as one of methanol, ethanol, isopropanol, acetic acid, water, and may be selected from a polar aprotic solvent, such as one of acetonitrile, acetone, or N, N-dimethylformamide.
The boron-doped silicon carbide supporting nickel and the preparation method thereof and the preparation method of aniline according to the present invention are further illustrated by the following specific examples.
Examples 1-4 production of SiC-B with different amounts of boron x 。
Example 1
Firstly, dissolving 14.23g of sucrose in 100ml of water, adding 0.22g of nickel nitrate, 12.47g of silica sol and 0.0386g of boric acid, uniformly mixing, reacting for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, standing, removing supernatant of the first product to obtain a precipitate, and drying; putting the precipitate into a tubular high-temperature furnace, introducing argon, carrying out programmed heating to 1450 ℃, carrying out constant-temperature reaction for 8 hours to obtain a second product, and naturally cooling the second product in an argon atmosphere; calcining the obtained second product in air at 700 ℃ for 3h to obtain a third product;soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid with the volume ratio of 1 0.01 。
Example 2
Firstly, dissolving 14.23g of sucrose in 100ml of water, adding 0.22g of nickel nitrate, 12.47g of silica sol and 0.193g of boric acid, uniformly mixing, reacting for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, standing, removing supernatant of the first product to obtain precipitate, and drying; putting the precipitate into a tubular high-temperature furnace, introducing argon, carrying out programmed heating to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product under the argon atmosphere; calcining the obtained second product in air at 700 ℃ for 3h to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid with the volume ratio of 1 0.05 。
Example 3
Firstly, dissolving 14.23g of sucrose in 100ml of water, adding 0.22g of nickel nitrate, 12.47g of silica sol and 0.386g of boric acid, uniformly mixing, reacting for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, standing, removing supernatant of the first product to obtain precipitate, and drying; putting the precipitate into a tubular high-temperature furnace, introducing argon, carrying out programmed heating to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product under the argon atmosphere; calcining the obtained second product in air at 700 ℃ for 3h to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid in a volume ratio of 1 0.1 。
Example 4
Firstly, dissolving 14.23g of sucrose in 100ml of water, adding 0.22g of nickel nitrate, 12.47g of silica sol and 1.93g of boric acid, uniformly mixing, reacting for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, standing, removing supernatant of the first product to obtain a precipitate, and drying; putting the precipitate into a tubular high-temperature furnace, introducing argon, carrying out programmed heating to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product under the argon atmosphere; the second product obtainedCalcining the mixture in air at 700 ℃ for 3 hours to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid with the volume ratio of 1 0.5 。
Example 5
(1) Preparation of catalyst 5% Ni/SiC
600mg of PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 ·6H 2 O, and finally 190mg of SiC carrier is added to form a suspension. Transferring the suspension to a micro-reactor, sealing the micro-reactor, washing with gas for three times, and introducing 2MPa H 2 And reacting at 150 ℃ for 2h. After the solution in the micro reaction kettle is cooled to room temperature, carrying out suction filtration and vacuum drying to obtain an intermediate product of the catalyst 5 percent Ni/SiC, and grinding the intermediate product.
Weighing 50mg of ground intermediate product, placing the intermediate product in a tube furnace, carrying out vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas at the temperature of 450 ℃ for 1 hour, and passivating the intermediate product for 1 hour under the protection of argon at room temperature to obtain the catalyst 5% Ni/SiC.
(2) Preparation of aniline by catalytic hydrogenation of nitrobenzene 1mmol of nitrobenzene, 10mL of solvent ethanol, 50mg of reduced catalyst 5% Ni/SiC in a 50mL sealed micro-reactor, hydrogen washing 3 times in the reactor, refilling hydrogen, maintaining the reaction pressure at 1MPa, reacting at 90 ℃ for 5h, after the reaction is finished, performing suction filtration on the reaction product to separate a solid phase and a liquid phase, recovering the solid phase, namely the catalyst 5% Ni/SiC, and performing gas chromatography on the liquid phase.
