CN113559907A - Nano-confinement nickel-based catalyst and preparation method and application thereof - Google Patents

Nano-confinement nickel-based catalyst and preparation method and application thereof Download PDF

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CN113559907A
CN113559907A CN202110837661.XA CN202110837661A CN113559907A CN 113559907 A CN113559907 A CN 113559907A CN 202110837661 A CN202110837661 A CN 202110837661A CN 113559907 A CN113559907 A CN 113559907A
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nickel
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杨明
华俊威
董媛
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China University of Geosciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J27/24—Nitrogen compounds
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The invention discloses a nano limited-area nickel-based catalyst and a preparation method and application thereof, belonging to the technical field of catalyst preparation. The nano limited-area nickel-based catalyst is obtained by taking silicon dioxide or aluminum oxide as a carrier, melamine or bipyridine as a nitrogen source and nickel as an active component through high-temperature calcination reduction, wherein the content of nickel in the catalyst is 8-26 wt%, and the particle size of the nickel is 5-15 nm; specific surface area of 400-600m2Per g, pore volume of 0.5-1.6cm3The pore diameter is 5-13 nm. The nickel-based catalyst has the characteristics of simple preparation, good stability and easy storage. Meanwhile, the nickel-based catalyst can improve the hydrogenation rate of the organic liquid hydrogen storage material and reduce the cost of the organic liquid hydrogen storage technology.

Description

Nano-confinement nickel-based catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a nano limited-area nickel-based catalyst, and a preparation method and application thereof.
Background
The hydrogen energy is considered as an ideal future energy source with wide sources, high heat value, cleanness and no pollution, but the problem of safe storage and transportation of the hydrogen energy restricts the large-scale practical application of the hydrogen energy. The organic liquid hydrogen storage technology has been widely researched due to the characteristics of high hydrogen storage capacity, safety and stability, wherein the hydrogenation process of the hydrogen storage material is a key link of the organic liquid hydrogen storage technology. The catalysts applied to the organic liquid hydrogen storage technology are mainly noble metal catalysts such as Pd, Pt, Ru, Rh and the like, and the noble metal catalysts have the problems of high cost, limited resources, easy poisoning and inactivation and the like, so that the research and development of novel efficient and cheap catalysts are of great significance.
The nickel catalyst has the advantages of high activity, low price and the like, and is widely applied to hydrogenation reaction.
For example, a nitrogen-doped clad core-shell structured nickel-iron alloy catalyst reported in chinese patent CN106732733A is prepared by preparing nickel-iron metal into Layered Double Hydroxides (LDHs), mixing with melamine and dicyandiamide to form a composite precursor, and finally calcining to obtain the catalyst, wherein the catalyst has uniform particle size, good dispersibility, and high activity for selective hydrogenation of o-chloronitrobenzene.
In the chinese patent CN108525670A, nickel and organic molecules form a precursor, which is then mixed with silica sol, and finally calcined once to obtain the catalyst, because the silicon carrier is a mesoporous structure, the supported nickel-based active component is limited in the pore channel, so the catalyst has good dispersibility, has good activity for selectively hydrogenating phenylpropyl aldehyde, and can be reacted within 4 hours.
However, the use of nickel for hydrogenation reactions of organic liquid hydrogen storage materials has been rarely reported.
Asahi peak et al at Zhejiang university, performed a hydrogenation test of ethylcarbazole using Raney nickel, which is highly active among nickel-based catalysts, and the ethylcarbazole and the activated Raney nickel (Raney-Ni) catalyst were placed in a stainless steel autoclave, and the stirring speed, temperature, and pressure were continuously monitored (Journal of Alloys and Compounds 2011, Vol. 509, pp. 152-156).
Wuyowa et Al, Beijing university general Ni/Al2O3And YH3The powders were mixed in a 4:1 mass ratio to prepare a 1 wt% Ni/Al2O3-YH3 catalyst for ethylcarbazole hydrogenation test (Journal of Materials Chemistry A2019, volume 7, page 16677, 16684).
