CN115041175B - Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound by using multi-metal oxide supported nickel catalyst - Google Patents

Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound by using multi-metal oxide supported nickel catalyst Download PDF

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CN115041175B
CN115041175B CN202210860171.6A CN202210860171A CN115041175B CN 115041175 B CN115041175 B CN 115041175B CN 202210860171 A CN202210860171 A CN 202210860171A CN 115041175 B CN115041175 B CN 115041175B
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刘安求
徐尔岗
王晓晨
高大明
蔡威盟
佘亚萍
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Hefei University
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    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
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    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
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    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/58—Radicals substituted by nitrogen atoms

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Abstract

A multi-metal oxide supported nickel catalyst, a preparation method and a method for preparing primary amine by using the multi-metal oxide supported nickel catalyst to catalyze and hydrogenate nitrile compounds relate to the technical field of heterogeneous catalysts. The multi-metal oxide supported nickel catalyst comprises Ni 0.5/Zn1.5Al1 Ox and the catalyst carrier comprises Zn 1.5Al1 Ox. Firstly, preparing NiZnAl layered double hydroxide by a hydrothermal method, and then preparing the multi-metal oxide supported nickel catalyst by calcination and reduction treatment. Compared with the traditional nickel catalyst Ni/Al 2O3 loaded by single metal oxide, the multi-metal oxide loaded nickel catalyst prepared by the invention has stronger acting force between metal and carrier due to the existence of Ni-Zn bond, so that the catalytic activity and the catalyst stability are obviously enhanced, thereby realizing the purpose of preparing corresponding primary amine by using non-noble metal catalyst to catalyze and hydrogenate nitrile compound under mild condition.

Description

Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound by using multi-metal oxide supported nickel catalyst
Technical Field
The invention relates to the technical field of heterogeneous catalysts, in particular to a multi-metal oxide supported nickel catalyst and a preparation method thereof. Meanwhile, the invention also discloses a method for preparing primary amine by catalyzing and hydrogenating the nitrile compound by using the catalyst.
Background
Primary amine is an important chemical intermediate and has wide application in dye, pigment, medicine, pesticide, high molecular polymer and other fields. Compared with other methods for synthesizing primary amine, the method for preparing primary amine by catalytic hydrogenation of nitrile compound has the advantages of high efficiency, environmental protection, simple treatment and rich raw material sources, and is a hot spot for current research.
In general, the catalytic hydrogenation of nitrile compounds may use homogeneous catalysts or heterogeneous catalysts. The heterogeneous catalyst has higher selectivity and activity, but has the inherent defect of difficult separation and recovery of the catalyst, and industrial production [Gomez,S.;Peters,J.A.;Maschmeyer,T.Adv.Synth.Catal.2002,344,1037-1057;Blaser,H.-U.;Malan,C.;Pugin,B.;Spindler,F.;Steiner,H.;Studer,M.Adv.Synth.Catal.2003,345,103-151;Werkmeister,S.;Junge,K.;Beller,M.Org.Process Res.Dev.2014,18,289-302.] is difficult to realize, so that the heterogeneous catalyst is generally adopted as the catalyst for preparing primary amine by catalyzing and hydrogenating nitrile compounds in the industry at present. In the heterogeneous catalyst, noble metal catalysts such as Pd-CuFe, pdCu, niPd and the like have good catalytic activity, and the corresponding primary amine [L.Liu,Y.H.Liu,Y.J.Ai,J.F.Li,J.J.Zhou,Z.B.Fan,H.J.Bao,R.H.Jiang,Z.N.Hu,J.T.Wang,K.Jing,Y.Wang,Q.L.Liang and H.B.Sun,iScience,2018,8,61–73;J.F.Li,L.Liu,Y.J.Ai,Z.N.Hu,Z.B.Liu,R.X.Guo,C.Zhang,H.M.Tian,J.J.Wu,M.Ruan and H.B.Sun,ChemistrySelect,2019,4,7346–7350.H.Goksu,S.F.Ho,O.Metin,K.Korkmaz,A.M.Garcia,M.S.Gu¨ltekin and S.Sun,ACS Catal.,2014,4,1777–1782], can be obtained with the yield of more than 90% under milder conditions, however, the noble metal catalysts are expensive, and are not beneficial to industrial production. Non-noble metal catalysts are also used in large amounts in this reaction and achieve good results [Y.M.Zhang,H.M.Yang,Q.Chi and Z.Z.Zhang,Chem-SusChem,2019,12,1246–1255;Y.Y.Cao,L.B.Niu,X.Wen,W.H.Feng,L.Huo andG.Y.Bai,J.Catal.,2016,339,9–13.;Nature Catalysis 2022,5,20–29], however, because of the lower activity of non-noble metal catalysts, the reaction often requires higher temperatures and pressures (80-120 ℃,30-50 bar).
