CN116116416A - Preparation of high-activity nickel-based catalyst and application of high-activity nickel-based catalyst in guaiacol hydrodeoxygenation - Google Patents

Preparation of high-activity nickel-based catalyst and application of high-activity nickel-based catalyst in guaiacol hydrodeoxygenation Download PDF

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CN116116416A
CN116116416A CN202211475556.7A CN202211475556A CN116116416A CN 116116416 A CN116116416 A CN 116116416A CN 202211475556 A CN202211475556 A CN 202211475556A CN 116116416 A CN116116416 A CN 116116416A
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nickel
guaiacol
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薛冰
曹菲
温哲
王非
许杰
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Changzhou University
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Abstract

The invention provides a preparation method of a high-activity nickel-based catalyst and application thereof in guaiacol hydrodeoxygenation, wherein the catalyst is prepared by taking nickel-aluminum layered double metal hydroxide with accurate and controllable structure as a precursor and adopting high-temperature roasting and reduction treatment. Wherein Ni used for preparing nickel-aluminum layered double hydroxide 2+ And Al 3+ The molar ratio is 2/1-4/1, the roasting temperature is 400-500 ℃, and the reduction temperature is 400-500 ℃; the guaiacol hydrodeoxygenation reaction is carried out in a batch high-pressure reaction kettle, the reaction temperature is 160-240 ℃, and the reaction time is 4-8 h. The high-activity nickel-based catalyst has the advantages of uniform dispersed metal phase, accurate and adjustable catalytic activity level, high specific surface area, strong metal-carrier interaction and the like, and is used in the hydrodeoxygenation reaction of guaiacolShows excellent catalytic performance and can convert guaiacol into cyclohexane with high selectivity.

Description

Preparation of high-activity nickel-based catalyst and application of high-activity nickel-based catalyst in guaiacol hydrodeoxygenation
Technical Field
The invention belongs to the technical field of chemical catalytic materials, and particularly relates to preparation of a high-activity nickel-based catalyst and application of the catalyst in guaiacol hydrodeoxygenation reaction.
Background
Guaiacol is the most commonly used lignin model compound, which can be selectively converted to cyclohexane and alkylphenol compounds by hydrodeoxygenation reactions. Early research efforts on guaiacol catalytic conversion focused mainly on traditional NiMoS 2 、CoMoS 2 Catalysts and supported noble metal catalysts, but these catalysts need to exhibit excellent hydrodeoxygenation properties under high hydrogen pressure and high temperature reaction conditions, and have a strong tendency to hydrogenate benzene rings, resulting in lower selectivity to the target product.
Under proper reaction conditions, the supported nickel-based catalyst has catalytic activity equivalent to that of a noble metal catalyst and is widely applied to hydrodeoxygenation reaction. The conventional preparation method of the supported nickel-based catalyst is to co-precipitate the salt and other metal salts, or impregnate a porous carrier with the salt solution, and then obtain a catalyst sample through high-temperature roasting and reduction treatment. However, the active component Ni of the supported nickel-based catalyst prepared by the conventional coprecipitation method has poor dispersity, and the phenomena of structural collapse and active component inactivation exist in the hydrothermal reaction process. Research shows that the geometric structure and the electronic structure of the active site of the supported metal catalyst directly influence the hydrogen adsorption capacity of the catalyst surface, so that the activity and the selectivity of the catalyst are determined, the dispersity of the active component of the surface of the supported nickel-based catalyst is improved, the catalytic activity of the surface active site of the supported nickel-based catalyst can be effectively improved by fine regulation and control, and the hydrothermal stability of the supported nickel-based catalyst can be obviously improved. The metal oxide derived from the layered double hydroxide has unique properties of high dispersibility and high stability, and has great application potential in the preparation of supported metal catalysts.
Based on the method, nickel-aluminum layered double metal hydroxide with accurate and controllable structure is used as a precursor, and the development of the supported nickel-based catalyst with uniformly dispersed metal phase and high catalytic activity has important significance for the selective hydrodeoxygenation reaction of guaiacol.