However, the catalyst is used for hydrogenation reaction of organic liquid hydrogen storage material, and still has the problems of slow reaction and low yield. In general, a catalyst prepared by doping nitrogen atoms or assembling the nitrogen atoms with organic molecules and then loading metals on a carrier has good dispersibility and thus has high activity, but the specific surface area is greatly reduced along with the increase of the loading capacity, pore channels are blocked, the activity is also reduced, so the loading capacity can only be maintained at low loading capacity, and in addition, the activity of the catalyst is insufficient for the full hydrogenation of large organic molecules with benzene rings, so the catalyst for the liquid hydrogen storage material needs to be improved.
Disclosure of Invention
Based on the above, the invention aims to provide a nano limited-area nickel-based catalyst, wherein the nickel content in the nickel-based catalyst is 8-26 wt%, and the particle size of the nickel is 5-15 nm;
the specific surface area of the catalyst is 400-600m2Per g, pore volume of 0.5-1.6cm3The pore diameter is 5-13 nm.
Another object of the present invention is to provide a method for preparing a nano confined nickel-based catalyst, which comprises the following steps:
(1) weighing a nickel source and a nitrogen source in a beaker, adding a proper amount of solvent, heating and refluxing in an oil bath at 80-110 ℃, and stirring until the nickel source and the nitrogen source are completely dissolved to obtain a green clear liquid;
(2) weighing 1-2.5g of carrier, adding the carrier into the green clear liquid obtained in the step (1), heating the carrier in an oil bath at the temperature of 100 ℃ and 130 ℃, and evaporating the solvent to dryness to obtain a viscous solid;
(3) putting the viscous solid in the step (2) into an oven, drying for 8-12h at the temperature of 60-80 ℃, and fully grinding the dried solid to obtain a green powder catalyst precursor;
(4) transferring the catalyst precursor in the step (3) into a tube furnace, and introducing inert gas and H2Calcining and reducing the mixed gas for 3-5h, standing and cooling to room temperature to obtain the nickel-based catalyst.
Preferably, the nickel source in the step (1) is nickel acetate or nickel chloride; the nitrogen source is melamine or 2, 2' -bipyridine; the solvent is one or two of water or absolute ethyl alcohol.
Preferably, the molar concentration ratio of the nickel source to the nitrogen source in the step (1) is 1: 2 to 4.
Preferably, the carrier in the step (2) is silica or alumina.
Preferably, the inert gas in the step (4) is Ar.
Preferably, H in the mixed gas in the step (4)2The volume content of (2) is 10%, and the flow rate of the mixed gas is 200-500 ml/min.
Preferably, the reduction temperature in the step (4) is 400-900 ℃, and the reduction time is 3-5 h.
The invention also provides the application of the catalyst in hydrogenation reaction of the organic liquid hydrogen storage material. The reaction is carried out in a high-temperature high-pressure reaction kettle, and the experimental process is as follows: placing an organic liquid hydrogen storage material and a catalyst into a reaction kettle, introducing pure hydrogen to empty air in the reaction kettle (avoid explosion in the reaction process), heating the reaction kettle to 130-160 ℃, introducing the hydrogen, starting reaction, sampling at intervals and testing the reaction rate, wherein the reaction temperature is 130-160 ℃, the hydrogen pressure is 5-8MPa, and the reaction speed is 400-600 r/min.
Preferably, the organic liquid hydrogen storage material is azopropylcarbazole.