Example 6
(1) Preparation of catalyst 5% Ni/SiC-B 0.01
600mg of PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 ·6H 2 O, finally 190mg of SiC-B is added 0.01 The carrier forms a suspension. Transferring the suspension to a micro-reactor, sealing the micro-reactor, washing with gas for three times, and introducing 2MPa H 2 And reacting at 150 ℃ for 2h. After the solution in the micro reaction kettle is cooled to room temperature, the solution is pumped and filtered, and the catalyst 5 percent is obtained by vacuum drying 0.01 The intermediate product of (4), milling the intermediate product.
Weighing 50mg of ground intermediate product, placing the intermediate product in a tube furnace, carrying out vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas at the temperature of 450 ℃ for 1h, and passivating the intermediate product in the atmosphere of argon at room temperature for 1h to obtain the catalyst 5% Ni/SiC-B 0.01 。
(2) Preparation of aniline by catalytic hydrogenation of nitrobenzene
Adding 1mmol of nitrobenzene, 10mL of solvent ethanol and 50mg of 5 percent catalyst Ni/SiC-B after reduction into a 50mL sealed micro reaction kettle 0.01 Washing the reaction kettle with hydrogen for 3 times, charging hydrogen again, maintaining the reaction pressure at 1MPa, reacting at 90 deg.C for 5h, filtering the reaction product after the reaction is finished, separating solid-liquid phase, recovering solid phase, i.e. catalyst 5% 0.01 And carrying out gas chromatography treatment on the liquid phase reaction liquid.
Example 7
(1) Preparation of catalyst 5% Ni/SiC-B 0.05 600mg of PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 6 water, finally 190mg of SiC-B are added 0.05 The carrier forms a suspension. Transferring the suspension to a micro-reactor, sealing the micro-reactor, washing with gas for three times, and introducing 2MPa H 2 And reacting at 150 ℃ for 2h. And after the solution is cooled to room temperature, carrying out suction filtration, vacuum drying and grinding to finish the first step of catalyst preparation.
Weighing 50mg of ground intermediate product, placing the intermediate product in a tube furnace, performing vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas at the temperature of 450 ℃ for 1 hour, and passivating the intermediate product in the atmosphere of argon at room temperature for 1 hour to obtain the 5% Ni/SiC-B catalyst 0.05 。
(2) Preparation of aniline by catalytic hydrogenation of nitrobenzene
50mL of a sealed microreactor was charged with 1mmol of nitrobenzene, 10mL of ethanol as a solvent, 50mg of reduced catalyst 5% 0.05 Washing the reaction kettle with hydrogen for 3 times, charging hydrogen again, maintaining the reaction pressure at 1MPa, reacting at 90 deg.C for 5h, and feeding the reaction product after the reaction is finishedSeparating the solid phase from the liquid phase by suction filtration and recovering the solid phase, i.e. the catalyst 5% 0.05 And carrying out gas chromatography treatment on the liquid phase.
Example 8
(1) Preparation of catalyst 5% Ni/SiC-B 0.1 600mg of PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 6 water, and finally 190mg of SiC-B 0.1 The carrier forms a suspension. Transferring the suspension to a micro-reactor, sealing the micro-reactor, washing with gas for three times, and charging 2MPa H 2 And reacting at 150 ℃ for 2h. After the solution in the micro reaction kettle is cooled to room temperature, the solution is filtered and vacuum dried to obtain the catalyst 5 percent 0.1 The intermediate product of (4), milling the intermediate product.
Weighing 50mg of ground intermediate product, placing the intermediate product in a tube furnace, carrying out vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas at the temperature of 450 ℃ for 1h, and passivating the intermediate product in the atmosphere of argon at room temperature for 1h to obtain the catalyst 5% Ni/SiC-B 0.1 。
(2) Preparation of aniline by catalytic hydrogenation of nitrobenzene
50mL of a sealed microreactor was charged with 1mmol of nitrobenzene, 10mL of ethanol as a solvent, 50mg of reduced catalyst 5% 0.1 Washing the reaction kettle with hydrogen for 3 times, charging hydrogen again, maintaining the reaction pressure at 1MPa, reacting at 90 deg.C for 5h, filtering the reaction product after the reaction is finished, separating solid-liquid phase, recovering solid phase, i.e. catalyst 5% 0.1 And carrying out gas chromatography treatment on the liquid phase.