Ni-based catalysts are used in various hydrogenation reactions due to their high catalytic activity. Zhang Zehui et Al designed a class of Ni-based catalysts Ni/Al 2O3 -600 for use in the catalytic hydrogenation of lignin and nitriles [ New j.chem.,2020,44,549-555], which are highly active but still require high temperatures (60-80 ℃) to efficiently catalyze the hydrogenation of nitriles, there remains a need to develop a non-noble metal catalyst that can efficiently catalyze the hydrogenation of nitriles to primary amines under mild conditions.
Disclosure of Invention
The invention aims to provide a multi-metal oxide supported nickel catalyst, a preparation method and a method for preparing primary amine by using the multi-metal oxide supported nickel catalyst to catalyze and hydrogenate nitrile compounds.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A multi-metal oxide supported nickel catalyst comprises Ni 0.5/Zn1.5Al1 Ox and a catalyst carrier Zn 1.5Al1 Ox. x is the number of O in the carrier molecule and is generally from 2 to 5.
A method for preparing a multi-metal oxide supported nickel catalyst comprises the steps of firstly preparing NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH by a hydrothermal method, and preparing the multi-metal oxide supported nickel catalyst Ni 0.5/Zn1.5Al1 Ox by calcination and reduction treatment; the method comprises the following specific steps:
1) Preparation of NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH:
Adding 2.5mmol of Ni (NO 3)2·6H2 O, 7.5mmol of Zn (NO 3)2·6H2 O, 5mmol of Al (NO 3)3·9H2 O, 37.5mmol of urea and 50mL of water into a hydrothermal kettle for hydrothermal reaction, standing and cooling the obtained product after the reaction is finished, centrifuging, washing with water, and drying to obtain NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH;
2) Preparation of Ni 0.5/Zn1.5Al1 Ox catalyst:
calcining the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH prepared in the step 1) in air at a certain temperature, and then reducing the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH by nitrogen-hydrogen mixed gas to obtain the Ni 0.5/Zn1.5Al1 Ox catalyst.
As a preferable technical scheme of the invention, in the preparation method of the multi-metal oxide supported nickel catalyst, the hydrothermal synthesis reaction temperature in the step 1) is 100-300 ℃ and the reaction time is 10-40 h. The calcination temperature in the air in the step 2) is 500-800 ℃ and the calcination time is 1-20 h. The volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen mixed gas is 9:1. The reaction temperature of the reduction of the nitrogen-hydrogen mixed gas is 500-800 ℃, the temperature rising rate is 1-5 ℃/min, and the reaction time is 2-5 h.
The invention also provides a method for preparing primary amine by catalyzing and hydrogenating nitrile compounds by utilizing the multi-metal oxide supported nickel catalyst, which comprises the steps of adding aromatic or aliphatic nitrile compounds and ammonia water into n-hexane, adding the multi-metal oxide supported nickel catalyst Ni 0.5/Zn1.5Al1 Ox into a reaction kettle after stirring, replacing air with hydrogen, introducing hydrogen with certain pressure, stirring and reacting at a certain temperature, and centrifugally separating the catalyst after the reaction is finished to obtain the corresponding primary amine product.