Disclosure of Invention
Aiming at the problems of low catalyst activity and selectivity, poor dispersity of active components, poor hydrothermal stability and the like in the existing guaiacol hydrodeoxygenation reaction, the invention provides a high-activity nickel-based catalyst which can be used in the guaiacol hydrodeoxygenation reaction, and the catalyst is obtained by taking nickel-aluminum layered double hydroxide with accurate and controllable structure as a precursor and performing high-temperature roasting and reduction treatment.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the high-activity nickel-based catalyst comprises the following steps:
(1) Weighing nickel nitrate hexahydrate, aluminum nitrate nonahydrate and 250mL of distilled water in a certain molar ratio, adding into a 500mL three-necked bottle, stirring to dissolve all the nickel nitrate hexahydrate, adding a certain amount of urea, reacting at 105 ℃ for 12h, ageing at 95 ℃ for 24h, cooling to room temperature, filtering, washing filter residues, and vacuum drying at 80 ℃ overnight to obtain nickel-aluminum layered double metal hydroxide, which is denoted as NiAl-LDH;
(2) Placing the nickel-aluminum layered double metal hydroxide obtained in the step (1) into a muffle furnace, roasting for 6 hours in an air atmosphere at a roasting temperature of 400-500 ℃ to obtain nickel-aluminum layered double metal oxide, and marking the nickel-aluminum layered double metal oxide as NiAl-LDO;
(3) Then the nickel-aluminum layered bimetallic oxide obtained in the step (2) is placed in a tube furnace for reduction for 6 hours in a hydrogen atmosphere, the reduction temperature is 400-500 ℃, and the high-activity nickel-based catalyst is obtained and is marked as Ni/Al 2 O 3 -LDH。
As a limitation of the present invention, ni in the nickel aluminum layered double hydroxide described in the step (1) of the present invention 2+ And Al 3+ The molar ratio is 2/1-4/1; the amount of urea used for preparing nickel-aluminum layered double hydroxide is cation Ni 2+ And Al 3+ 3 times the total moles charged.
As a further limitation of the present invention, the firing temperature in step (2) of the present invention is 450℃and the reduction temperature in step (3) is 450 ℃.
The high-activity nickel-based catalyst prepared by the method is applied to the hydrodeoxygenation reaction of guaiacol according to the following method:
(1) Adding a certain amount of guaiacol, a high-activity nickel-based catalyst and n-hexane into a 100mL batch high-pressure reaction kettle;
(2) And (3) replacing the gas with nitrogen and hydrogen respectively, then filling hydrogen with initial pressure of 3MPa, setting a certain stirring speed, setting the reaction temperature to 160-240 ℃ and the reaction time to 4-8 h, rapidly cooling the reaction kettle to room temperature after the reaction is finished, filtering to obtain a reaction solution, and analyzing the product by using gas chromatography.
As the limitation of the application of the high-activity nickel-based catalyst, the mass ratio of the guaiacol to the catalyst is 2:1-8:1.
After the technical scheme is adopted, the invention has the following beneficial effects:
1. the invention takes nickel-aluminum layered double metal hydroxide as a precursor to prepare the high-activity nickel-based catalyst Ni/Al with uniform dispersed metal phase, accurate and adjustable catalytic activity site, high specific surface area and strong metal-carrier interaction 2 O 3 。
The principle of high catalytic activity of the catalyst is mainly due to the fact that in general, the layered double hydroxide has the chemical formula [ M ] 1-x 2+ M x 3+ (OH) 2 ] x+ [A x/n ] n- .mH 2 O, where M 2+ And M 3+ Represents divalent and trivalent laminate metal cations, respectively, and interlayer anions A n- Through electrostatic interactions of the charges into the layers. The layered double hydroxide has adjustable property, and different active metal elements can be introduced into the layered structure by adjusting the types of the introduced metal cations and the proportion of the bitrivalent metal cations; the particle size and distribution of the active metal can also be controlled by changing the synthesis method and synthesis conditions; under the restriction of lattice positioning effect, metal ions are mutually highly dispersed on the layered double hydroxide laminate, and after high-temperature roasting and reduction treatment, the metal ions are removedOther metal components than the active metal can be converted to the corresponding oxides to act as promoters and spacers, thereby obtaining a metal catalyst with highly dispersed metal active sites.