Example 9
(1) Preparation of catalyst 5% Ni/SiC-B 0.5
600mg of PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 ·6H 2 O, and finally 190mg of SiC-B are added 0.5 The carrier forms a suspension. Transferring the suspension to a micro-reactor, sealing the micro-reactor, washing with gas for three times, and introducing 2MPa H 2 And reacting at 150 ℃ for 2h. After the solution in the micro reaction kettle is cooled to room temperature, carrying out suction filtration, and carrying out vacuum drying to obtain the catalyst5％Ni/SiC-B 0.5 The intermediate product of (4), milling the intermediate product.
Weighing 50mg of ground intermediate product, placing the intermediate product in a tube furnace, carrying out vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas at the temperature of 450 ℃ for 1h, and passivating the intermediate product in the atmosphere of argon at room temperature for 1h to obtain the catalyst 5% Ni/SiC-B 0.5 。
(2) Preparation of aniline by catalytic hydrogenation of nitrobenzene
50mL of a sealed microreactor was charged with 1mmol of nitrobenzene, 10mL of ethanol as a solvent, 50mg of reduced catalyst 5% 0.5 Washing the reaction kettle with hydrogen for 3 times, charging hydrogen again, maintaining the reaction pressure at 1MPa, reacting at 90 deg.C for 5h, filtering the reaction product after the reaction is finished, separating solid-liquid phase, recovering solid phase, i.e. catalyst 5% 0.5 And carrying out gas chromatography treatment on the liquid phase.
In the preparation of 200mg of 5% Ni-loaded SiC-Bx in examples 5-9, 600mg of PVP was replaced with 700mg of Polyacrylamide (PAM), niCl 2 ·6H 2 O as Ni (NO) 3 ·6H 2 Alternative to O, H 2 O:Ni(NO) 3 ·6H 2 Volume ratio of O18.3 2 O:NiCl 2 ·6H 2 O is 18.7 2 O:Ni(NO) 3 Or NiCl 2 ·6H 2 The total amount of O and water was 20ml.
SiC-B obtained in examples 1 to 4 x See fig. 3 and 4 for experimental results. FIG. 3 left-hand diagram showing SiC-B x XRD spectrum of (1), right graph shows SiC-B x (111) The partial enlarged spectrum of the crystal face, the curves marked with a to e from bottom to top in the left and right figures represent SiC-B with X =0, 0.01, 0.05, 0.1, 0.5 x Spectra. In an XRD spectrogram, the three main peaks of SiC are 35.7 degrees, 60.0 degrees and 71.8 degrees, and the angles of the three main peaks are not obviously moved by B doping, so that the crystal structure of the SiC is not influenced by the B doping. FIG. 3 shows pure SiC (111) and SiC-B on the right x (111) An enlarged view of the crystal plane shows that pure SiC (111) 2. Theta. Is 35.7 deg.. When X is 0.01, 0.05, 0.1, 0.5 SiC-B x Is slightly shifted toward a high angle by 2 theta of the (111) crystal planeFrom about 0.01 ° to about 0.05 °.
The position of the peak in fig. 4 represents an element, the area of the peak represents the amount of the element, the mass fractions of four elements of carbon (C), silicon (Si), boron (B) and oxygen (O) and the position of the peak representing the element are shown in the upper left corner of fig. 4, respectively, and it can be seen from fig. 4 that B is successfully doped into the silicon carbide crystal.