As a preferred embodiment of the present invention, in the primary amine production method, the molar ratio of ammonia water to nitrile compound is 5-30:1, preferably 10-20:1, more preferably 13:1. 10 to 80mg of catalyst, preferably 30 to 50mg of catalyst, more preferably 40mg of catalyst, are added per 1mmol of nitrile compound. The pressure of the hydrogen used for the hydrogenation is from 1 to 40bar, preferably from 5 to 20bar, more preferably 10bar. The hydrogenation reaction temperature is 30 to 80 ℃, preferably 30 to 60 ℃, more preferably 30 ℃; the hydrogenation reaction time is 10 to 48 hours, preferably 12 to 24 hours.
Although conventional single metal oxide supported Ni-based catalysts such as Ni/Al 2O3 have high catalytic activity, the activity and stability of the catalyst are required to be improved due to insufficient force between the metal and the support. According to the invention, zn element is introduced on the basis of the traditional Ni/Al 2O3, a type of Ni 0.5/Zn1.5Al1 Ox catalyst is prepared, and compared with the traditional single metal oxide supported nickel catalyst Ni/Al 2O3, the multi-metal oxide supported nickel catalyst prepared by the invention has the advantages that the action force between metal and carrier is stronger due to the existence of Ni-Zn bond, so that the catalytic activity and the catalyst stability are obviously enhanced, the nitrile compound can be selectively hydrogenated under the mild condition (30-80 ℃ and 10bar H 2) to prepare the corresponding primary amine, and the yield is mostly more than 90%, so that the purpose of preparing the corresponding primary amine by catalyzing the nitrile compound with the non-noble metal catalyst under the mild condition is realized.
Compared with the existing method for preparing primary amine by using nitrile compounds as raw materials, the method has more advantages due to the use of the carrier capable of stabilizing metal and improving catalytic activity, and is specifically characterized in that:
1) The catalyst has high reaction activity and selectivity, and the conversion rate of raw materials can reach 99.6 percent and the yield of the benzyl amine can reach 93.8 percent by taking the benzonitrile as an example.
2) The catalytic reaction condition is mild, hydrogen is used as a hydrogen source, the reaction can be carried out at 30 ℃, the reaction time is short, and the method is favorable for large-scale production.
3) The catalyst is simple to synthesize, the metal used is Ni, and the price is relatively lower than that of a noble metal catalyst.
4) The catalyst used in the invention is a multi-metal supported Ni catalyst, and the catalyst has a stable structure and can be recycled, so that the production cost can be reduced.
Drawings
FIG. 1 is an XRD pattern of a Ni 0.5/Zn1.5Al1 Ox catalyst prepared in accordance with an example of the present invention, the XRD being carried out on a Bruker ADVANCED D8 powder diffractometer, with a2 theta range of 10-80 deg. and a scan rate of 0.016 deg./s.
Wherein NiZnAlOx-500 means that the catalyst was reduced by a nitrogen-hydrogen mixture (N 2∶H2 =9:1, v/v) at 500 ℃, and NiZnAlOx-600 and NiZnAlOx-650 synthesis methods are substantially the same as NiZnAlOx-500 except that the reduction temperatures are 600 ℃ and 650 ℃, respectively. NiZnAlOx-air indicates that the catalyst has not been reduced.
As can be seen from FIG. 1, characteristic peaks of Ni-Zn and AlNi 3 appear on XRD patterns of NiZnAlOx-500, niZnAlOx-600 and NiZnAlOx-650 reduced with hydrogen, except NiZnAlOx-air, indicating that the Ni-Zn alloy is indeed present in the actual catalyst.
Fig. 2 is a temperature programmed reduction chart (H 2 -TPR chart) of a Ni 0.5/Zn1.5Al1 Ox catalyst prepared according to an example of the present invention.