2. Compared with the prior art, under the same reaction conditions, the conversion rate of the guaiacol can reach 100 percent, the selectivity of the cyclohexane can reach 95 percent, and the yield of the cyclohexane is obviously improved; when the conversion rate of the guaiacol and the selectivity of the cyclohexane are the same as those of the prior art, the reaction temperature is lower, and the reaction condition is milder, so that the high-activity nickel-based catalyst disclosed by the invention has excellent catalytic performance on the hydrodeoxygenation reaction of the guaiacol.
Drawings
FIG. 1 is a high dispersion Ni/Al obtained in example 2 2 O 3 -LDH catalyst XRD pattern; as can be seen from the figure, niAl-LDH shows a relatively complete and pure hydrotalcite-like crystal phase with a molecular formula of Ni 2 Al(CO 3 ) 2 (OH) 3 (PDF#48-0594) is that the interlayer anion is CO 3 2- Wherein a high and sharp diffraction peak at a lower 2 theta value indicates the presence of a distinct lamellar structure; niAl-LDO was mainly NiO phase (PDF#65-6920), and Al was not found 2 O 3 Diffraction peaks of (2); ni/Al 2 O 3 In the LDH, ni 2+ Is reduced to pure Ni 0 Phase (PDF # 65-0380), no Al was found 2 O 3 Is a diffraction peak of (2).
Detailed Description
The invention will be further illustrated with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the practice of the invention.
Example 1
Weighing 58.158g of nickel nitrate hexahydrate, 37.513g of aluminum nitrate nonahydrate and 250mL of water, adding into a 500mL three-necked flask, stirring to dissolve all the nickel nitrate hexahydrate, adding 126.126g of urea, uniformly mixing, heating to 105 ℃ for reaction for 12h, stopping stirring, cooling to 95 ℃ for ageing for 24h, cooling to room temperature, filtering and washing to obtain filter residuesVacuum drying at 80deg.C overnight, placing in a muffle furnace, roasting at 400deg.C for 6 hr in air atmosphere, placing the obtained solid in a tube furnace, and reducing at 400deg.C for 6 hr in hydrogen atmosphere to obtain Ni 2+ /Al 3+ Ni/Al of 2/1 2 O 3 -LDH catalyst.
Example 2
Weighing 58.158g of nickel nitrate hexahydrate, 37.513g of aluminum nitrate nonahydrate and 250mL of water, adding into a 500mL three-port bottle, stirring to dissolve all the materials, adding 126.126g of urea, uniformly mixing, heating to 105 ℃ for reaction for 12h, stopping stirring, cooling to 95 ℃ for aging for 24h, cooling to room temperature, filtering and washing to obtain filter residues, drying at 80 ℃ in vacuum overnight, placing in a muffle furnace, roasting at 450 ℃ for 6h in an air atmosphere, placing the obtained solid in a tubular furnace, reducing at 450 ℃ for 6h in a hydrogen atmosphere to obtain Ni 2+ /Al 3+ Ni/Al of 2/1 2 O 3 -LDH catalyst.
Example 3
Weighing 58.158g of nickel nitrate hexahydrate, 37.513g of aluminum nitrate nonahydrate and 250mL of water, adding into a 500mL three-port bottle, stirring to dissolve all the materials, adding 126.126g of urea, uniformly mixing, heating to 105 ℃ for reaction for 12h, stopping stirring, cooling to 95 ℃ for aging for 24h, cooling to room temperature, filtering and washing to obtain filter residues, drying at 80 ℃ in vacuum overnight, placing in a muffle furnace, roasting at 500 ℃ for 6h in an air atmosphere, placing the obtained solid in a tubular furnace, and reducing at 500 ℃ for 6h in a hydrogen atmosphere to obtain Ni 2+ /Al 3+ Ni/Al of 2/1 2 O 3 -LDH catalyst.