The results of catalytic hydrogenation of nitrobenzene to aniline in examples 5-9 are shown in Table I
Watch 1
Figure BDA0003713087740000101
It can be seen from table one that the doping of the boron atom (B) has a significant effect on the improvement of the catalytic effect of the nickel-loaded boron-doped silicon carbide, and the doping of B successfully improves the catalytic performance, wherein the activity of the nickel-loaded boron-doped silicon carbide is increased with the increase of the doping amount of the boron atom, the catalytic efficiency is increased, and the selectivity of the directional hydrogenation is improved. Sp of boron atom 2 The hybridization mode changes the charge density distribution of the catalyst, simultaneously provides an empty orbit to receive electrons, and the p orbit in an occupied state can transfer the electrons to the silicon carbide surface to adsorb nitrobenzene. The conversion and selectivity of nickel-loaded boron-doped silicon carbide catalysts loaded with different amounts of nickel are shown in table two:
Figure BDA0003713087740000102
Figure BDA0003713087740000111
as can be seen from table two, the higher the content of the supported nickel is, the higher the conversion of the nickel-supported boron-doped silicon carbide catalyst is, with the same doping amount of boron; under the condition of the same doping amount of boron, the content of the supported nickel is different, and the selectivity of the nickel-supported boron-doped silicon carbide catalyst is not obviously changed and is maintained at a higher level.
The nickel-loaded boron-doped silicon carbide prepared in examples 5 to 9 all have 5% of nickel loading, and have relatively good catalytic activity and directional hydrogenation selectivity, and particularly, the nickel-loaded boron-doped silicon carbide prepared in example 9 also has excellent catalytic activity, the conversion rate of nitrobenzene reaches 100%, and the selectivity reaches 100%. Therefore, the boron-doped silicon carbide loaded with nickel with higher catalytic activity can be generated under the condition of loading a small amount of nickel, and meanwhile, the cost of the boron-doped silicon carbide loaded with nickel is reduced due to lower price and less loading amount of nickel, so that the boron-doped silicon carbide loaded with nickel can be widely applied to the preparation of aniline.
During the reaction process of preparing aniline by catalytic hydrogenation of nitrobenzene catalyzed by nickel-loaded boron-doped silicon carbide, aniline and water are generated in the reaction process of hydrogen and nitrobenzene, and no other substances are generated, so that the pollution generated in the aniline production process in the prior art is reduced, and the wide application of the preparation method of nickel-loaded boron-doped silicon carbide-catalyzed aniline is facilitated.
Example 10 includes example 10A, example 10B, example 10C, example 10D and example 10E, wherein example 10A is the same as example 9, and example 10B, example 10C, example 10D, example 10E and example 10A are substantially the same, except that the catalyst 5 is "% Ni/SiC-B% 0.5 The time for nitrobenzene hydrogenation reaction is reduced.
The results of catalytic hydrogenation of nitrobenzene to aniline in examples 10A-10E are shown in Table III
Watch III
Catalyst and process for preparing same Time (h) Conversion (%) Selectivity (%)
Example 10A 5％Ni/SiC-B 0.5 5 99.9 99.9
Example 10B 5％Ni/SiC-B 0.5 4 78.1 96.2
Example 10C 5％Ni/SiC-B 0.5 3 60.1 97.1
Example 10D 5％Ni/SiC-B 0.5 2 56.2 99.9
Example 10E 5％Ni/SiC-B 0.5 1 23.2 99.9
From the table III, it can be obtained that under the same conditions of the carrier, the transition metal is used as the active component of the reaction, the difference of the reaction performance of the nitrobenzene catalytic hydrogenation for preparing aniline has a close relationship with the time factor, and the conversion rate of nitrobenzene is reduced along with the reduction of the reaction time of hydrogenation of nitrobenzene participated in by the nickel-loaded boron-doped silicon carbide.

Claims (10)

1. The boron-doped silicon carbide loaded with nickel is characterized in that the boron-doped silicon carbide loaded with nickel is SiC-B x Nickel is loaded on a carrier, the loading amount of the nickel on the nickel-loaded boron-doped silicon carbide is 1-30%, and the SiC-B x Wherein X is any value between 0.01 and 0.5.