From the figure it can be seen that the reduced catalysts NiZnAlOx-500, niZnAlOx-600 and NiZnAlOx-650 have a higher reduction temperature than the unreduced catalysts NiZnAlOx-air, indicating a higher stability of the reduced catalysts, while in combination with the XRD pattern of the catalysts (FIG. 1) it can be seen that the reduced catalysts contain Ni-Zn alloy, which indicates that the Ni-Zn bonds formed by the catalysts do improve the stability of the catalysts. Wherein NiZnAlOx-600 has a reduction temperature as high as 680 deg.C, which is higher than NiZnAlOx-500 and NiZnAlOx-650.
FIG. 3 is a reaction scheme for preparing benzyl amine by catalytic hydrogenation of benzonitrile using NiZnAlOx catalyst. As can be seen from the figure, there are side reactions and secondary amine and other by-products in the catalytic reaction, so it is important to develop a catalyst with high selectivity for the reaction. Meanwhile, the addition of a certain amount of ammonia water can also help to improve the selectivity of preparing the benzyl amine by catalyzing and hydrogenating the benzonitrile.
Detailed Description
The preparation method and the catalytic hydrogenation process of the present invention are described in detail by means of specific examples. The nitrile compounds used in the examples were purchased from national pharmaceutical chemicals Co., ltd or carbofuran chemical technology Co., ltd and were analytically pure in purity. The conversion of the nitrile compound and the yield of the primary amine were analyzed by gas chromatography. The gas phase was carried out on an Agilent 7890A gas chromatograph and the samples were separated using a cross-linked capillary HP-5 column (30 m 0.32mm 0.4 mm) and detected using a hydrogen flame ionization detector. The analysis conditions were that the carrier gas was nitrogen, the flow rate was 40mL min -1, the sample inlet temperature was 300 ℃, the column temperature was programmed to 280℃and maintained for 0.5h, the detector temperature was 300℃and the conversion and yield were determined using ethylbenzene as an internal standard.
Taking benzonitrile as an example, the conversion rate is calculated as follows:
Conversion of benzonitrile= (amount of benzonitrile substance after 1-reaction/amount of initial benzonitrile substance) ×100%.
The calculation formula of the yield of the benzyl amine is as follows:
Yield of benzylamine= (amount of material of benzylamine produced after reaction/amount of initial benzonitrile material) ×100%.
Example 1
1) Preparation of NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH:
2.5mmol of Ni (NO 3)2·6H2 O, 7.5mmol of Zn (NO 3)2·6H2 O, 5mmol of Al (NO 3)3·9H2 O, 37.5mmol of urea and 50mL of water) are added into a hydrothermal kettle to react for 24 hours at 100 ℃, and after the reaction is finished, the obtained product is kept stand and cooled, centrifuged, washed with water and dried to obtain the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH.
2) Preparation of Ni 0.5/Zn1.5Al1 Ox catalyst:
Calcining the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH prepared in the step 1) in the air at 600 ℃ for 2 hours, then reducing by nitrogen-hydrogen mixed gas (N 2∶H2 =9:1, v/v), heating up at 3 ℃/min during reduction, heating up to 600 ℃ and then keeping for 2 hours to obtain the Ni 0.5/Zn1.5Al1 Ox catalyst, which is recorded as NiZnAlOx-600 catalyst.
3) Catalytic hydrogenation to produce benzylamine:
0.5mmol of benzonitrile and 200uL of concentrated ammonia water are added into a reaction kettle, 10mL of normal hexane is stirred, then 20mg NiZnAlOx-600 catalyst is added, after air is replaced by hydrogen, 10bar of hydrogen is introduced, after the reaction is completed under stirring at 30 ℃ for 12 hours, ethylbenzene is added as an internal standard, 20mL of acetonitrile is added to dilute the reaction solution, the reaction conversion rate is 99.6% by sampling through gas chromatography, and the yield is 93.8%.