Example 4
Weighing 65.428g of nickel nitrate hexahydrate, 28.135g of aluminum nitrate nonahydrate and 250mL of water, adding into a 500mL three-port bottle, stirring to dissolve all the materials, adding 121.621g of urea, uniformly mixing, heating to 105 ℃ for reaction for 12h, stopping stirring, cooling to 95 ℃ for aging for 24h, cooling to room temperature, filtering and washing to obtain filter residues, drying at 80 ℃ in vacuum overnight, placing in a muffle furnace, roasting at 450 ℃ for 6h in an air atmosphere, placing the obtained solid in a tubular furnace, reducing at 450 ℃ for 6h in a hydrogen atmosphere to obtain Ni 2+ /Al 3+ Is 3/1Ni/Al 2 O 3 -LDH catalyst.
Example 5
Weighing 69.790g of nickel nitrate hexahydrate, 22.508g of aluminum nitrate nonahydrate and 250mL of water, adding into a 500mL three-port bottle, stirring to dissolve all the materials, adding 118.919g of urea, uniformly mixing, heating to 105 ℃ for reaction for 12h, stopping stirring, cooling to 95 ℃ for aging for 24h, cooling to room temperature, filtering and washing to obtain filter residues, drying at 80 ℃ in vacuum overnight, placing in a muffle furnace, roasting at 450 ℃ for 6h in an air atmosphere, placing the obtained solid in a tubular furnace, reducing at 450 ℃ for 6h in a hydrogen atmosphere to obtain Ni 2+ /Al 3+ Ni/Al of 4/1 2 O 3 -LDH catalyst.
Example 6
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 160 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 80.2% and the selectivity to cyclohexane was 67.6%.
Example 7
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 180 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 91.4% and the cyclohexane selectivity was 79.9%.
Example 8
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 95.2%.
Example 9
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 220 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 86.5%.
Example 10
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 240 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 81.4%.
Example 11
Ni prepared in example 1 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 73.8%.
Example 12
Ni prepared in example 3 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 58.3%.
Example 13
Ni prepared in example 4 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the selectivity to cyclohexane was 87.5%.
Example 14
Ni prepared in example 5 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 96.5% and the cyclohexane selectivity was 83.7%.
Example 15
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 4 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 81.6% and the cyclohexane selectivity was 82.1%.
Example 16
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 8 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 79.6%.
Example 17
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.1g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 80.6%.
Example 18
Ni prepared in example 2 2+ /Al 3+ Ni/Al of 2/1 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.3g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 79.9%.
Example 19
Ni prepared in example 2 2+ /Al 3+ Is 2/1Ni/Al 2 O 3 LDH catalyst is applied to the reaction.
0.8g of guaiacol, 0.4g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this example, the conversion of guaiacol was 100% and the cyclohexane selectivity was 70.4%.
Comparative example 1
Ni prepared by traditional coprecipitation hydrothermal method 2+ /Al 3+ Preparing hydrotalcite-based Ni/Al by taking 2/1 of NiAl-LDH as precursor 2 O 3 A catalyst, which is applied to the reaction.
0.8g of guaiacol, 0.2g of catalyst and 40mL of normal hexane are weighed and added into a 100mL batch high-pressure reaction kettle, the nitrogen and the hydrogen are respectively used for replacing the gases for 3 times, then the hydrogen with the initial pressure of 3MPa is filled, the stirring speed is set to be 600rpm, the reaction temperature is set to be 200 ℃, the reaction time is set to be 6 hours, the reaction kettle is rapidly cooled to room temperature, the reaction liquid is obtained by filtration, and the conversion rate of the guaiacol and the selectivity of the cyclohexane are quantitatively analyzed by gas chromatography. In this comparative example, the conversion of guaiacol was 100% and the selectivity to cyclohexane was 56.5%.
