CN115041175A - Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound with 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 with multi-metal oxide supported nickel catalyst Download PDFInfo
- Publication number
- CN115041175A CN115041175A CN202210860171.6A CN202210860171A CN115041175A CN 115041175 A CN115041175 A CN 115041175A CN 202210860171 A CN202210860171 A CN 202210860171A CN 115041175 A CN115041175 A CN 115041175A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal oxide
- reaction
- supported nickel
- oxide supported
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- -1 nitrile compound Chemical class 0.000 title claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 title claims abstract 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910018605 Ni—Zn Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 31
- 150000003141 primary amines Chemical class 0.000 description 19
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 208000012839 conversion disease Diseases 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910001151 AlNi Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A multi-metal oxide supported nickel catalyst, a preparation method and a method for preparing primary amine by using the 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 /Zn 1.5 Al 1 Ox, the catalyst carrier is Zn 1.5 Al 1 Ox. Firstly, preparing NiZnAl layered double hydroxide by a hydrothermal method, and then preparing the multi-metal oxide supported nickel catalyst by calcining and reducing treatment. Ni/Al catalyst supported by traditional single metal oxide 2 O 3 Compared with the prior art, in the nickel catalyst loaded by the multi-metal oxide prepared by the invention, because the Ni-Zn bond exists, the acting force between the metal and the carrier is stronger, so that the catalytic activity and the catalyst stability are obviously enhanced, and the aim of preparing corresponding primary amine by using a non-noble metal catalyst to catalyze and hydrogenate nitrile compounds under a mild condition is fulfilled.
Description
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 using the catalyst to catalyze and hydrogenate nitrile compounds.
Background
Primary amine is an important chemical intermediate, and has wide application in the aspects of dyes, pigments, medicines, pesticides, high molecular polymers and the like. Compared with other methods for synthesizing primary amine, the method for preparing primary amine by catalytic hydrogenation of nitrile compounds is efficient, environment-friendly, simple in treatment and rich in raw material sources, and is a hotspot of current research.
Generally, the catalytic hydrogenation of nitrile compounds can be carried out using homogeneous or heterogeneous catalysts. Heterogeneous catalysts are high in both selectivity and activity, but have the inherent disadvantage of difficulty in catalyst separation and recovery, and are difficult to realize in industrial production [ Gomez, s.; peters, j.a.; maschmeyer, T.Adv.Synth.Catal.2002,344, 1037-1057; blast, h. -u.; malan, C.; pugin, b.; spindler, f.; steiner, h.; studer, m.adv.synth.call.2003, 345, 103-151; werkmeister, s.; junge, k.; beller, M.org.Process Res.Dev.2014,18,289-302 ] thus the current commercial catalysts for the catalytic hydrogenation of nitrile compounds to produce primary amines generally employ heterogeneous catalysts. Among heterogeneous catalysts, noble metal catalysts such as Pd-CuFe, PdCu and NiPd have good catalytic activity, and can obtain corresponding primary amines [ 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.Jiang, Y.Wang, Q.L.Liang and H.B.Sun, iSience, 2018, 61-73 with a yield of more than 90% under mild conditions; 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, chemistry select,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-. Non-noble metal catalysts are also used in large quantities for this reaction and good results are achieved [ Y.M.Zhang, H.M.Yang, Q.Chi and Z.Z.Zhang, Chem-Suschem,2019,12, 1246-; y.y.cao, l.b.niu, x.wen, w.h.feng, l.huo and g.y.bai, j.catal.,2016,339, 9-13; nature Catalysis 2022,5, 20-29 ], however higher temperatures and pressures (80-120 ℃, 30-50bar) are often required for the reaction due to the lower activity of the non-noble metal catalyst.
Ni-based catalysts are used in various hydrogenation reactions due to their high catalytic activity. Zhang Hui et Al designed a kind of Ni base catalyst Ni/Al 2 O 3 600 and their use in the catalytic hydrogenation of lignin and nitrile compounds [ New J. chem.,2020,44, 549-555-]The catalyst has high activity, but the nitrile compound can be efficiently catalyzed and hydrogenated at a high temperature (60-80 ℃), so that the development of a non-noble metal catalyst capable of efficiently catalyzing and hydrogenating the nitrile compound to prepare primary amine under mild conditions is still needed.