2. A preparation method of boron-doped silicon carbide loaded with nickel is characterized by comprising the following steps:
s1: adding SiC-B into a first reaction vessel x Mixing with dispersant, water and nickel salt to form a mixed solution, and charging 2MPaH 2 Reacting for 1-3h at 100-200 ℃ to obtain an intermediate product;
s2: reducing the intermediate product in a tubular furnace at 450-600 ℃ for 1-3h by using a hydrogen-nitrogen mixed gas to obtain the nickel-loaded boron-doped silicon carbide,
wherein the SiC-B x Wherein X is any value between 0.01 and 0.5,
the dispersing agent is selected from one or more of polyvinylpyrrolidone and polyvinylpyrrolidone,
the nickel salt is selected from one or more of nickel nitrate hexahydrate, nickel sulfate, nickel acetate tetrahydrate and nickel chloride hexahydrate.
3. The method of preparing nickel-loaded, boron-doped silicon carbide according to claim 2, comprising a post-treatment after step S2: and passivating the nickel-loaded boron-doped silicon carbide for 1h under the protection of inert gas at room temperature.
4. The method of preparing nickel-supporting boron-doped silicon carbide according to claim 2, wherein in step S1, the reaction temperature is 150 ℃ and the reaction time is 2 hours.
5. The method of preparing nickel-loaded boron-doped silicon carbide according to claim 2,
the method comprises the following intermediate processing steps after the step S1 and before the step S2: cooling, filtering, vacuum drying and grinding the intermediate product,
the reduction reaction temperature of the intermediate product in the S2 is 450 ℃, and the reduction reaction time is 1h.
6. The method of preparing nickel-loaded boron-doped silicon carbide according to claim 2, wherein the SiC-B x The preparation method comprises the following steps:
s01: dissolving a carbon source in a first solvent, adding a silicon source, metal salt and boride to obtain a mixed solution, reacting the mixed solution at 150-200 ℃ for 2-7h to obtain a first product, standing, and removing the supernatant of the first product to obtain a precipitate;
s02: placing the precipitate in an inert atmosphere, and carrying out carbothermic reduction reaction for 3-30h at 1000-1500 ℃ to obtain a second product;
s03: placing the second product in the air, and calcining for 2-8h at 500-900 ℃ to obtain a third product;
s04: soaking the third product in a mixture of hydrochloric acid and hydrofluoric acid with the volume ratio of 1-5 for 12-48h to obtain the SiC-B x ，
Wherein the molar ratio of the carbon source to the silicon source in the mixed solution of S01 is 0.1 to 20, and the molar ratio of the silicon source to the metal salt is 0.5:1-5, the molar ratio of the silicon source to the boride is 0.01.
7. The method for preparing the nickel-loaded boron-doped silicon carbide according to claim 2, wherein the carbon source is selected from one or more of sucrose, biomass, polystyrene sulfonic acid resin and graphite, the silicon source is selected from one or more of silica sol, water glass and polycarbosilane, the metal salt is selected from one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the boride is selected from one or more of boric acid, sodium borax borohydride, 3-aminophenylboronic acid, trialkylborane, boron trifluoride-methanol and ammonia borane.
8. The preparation method of aniline is characterized by comprising the following steps:
a, preparing the nickel-loaded boron-doped silicon carbide;
b, adding nitrobenzene, a second solvent and the boron-doped silicon carbide loaded with nickel into a second reaction vessel, introducing a reducing agent hydrogen gas for heating, carrying out reduction reaction to obtain the aniline,
wherein the volume ratio of the nitrobenzene to the second solvent is 0.1-1 to 5-20, the molar ratio of the nitrobenzene to the nickel-loaded boron-doped silicon carbide is 1-10,
after the hydrogen is filled, the pressure in the second container is 0.5-6MPa, the reduction reaction temperature is 20-100 ℃, and the reduction reaction time is 2-8h.
9. The process for producing aniline according to claim 8, wherein the reduction reaction temperature is 90 ℃ and the reduction reaction time is 5 hours.
10. The method of claim 8, wherein the second solvent is one or more of methanol, ethanol, acetonitrile, or N, N-dimethylformamide.
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