TABLE 1 high activity Ni/Al obtained by different preparation methods 2 O 3 Catalyst
Examples Ni 2+ /Al 3+ Firing temperature Reduction temperature
Example 1 2/1 400 400
Example 2 2/1 450 450
Example 3 2/1 500 500
Example 4 3/1 450 450
Example 5 4/1 450 450
Table 2 comparison of catalytic activity of examples and comparative examples
Figure BDA0003959180830000081
It can be seen from tables 1 and 2 that the catalyst obtained by the present invention was used in the hydrodeoxygenation of guaiacol, and had good catalytic performance as compared with the catalyst obtained by the prior art. Wherein, the nickel-aluminum layerNi for use as a double metal hydroxide 2+ And Al 3+ Molar ratio, firing temperature and reduction temperature to the resulting highly dispersed Ni/Al 2 O 3 The catalytic performance of the LDH catalyst is greatly influenced, the conversion rate of guaiacol and the selectivity of cyclohexane are obviously improved compared with the prior art, the conversion rate of guaiacol can reach 100%, the selectivity of cyclohexane can reach 95.2%, and the catalyst has mild preparation conditions and low cost when the catalytic activity is the same.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (6)

1. The preparation method of the high-activity nickel-based catalyst is characterized by comprising the following steps:
(1) Weighing nickel nitrate hexahydrate, aluminum nitrate nonahydrate and 250mL of distilled water in a certain molar ratio, adding the nickel nitrate hexahydrate, the aluminum nitrate nonahydrate and the distilled water into a 500mL three-necked flask, stirring to dissolve the nickel nitrate hexahydrate, adding a certain amount of urea, reacting for 12h at 105 ℃, ageing for 24h at 95 ℃, cooling to room temperature, filtering, washing the filter residue, and drying the filter residue at 80 ℃ in vacuum overnight to obtain nickel-aluminum layered double metal hydroxide, which is denoted as NiAl-LDH;
(2) Placing the nickel-aluminum layered double metal hydroxide obtained in the step (1) into a muffle furnace, roasting for 6 hours in an air atmosphere at a roasting temperature of 400-500 ℃ to obtain nickel-aluminum layered double metal oxide, and marking the nickel-aluminum layered double metal oxide as NiAl-LDO;
(3) Then the nickel-aluminum layered bimetallic oxide obtained in the step (2) is placed in a tube furnace for reduction for 6 hours in a hydrogen atmosphere, the reduction temperature is 400-500 ℃, and the high-activity nickel-based catalyst is obtained and is marked as Ni/Al 2 O 3 -LDH。
2. The method for preparing a high activity nickel-based catalyst according to claim 1, wherein Ni in the nickel-aluminum layered double hydroxide in the step (1) 2+ And Al 3+ The molar ratio is 2/1-4/1.
3. The method for preparing a high activity nickel-based catalyst according to claim 1, wherein the amount of urea used for preparing the nickel-aluminum layered double hydroxide in the step (1) is cationic Ni 2+ And Al 3+ 3 times the total moles charged.
4. The method for preparing a high activity nickel-based catalyst according to claim 1, wherein the calcination temperature in the step (2) is 450 ℃, and the reduction temperature in the step (3) is 450 ℃.
5. Use of a highly active nickel-based catalyst according to claim 1 in the hydrodeoxygenation of guaiacol, characterized in that the catalyst is used in particular in the following way:
(1) Adding a certain amount of guaiacol, a high-activity nickel-based catalyst and n-hexane into an intermittent high-pressure reaction kettle, respectively replacing the gases with nitrogen and hydrogen, and then filling hydrogen with initial pressure of 3 MPa;
(2) Setting the reaction temperature to 160-240 ℃ and the reaction time to 4-8 h under the stirring state, rapidly cooling the reaction kettle to room temperature after the reaction is finished, filtering to obtain a reaction liquid, and analyzing the product by using gas chromatography.
6. The use of a high activity nickel-based catalyst according to claim 5 in hydrodeoxygenation of guaiacol, wherein the mass ratio of guaiacol to high activity nickel catalyst in step (1) is 2:1-8:1.
CN202211475556.7A 2022-11-23 2022-11-23 Preparation of high-activity nickel-based catalyst and application of high-activity nickel-based catalyst in guaiacol hydrodeoxygenation Pending CN116116416A (en)

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