Disclosure of Invention
The invention aims to provide a multi-metal oxide supported nickel catalyst, a preparation method and application thereofThe method for preparing primary amine by using the nitrile compound as catalyst, and the traditional nickel catalyst Ni/Al loaded by single metal oxide 2 O 3 Compared with the prior art, the nickel catalyst loaded with the multi-metal oxide has stronger acting force between metal and a carrier due to the existence of Ni-Zn bonds, so that the catalytic activity and the catalyst stability are obviously enhanced.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a multi-metal oxide supported nickel catalyst is composed of Ni 0.5 /Zn 1.5 Al 1 Ox, the catalyst carrier is Zn 1.5 Al 1 Ox. x is the number of O in the carrier molecule, and generally, x is 2-5.
A process for preparing the multi-metal oxide carried Ni catalyst includes such steps as hydrothermal preparing NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 LDH, preparation of multi-metal oxide supported nickel catalyst Ni by calcination and reduction treatment 0.5 /Zn 1.5 Al 1 Ox; the method comprises the following specific steps:
1) NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 Preparation of LDH:
2.5mmol of Ni (NO) 3 ) 2 ·6H 2 O, 7.5mmol of Zn (NO) 3 ) 2 ·6H 2 O, 5mmol of Al (NO) 3 ) 3 ·9H 2 Adding O, 37.5mmol urea and 50mL 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 the NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 -LDH；
2)、Ni 0.5 /Zn 1.5 Al 1 Preparation of the Ox catalyst:
the NiZnAl layered double hydroxide Ni prepared in the step 1) is added 0.5 /Zn 1.5 Al 1 calcining-LDH in air at a certain temperature, and then reducing by using mixed gas of nitrogen and hydrogen to obtain Ni 0.5 /Zn 1.5 Al 1 And an Ox catalyst.
As a preferred technical scheme, 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. In the step 2), the calcination temperature in the air 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 nitrogen-hydrogen mixed gas reduction is 500-800 ℃, the heating rate is 1-5 ℃/min, and the reaction time is 2-5 h.
The invention also provides a method for preparing primary amine by using the multi-metal oxide supported nickel catalyst to catalyze and hydrogenate nitrile compounds, and specifically, the aromatic or aliphatic nitrile compounds and ammonia water are added into n-hexane, and after stirring, the multi-metal oxide supported nickel catalyst Ni is added into n-hexane 0.5 /Zn 1.5 Al 1 Adding Ox into a reaction kettle, replacing air with hydrogen, introducing hydrogen with a certain pressure, stirring and reacting at a certain temperature, and centrifugally separating the catalyst after the reaction is finished to obtain a corresponding primary amine product.
According to the preferable technical scheme of the invention, in the primary amine preparation method, the molar ratio of ammonia water to nitrile compounds is 5-30: 1, preferably 10-20: 1, and more preferably 13: 1. 10-80 mg of catalyst is added to 1mmol of nitrile compound, preferably 30-50 mg of catalyst, and more preferably 40mg of catalyst. The pressure of the hydrogen used in the hydrogenation reaction is 1 to 40bar, preferably 5 to 20bar, and more preferably 10 bar. The hydrogenation reaction temperature is 30-80 ℃, preferably 30-60 ℃, and more preferably 30 ℃; the hydrogenation reaction time is 10-48 h, preferably 12-24 h.
Although conventional single metal oxide supported Ni based catalysts such as Ni/Al 2 O 3 The catalyst has high catalytic activity, but the acting force between the metal and the carrier is not strong enough, so the activity and the stability of the catalyst are required to be improved. The invention is based on the conventional Ni/Al 2 O 3 Zn element is introduced on the basis of the Ni 0.5 /Zn 1.5 Al 1 Ox catalyst, Ni/Al catalyst supported on conventional single metal oxide 2 O 3 In contrast, in the multi-metal oxide supported nickel catalyst prepared by the invention, due to the existence of Ni-Zn bond, the action between metal and carrierThe strength is stronger, the catalytic activity and the catalyst stability are obviously enhanced, and the catalyst is prepared under mild conditions (30-80 ℃,10 bar H) 2 ) The method can selectively hydrogenate nitrile compounds to prepare corresponding primary amine, and the yield of most of the primary amine reaches over 90 percent, thereby realizing the purpose of preparing the corresponding primary amine by using a non-noble metal catalyst to catalyze and hydrogenate the nitrile compounds under mild conditions.