The nickel-based catalyst provided by the invention uses silicon dioxide or aluminum oxide as a carrier, uses melamine or 2, 2' -bipyridine as a nitrogen source, is loaded on the carrier together with an active component nickel, and is subjected to high-temperature calcination reduction to obtain the catalyst. The catalyst improves the loading capacity to break through higher activity by increasing the doping amount of nitrogen atoms under the condition of ensuring higher dispersity, nickel metal has a domain limiting effect by coordinating with the nitrogen atoms to achieve the aim of dispersing, the preparation is simple, the stability is good, the storage is easy, the nickel metal is only slightly inactivated after being exposed in the air for a long time, and the nickel metal can replace a noble metal catalyst to be applied to an organic liquid hydrogen storage technology so as to greatly reduce the cost of the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Ni catalyst prepared by the invention can be applied to hydrogenation reaction of organic liquid hydrogen storage materials, has high catalytic activity and good stability, and can be repeatedly used.
(2) The catalyst prepared by the method is a non-noble metal catalyst, and noble metals are not added, so that the cost of the catalyst is greatly reduced.
(3) Ni has good dispersibility on the support and the metal particle size remains at the nanometer level.
(4) The preparation method is simple in preparation process, low in equipment requirement and capable of being produced and applied in a large scale.
Drawings
FIG. 1 is a graph showing the physical adsorption and desorption of the catalyst in example 1;
FIG. 2 is a graph showing the pore size distribution of the catalyst in example 1;
FIG. 3 is a TEM image of the catalyst of example 1;
FIG. 4 is a HRTEM image of the catalyst of example 1;
FIG. 5 is an X-ray diffraction pattern of the catalyst of example 1;
FIG. 6 is a graph of the catalyst of example 2 versus the reaction rate for the hydrogenation of azopropylcarbazole;
FIG. 7 is a graph of the amount of hydrogen carried by the catalyst of example 3 in a cyclic hydrogenation reaction of azopropylcarbazole;
FIG. 8 is a graph of the hydrogen loading in the hydrogenation of azopropylcarbazole over time for the catalysts of example 2 and comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
A nanometer limited nickel-based catalyst is prepared by the following steps:
(1) nickel acetate 1.035g (Ni wt% ═ 14, Mw 248.8) and melamine 1.572g (C) were weighed out3H6N6Mw 126g/mol, molar ratio 1:3) in a 250ml beaker, adding 100ml water, heating and refluxing in a fume hood at 90 ℃ for 60min, at which time the raw material is completely dissolved to obtain a green clear liquid;
(2) weighing 1.500g of silicon dioxide, adding the silicon dioxide into the green clear liquid obtained in the step (1), heating an oil bath kettle to 120 ℃, and evaporating the solvent to dryness to obtain a viscous solid;
(3) putting the viscous solid in the step (2) into an oven, drying at 70 ℃ for 8h, and fully grinding the dried solid to obtain a green powder catalyst precursor;
(4) transferring the catalyst precursor in the step (3) to a tube furnace, and introducing Ar and H2In which H is2The volume content is 10 percent, the nickel-based catalyst Ni-N-C/SiO is obtained after calcining reduction for 4 hours at 700 ℃, standing and cooling to room temperature2。
The physical adsorption and desorption curve of the catalyst is shown in figure 1, the pore size distribution is shown in figure 2, and the specific surface area of the catalyst is 400-600m2Per g, pore volume of 0.5-1.6cm3(ii)/g, the pore diameter is 5.0-13.0 nm. The catalyst was well dispersed as shown in FIG. 3 in a TEM image and FIG. 4 in an HRTEM image, and it was found from FIGS. 3 and 4 that the particle size of nickel was mostly in the range of 5 to 15 nm. The X-ray diffraction spectrum of the catalyst is shown in figure 5.
Example 2
The nano-confinement nickel-based catalyst prepared in example 1 was used in the hydrogenation experiment of the organic liquid hydrogen storage material:
0.2g of the catalyst and 2.0g of the azopropylcarbazole are added into 40ml of cyclohexane solvent to react, the reaction pressure is 7MPa, the reaction temperature is 150 ℃, the rotating speed is 600r/min, the reaction time is 90min, the total hydrogenation of the azopropylcarbazole can be realized, no other by-products are generated, and the hydrogenation reaction rate of the catalyst to the azopropylcarbazole is shown in figure 6.