Example 2
1) Preparation of NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH:
2.5mmol of Ni (NO 3)2·6H2 O, 7.5mmol of Zn (NO 3)2·6H2 O, 5mmol of Al (NO 3)3·9H2 O, 37.5mmol of urea and 50mL of water) are added into a hydrothermal kettle to react for 24 hours at 100 ℃, and after the reaction is finished, the obtained product is kept stand and cooled, centrifuged, washed with water and dried to obtain the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH.
2) Preparation of Ni 0.5/Zn1.5Al1 Ox catalyst:
Calcining the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH prepared in the step 1) in the air at 600 ℃ for 2 hours, then reducing by nitrogen-hydrogen mixed gas (N 2∶H2 =9:1, v/v), heating up at 3 ℃/min during reduction, heating up to 500 ℃ and then keeping for 2 hours to obtain the Ni 0.5/Zn1.5Al1 Ox catalyst, which is recorded as NiZnAlOx-500 catalyst.
3) Catalytic hydrogenation to produce benzylamine:
0.5mmol of benzonitrile and 200uL of concentrated ammonia water are added into a reaction kettle, 10mL of normal hexane is stirred, then 20mg NiZnAlOx-500 catalyst is added, after air is replaced by hydrogen, 10bar of hydrogen is introduced, after the reaction is completed under stirring at 30 ℃ for 4 hours, ethylbenzene is added as an internal standard, 20mL of acetonitrile is added to dilute the reaction solution, the reaction conversion rate is 51.1% by sampling through gas chromatography, and the yield is 48.6%.
Example 3
1) Preparation of NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH:
2.5mmol of Ni (NO 3)2·6H2 O, 7.5mmol of Zn (NO 3)2·6H2 O, 5mmol of Al (NO 3)3·9H2 O, 37.5mmol of urea and 50mL of water) are added into a hydrothermal kettle to react for 24 hours at 100 ℃, and after the reaction is finished, the obtained product is kept stand and cooled, centrifuged, washed with water and dried to obtain the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH.
2) Preparation of Ni 0.5/Zn1.5Al1 Ox catalyst:
Calcining the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH prepared in the step 1) in the air at 600 ℃ for 2 hours, then reducing by nitrogen-hydrogen mixed gas (N 2∶H2 =9:1, v/v), heating up at 3 ℃/min during reduction, heating up to 650 ℃, and keeping for 2 hours to obtain the Ni 0.5/Zn1.5Al1 Ox catalyst, which is recorded as NiZnAlOx-650 catalyst.
3) Catalytic hydrogenation to produce benzylamine:
0.5mmol of benzonitrile and 200uL of concentrated ammonia water are added into a reaction kettle, 10mL of normal hexane is stirred, then 20mg NiZnAlOx-650 catalyst is added, after air is replaced by hydrogen, 10bar of hydrogen is introduced, after the reaction is completed under stirring at 30 ℃ for 12 hours, ethylbenzene is added as an internal standard, 20mL of acetonitrile is added to dilute the reaction solution, the reaction conversion rate is 98.3% by sampling through gas chromatography, and the yield is 92.1%.
Example 4
Other amine preparation examples:
Concentrated ammonia water (the addition amount is shown in table 1), 0.5mmol of substrate and 10mL of n-hexane are added into a reaction kettle, 20mg NiZnAlOx-600 catalyst (prepared in example 1) is added after stirring, hydrogen is used for replacing air, 10bar of hydrogen is introduced for stirring reaction (the conditions are shown in table 1), ethylbenzene is added as an internal standard after the reaction is finished, 20mL of acetonitrile is added for diluting the reaction solution, and the reaction conversion rate and the yield are measured by gas chromatography by sampling. The results are shown in Table 1.