Compared with the prior method for preparing primary amine by taking nitrile compounds as raw materials, the method has more advantages because the carrier capable of stabilizing metal and improving catalytic activity is used, and is particularly shown in the following steps:
1) the catalyst has high reaction activity and selectivity, and taking cyanobenzene as an example, the conversion rate of the raw material can reach 99.6%, and the yield of the benzylamine can reach 93.8%.
2) The catalytic reaction conditions are 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 used metal is Ni, and the price is relatively lower than that of a noble metal catalyst.
4) The catalyst used in the invention is a Ni catalyst loaded by multiple metals, and the catalyst has a stable structure and can be recycled, so that the production cost can be reduced.
Drawings
FIG. 1 shows Ni prepared according to an example of the present invention 0.5 /Zn 1.5 Al 1 XRD pattern of Ox catalyst, carried out on a Bruker advanced D8 powder diffractometer, in the 2 theta range 10-80 deg. with a scan rate of 0.016 deg./s.
Wherein NiZnAlOx-500 means that the catalyst is formed by mixing nitrogen and hydrogen (N) at 500 DEG C 2 ∶H 2 V/v) and the synthetic methods of NiZnAlOx-600 and NiZnAlOx-650 are substantially the same as NiZnAlOx-500 except that the reduction temperatures are 600 ℃ and 650 ℃, respectively. NiZnAlOx-air means that the catalyst has not been reduced.
As can be seen from FIG. 1, except for NiZnAlOx-air, Ni-Zn and AlNi appeared on XRD patterns of NiZnAlOx-500, NiZnAlOx-600 and NiZnAlOx-650 which had undergone hydrogen reduction 3 The characteristic peaks indicate that the Ni-Zn alloy is actually present in the catalyst.
FIG. 2 shows Ni prepared according to an example of the present invention 0.5 /Zn 1.5 Al 1 Programmed temperature reduction image (H) of Ox catalyst 2 -TPR map).
From the figure, it can be seen that the reduced catalysts NiZnAlOx-500, NiZnAlOx-600 and NiZnAlOx-650 have higher reduction temperature than the unreduced catalyst NiZnAlOx-air, which indicates that the reduced catalyst has higher stability, and meanwhile, in combination with the XRD pattern (figure 1) of the catalyst, the reduced catalyst contains Ni-Zn alloy, which indicates that the Ni-Zn bond formed by the catalyst can actually improve the stability of the catalyst. Wherein the reduction temperature of the NiZnAlOx-600 is up to 680 ℃, which is higher than that of both NiZnAlOx-500 and NiZnAlOx-650.
FIG. 3 is a reaction mechanism route for preparing benzylamine by catalytic hydrogenation of benzonitrile using a NiZnAlOx catalyst. As can be seen from the figure, since a side reaction occurs in the catalytic reaction and a secondary amine or other by-product is produced, it is important to develop a catalyst having high selectivity for the reaction. Meanwhile, the addition of a certain amount of ammonia water can also contribute to improving the selectivity of preparing the benzylamine by catalytically hydrogenating the benzonitrile.
Detailed Description
The preparation method and the catalytic hydrogenation process of the present invention are described in detail by the following specific examples. The nitrile compounds used in the examples were purchased from the national pharmaceutical group chemical agents Co., Ltd or from the Bailingwei chemical technology Co., Ltd, and the purity was analytical. The conversion of nitrile compounds and the yield of primary amines were analyzed by gas chromatography. The gas phase was carried out on an Agilent 7890A gas chromatograph, and the sample was separated on a cross-linked capillary HP-5 column (30 m.times.0.32 mm. times.0.4 mm) and detected with a hydrogen flame ionization detector. The analysis conditions were that the carrier gas was nitrogen and the flow rate was 40mL min -1 The injection inlet temperature is 300 ℃, the column temperature program is heated to 280 ℃ and kept for 0.5h, the detector temperature is 300 ℃, and the conversion rate and the yield are determined by taking ethylbenzene as an internal standard.
Taking benzonitrile as an example, the conversion rate calculation formula is as follows:
the conversion of benzonitrile ═ 100% (1-amount of material of benzonitrile after reaction/amount of initial material of benzonitrile).