Example 3
The nano-confinement nickel-based catalyst prepared in example 1 was used in the cyclic hydrogenation experiment of the organic liquid hydrogen storage material:
0.2g of the catalyst and 2.0g of azopropylcarbazole are added into 40ml of cyclohexane solvent for reaction, the reaction pressure is 7MPa, the reaction temperature is 150 ℃, and the rotating speed is 600 r/s. The hydrogenation data results are shown in figure 7. As can be seen from fig. 7, the hydrogenation performance is gradually reduced in five times of the cyclic hydrogenation experiments, but all the hydrogenation experiments can basically realize complete hydrogenation within 180min, which indicates that the catalyst can be recycled for multiple times, and the hydrogenation performance is not greatly reduced.
Example 4
A nanometer limited nickel-based catalyst is prepared by the following steps:
(1) nickel chloride 0.988g (Ni wt% 14, Mw 248.8) and melamine 1.572g (C)3H6N6Mw 126g/mol, molar ratio 1:3) in a 250ml beaker, adding 100ml water, heating and refluxing in a fume hood at 90 ℃ for 60min, at which time the raw material is completely dissolved to obtain a green clear liquid;
steps (2) to (4) were the same as in example 1.
Example 5
The carrier was replaced with 219m specific surface area2A catalyst having a specific surface area of 215.32m measured by a nitrogen desorption/physical test, prepared by the method of example 1, was prepared from alumina in a nano-sized, limited-area nickel-based catalyst2/g。
The hydrogenation experiment of the organic liquid hydrogen storage material is carried out on the nano-confinement nickel-based catalyst according to the method of the embodiment 2,
the result shows that the catalyst has good hydrogenation effect on the azopropylcarbazole.
Examples 6 to 16
The reaction conditions (molar ratio of nickel acetate to melamine, and temperature of calcination reduction) were modified, and the remaining steps were carried out to prepare a nano-confinement nickel-based catalyst having a nickel content of 8% to 26% according to the method of example 1, as shown in table 1:
TABLE 1
Figure BDA0003177821200000051
Figure BDA0003177821200000061
Comparative example 1
Commercially available 0.5 wt% Ru/Al2O3The catalyst was comparative example 1.
The catalysts of example 2 and comparative example 1 were used to conduct a Nitrogenopropylcarbazole (NPCZ) hydrogenation experiment as follows:
0.2g of the catalyst and 2.0g of azopropylcarbazole are added into 40ml of cyclohexane solvent for reaction, the reaction pressure is 7MPa, the reaction temperature is 150 ℃, the rotating speed is 600r/min, and the hydrogen loading amount of the catalytic NPCZ is changed along with time as shown in figure 8.
As can be seen from FIG. 8, example 1 only requires about 90 minutes for the hydrogenation of the NECZ and comparative example 1, under the same experimental conditions, is commercially available at 0.5 wt% Ru/Al2O3The catalyst did not react completely in 240 minutes.
Comparative example 2
An activated Raney nickel catalyst (Raney-Ni) prepared by Asahi peak, et al, Zhejiang university (Journal of Alloys and Compounds 2011, Vol.509, pp.152-156) was used as comparative example 2.
Comparative example 3
1 wt% Ni/Al prepared by Wuyor et Al, Beijing university2O3-YH3The catalyst (Journal of Materials Chemistry A2019, volume 7, page 16677-16684) is comparative example 3.
The catalysts prepared in example 1 and comparative examples 2-3 were used for the ethyl carbazole hydrogenation reaction, respectively, and the results are shown in table 2:
TABLE 2
Figure BDA0003177821200000062
Figure BDA0003177821200000071
As can be seen from Table 2, under similar reaction conditions, hydrogenation of NECZ by Raney-Ni did not completely react within 2.5h, and 1 wt% Ni/Al reacted within the same time2O3-YH3The higher reaction conditions are required, which indicates that the catalyst prepared in example 1 has high catalytic activity, superior to raney nickel catalyst and previously reported nickel-based catalyst.