Preparation of primary amine by catalytic hydrogenation of nitriles in tables 1 NiZnAlOx-600
Therefore, the multi-metal oxide supported nickel catalyst NiZnAlOx prepared by the method can efficiently and selectively catalyze the hydrogenation of nitrile compounds to prepare primary amine under relatively mild conditions, and the reactivity and the selectivity of the catalyst are high.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (17)

1. A method for preparing a multi-metal oxide supported nickel catalyst is characterized in that a hydrothermal method is utilized to prepare NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH, and then calcination and reduction treatment are carried out to prepare the multi-metal oxide supported nickel catalyst Ni 0.5/Zn1.5Al1 Ox; the method comprises the following specific steps:
1) Preparation of NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH:
Adding 2.5mmol of Ni (NO 3)2⋅6H2 O, 7.5mmol of Zn (NO 3)2⋅6H2 O, 5mmol of Al (NO 3)3⋅9H2 O, 37.5mmol of urea and 50mL of water into a hydrothermal kettle for hydrothermal reaction, standing and cooling the obtained product after the reaction is finished, centrifuging, washing with water, and drying to obtain NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH;
2) Preparation of Ni 0.5/Zn1.5Al1 Ox catalyst:
Calcining the NiZnAl layered double hydroxide Ni 0.5/Zn1.5Al1 -LDH prepared in the step 1) in air at a certain temperature, and then reducing by nitrogen-hydrogen mixed gas to obtain the Ni 0.5/Zn1.5Al1 Ox catalyst, wherein the catalyst carrier is Zn 1.5Al1 Ox, and x is 2-5.
2. The method according to claim 1, wherein the hydrothermal synthesis reaction temperature in step 1) is 100-300 ℃ and the reaction time is 10-40 hours.
3. The method according to claim 1, wherein in the step 2), the calcination temperature in the air is 500-800 ℃ and the calcination time is 1-20 hours; the reaction temperature of the reduction of the nitrogen-hydrogen mixed gas is 500-800 ℃, the heating rate is 1-5 ℃/min, and the reaction time is 2-5 h.
4. The method according to claim 1, wherein the volume ratio of nitrogen to hydrogen in the nitrogen-hydrogen mixture in step 2) is 9:1.
5. The method for preparing primary amine by catalyzing and hydrogenating nitrile compounds by using the multi-metal oxide supported nickel catalyst prepared by the method as claimed in claim 1 is characterized in that aromatic or aliphatic nitrile compounds and ammonia water are added into n-hexane, after stirring, the multi-metal oxide supported nickel catalyst Ni 0.5/Zn1.5Al1 Ox is added into a reaction kettle, after air is replaced by hydrogen, hydrogen with a certain pressure is introduced, stirring reaction is carried out at a certain temperature, and after the reaction is finished, the catalyst is centrifugally separated, so that the corresponding primary amine product is obtained.
6. The method of claim 5, wherein the molar ratio of ammonia to nitrile is 5-30:1.
7. The method of claim 6, wherein the molar ratio of ammonia to nitrile is 10-20:1.
8. The method of claim 7, wherein the molar ratio of ammonia to nitrile is 13:1.
9. The method of claim 5, wherein 10 to 80 mg of catalyst is added per 1 mmol nitrile compound.
10. The method of claim 9, wherein 30 to 50mg of catalyst is added per 1 mmol nitrile compound.
11. The method of claim 10, wherein 40 mg of catalyst is added per 1 mmol nitrile compound.
12. The method according to claim 5, wherein the pressure of the hydrogen used in the hydrogenation reaction is 1 to 40 bar.
13. The method of claim 12, wherein the hydrogen used in the hydrogenation reaction is at a pressure of 5 to 20 bar.
14. The method of claim 13, wherein the hydrogen used in the hydrogenation reaction is at a pressure of 10 bar.
15. The method of claim 5, wherein the hydrogenation reaction temperature is 30-80 ℃ and the hydrogenation reaction time is 10-48 hours.
16. The method of claim 15, wherein the hydrogenation reaction temperature is 30-60 ℃ and the hydrogenation reaction time is 12-24 hours.
17. The method of claim 16, wherein the hydrogenation reaction temperature is 30 ℃.
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