The calculation formula of the yield of the benzylamine is as follows:
the yield of benzylamine (amount of benzylamine substance generated after the reaction/amount of initial benzonitrile substance) × 100%.
Example 1
1) NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 Preparation of LDH:
2.5mmol of Ni (NO) 3 ) 2 ·6H 2 O, 7.5mmol of Zn (NO) 3 ) 2 ·6H 2 O, 5mmol of Al (NO) 3 ) 3 ·9H 2 Adding O, 37.5mmol urea and 50mL water into a hydrothermal kettle, reacting for 24h at 100 ℃, standing and cooling the obtained product after the reaction is finished, centrifuging, washing with water, and drying to obtain the NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 -LDH。
2)、Ni 0.5 /Zn 1.5 Al 1 Preparation of the Ox catalyst:
the NiZnAl layered double hydroxide Ni prepared in the step 1) is added 0.5 /Zn 1.5 Al 1 Calcination of-LDH in air at 600 ℃ for 2h, followed by a nitrogen-hydrogen mixture (N) 2 ∶H 2 Reducing at a speed of 3 ℃/min (9: 1, v/v), heating to 600 ℃, and keeping for 2h to obtain Ni 0.5 /Zn 1.5 Al 1 And the catalyst of Ox is marked as NiZnAlOx-600 catalyst.
3) And preparing the benzylamine by catalytic hydrogenation:
adding 0.5mmol of benzonitrile, 200uL of concentrated ammonia water and 10mL of n-hexane into a reaction kettle, stirring, adding 20mg of NiZnAlOx-600 catalyst, replacing air with hydrogen, introducing 10bar of hydrogen, stirring at 30 ℃ for reaction for 12h, adding ethylbenzene as an internal standard after the reaction is finished, adding 20mL of acetonitrile to dilute the reaction solution, sampling, and determining the reaction conversion rate to be 99.6% and the yield to be 93.8% by gas chromatography.
Example 2
1) NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 Preparation of LDH:
2.5mmol of Ni (NO) 3 ) 2 ·6H 2 O, 7.5mmol of Zn (NO) 3 ) 2 ·6H 2 O, 5mmol of Al (NO) 3 ) 3 ·9H 2 Adding O, 37.5mmol urea and 50mL water into a hydrothermal kettle, reacting for 24h at 100 ℃, standing and cooling the obtained product after the reaction is finished, centrifuging, washing with water, and drying to obtain the NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 -LDH。
2)、Ni 0.5 /Zn 1.5 Al 1 Preparation of the Ox catalyst:
the NiZnAl layered double hydroxide Ni prepared in the step 1) 0.5 /Zn 1.5 Al 1 Calcination of-LDH in air at 600 ℃ for 2h, followed by a nitrogen-hydrogen mixture (N) 2 ∶H 2 Reducing at a speed of 3 ℃/min (9: 1, v/v), heating to 500 ℃, and keeping for 2h to obtain Ni 0.5 /Zn 1.5 Al 1 And the catalyst of Ox is marked as NiZnAlOx-500 catalyst.
3) And preparing the benzylamine by catalytic hydrogenation:
adding 0.5mmol of benzonitrile, 200uL of concentrated ammonia water and 10mL of n-hexane into a reaction kettle, stirring, adding 20mg of NiZnAlOx-500 catalyst, replacing air with hydrogen, introducing 10bar of hydrogen, stirring at 30 ℃ for reaction for 4 hours, adding ethylbenzene as an internal standard after the reaction is finished, adding 20mL of acetonitrile to dilute the reaction solution, sampling, and determining the reaction conversion rate to be 51.1% and the yield to be 48.6% by gas chromatography.
Example 3
1) NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 Preparation of LDH:
2.5mmol of Ni (NO) 3 ) 2 ·6H 2 O, 7.5mmol of Zn (NO) 3 ) 2 ·6H 2 O, 5mmol of Al (NO) 3 ) 3 ·9H 2 Adding O, 37.5mmol urea and 50mL water into a hydrothermal kettle, reacting for 24h at 100 ℃, standing and cooling the obtained product after the reaction is finished, centrifuging, washing with water, and drying to obtain the NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 -LDH。
2)、Ni 0.5 /Zn 1.5 Al 1 Preparation of the Ox catalyst:
the NiZnAl layered double hydroxide Ni prepared in the step 1) is added 0.5 /Zn 1.5 Al 1 Calcination of-LDH in air at 600 ℃ for 2h, followed by a nitrogen-hydrogen mixture (N) 2 ∶H 2 Reducing at a speed of 3 ℃/min at the time of reduction, heating to 650 ℃, and keeping for 2h to obtain Ni 0.5 /Zn 1.5 Al 1 And the catalyst of Ox is marked as NiZnAlOx-650 catalyst.