The nickel-based catalysts prepared in examples 1 and 4-16 were used to perform the propylcarbazole hydrogenation reactions, respectively, with reaction times and yields as shown in table 3:
TABLE 3
Numbering Hydrogen storage molecules Reaction conditions Reaction time, min Yield%
Example 1 NPCZ 150℃，7MPa 90 100
Example 4 NPCZ 150℃，7MPa 120 100
Example 5 NPCZ 150℃，7MPa 180 96
Example 6 NPCZ 150℃，7MPa 90 100
Example 7 NPCZ 150℃，7MPa 90 100
Example 8 NPCZ 150℃，7MPa 120 98
Example 9 NPCZ 150℃，7MPa 120 100
Example 10 NPCZ 150℃，7MPa 120 98
Example 11 NPCZ 150℃，7MPa 120 45
Example 12 NPCZ 150℃，7MPa 180 80
Example 13 NPCZ 150℃，7MPa 100 100
Example 14 NPCZ 150℃，7MPa 90 100
Example 15 NPCZ 150℃，7MPa 100 98
Example 16 NPCZ 150℃，7MPa 120 100
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A nanometer limited nickel-based catalyst is characterized in that the nickel content in the nickel-based catalyst is 8-26 wt%, and the particle size of nickel is 5-15 nm;
the specific surface area of the catalyst is 400-600m2Per g, pore volume of 0.5-1.6cm3The pore diameter is 5-13 nm.
2. The method for preparing a nano-confinement nickel-based catalyst according to claim 1, comprising the steps of:
(1) weighing a nickel source and a nitrogen source in a beaker, adding a proper amount of solvent, heating and refluxing in an oil bath at 80-110 ℃, and stirring until the nickel source and the nitrogen source are completely dissolved to obtain a green clear liquid;
(2) weighing 1-2.5g of carrier, adding the carrier into the green clear liquid obtained in the step (1), heating the carrier in an oil bath at the temperature of 100 ℃ and 130 ℃, and evaporating the solvent to dryness to obtain a viscous solid;
(3) putting the viscous solid in the step (2) into an oven, drying for 8-12h at the temperature of 60-80 ℃, and fully grinding the dried solid to obtain a green powder catalyst precursor;
(4) transferring the catalyst precursor in the step (3) into a tube furnace, and introducing inert gas and H2Calcining and reducing the mixed gas for 3-5h, standing and cooling to room temperature to obtain the nickel-based catalyst.
3. The method according to claim 2, wherein the nickel source in step (1) is nickel acetate or nickel chloride; the nitrogen source is melamine or 2, 2' -bipyridine; the solvent is one or two of water or absolute ethyl alcohol.
4. The method according to claim 2, wherein the molar concentration ratio of the nickel source to the nitrogen source in step (1) is 1: 2 to 4.
5. The method according to claim 2, wherein the carrier in the step (2) is silica or alumina.
6. The production method according to claim 2, wherein the inert gas in the step (4) is Ar.
7. The method according to claim 2, wherein H in the mixed gas of the step (4)2The volume content of (2) is 10%, and the flow rate of the mixed gas is 200-500 ml/min.
8. The method as claimed in claim 2, wherein the reduction temperature in step (4) is 400-900 ℃ and the reduction time is 3-5 h.
9. The use of the nano-confined nickel-based catalyst as claimed in claim 1, wherein the catalyst is used in hydrogenation reaction of organic liquid hydrogen storage material.
10. The use of the nano-confined nickel-based catalyst as claimed in claim 9 wherein the organic liquid hydrogen storage material is azopropylcarbazole.
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