3) And preparing the benzylamine by catalytic hydrogenation:
adding 0.5mmol of benzonitrile, 200uL of concentrated ammonia water and 10mL of n-hexane into a reaction kettle, stirring, adding 20mg of NiZnAlOx-650 catalyst, replacing air with hydrogen, introducing 10bar of hydrogen, stirring at 30 ℃ for reaction for 12h, adding ethylbenzene as an internal standard after the reaction is finished, adding 20mL of acetonitrile to dilute the reaction solution, sampling, determining the reaction conversion rate to be 98.3% by gas chromatography, and obtaining the yield to be 92.1%.
Example 4
Other amine materials preparation examples:
adding concentrated ammonia water (the addition amounts are shown in table 1), 0.5mmol of substrate and 10mL of n-hexane into a reaction kettle, stirring, adding 20mg of NiZnAlOx-600 catalyst (prepared in example 1), replacing air with hydrogen, introducing 10bar of hydrogen, stirring for reaction (the conditions are shown in table 1), adding ethylbenzene as an internal standard after the reaction is finished, adding 20mL of acetonitrile to dilute the reaction solution, sampling, and measuring the reaction conversion rate and the yield through gas chromatography. The results are shown in Table 1.
TABLE 1 preparation of primary amines by catalytic hydrogenation of nitrile compounds with NiZnAlOx-600
Therefore, the prepared multi-metal oxide supported nickel catalyst NiZnAlOx can efficiently and selectively catalyze and hydrogenate nitrile compounds to prepare primary amine under relatively mild conditions, and the catalyst has high reaction activity and selectivity.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. A multi-metal oxide supported nickel catalyst is composed of Ni 0.5 /Zn 1.5 Al 1 Ox, the catalyst carrier is Zn 1.5 Al 1 Ox, wherein x is 2-5.
2. A process for preparing a nickel-on-multimetal oxide catalyst as claimed in claim 1, characterized in that the NiZnAl layered double hydroxide Ni is first prepared by hydrothermal method 0.5 /Zn 1.5 Al 1 LDH, preparation of multi-metal oxide supported nickel catalyst Ni by calcination and reduction treatment 0.5 /Zn 1.5 Al 1 Ox; the method comprises the following specific steps:
1) NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 Preparation of LDH:
2.5mmol of Ni (NO) 3 ) 2 ·6H 2 O, 7.5mmol of Zn (NO) 3 ) 2 ·6H 2 O, 5mmol of Al (NO) 3 ) 3 ·9H 2 Adding O, 37.5mmol urea and 50mL 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 the NiZnAl layered double hydroxide Ni 0.5 /Zn 1.5 Al 1 -LDH；
2)、Ni 0.5 /Zn 1.5 Al 1 Preparation of the Ox catalyst:
the NiZnAl layer prepared in the step 1) is addedBihydrido oxide Ni 0.5 /Zn 1.5 Al 1 calcining-LDH in air at a certain temperature, and then reducing by using mixed gas of nitrogen and hydrogen to obtain Ni 0.5 /Zn 1.5 Al 1 And an Ox catalyst.
3. The method of claim 2, wherein the hydrothermal synthesis reaction temperature in step 1) is 100 to 300 ℃ and the reaction time is 10 to 40 hours.
4. The method of claim 2, wherein the calcination temperature in air in step 2) is 500 to 800 ℃, and the calcination time is 1 to 20 hours; the reaction temperature of the nitrogen-hydrogen mixed gas reduction is 500-800 ℃, the heating rate is 1-5 ℃/min, and the reaction time is 2-5 h.
5. The method according to claim 2, wherein the volume ratio of the nitrogen to the hydrogen in the nitrogen-hydrogen mixed gas in the step 2) is 9: 1.
6. The method for producing a primary amine by catalytic hydrogenation of a nitrile compound using the multimetal oxide supported nickel catalyst according to claim 1, wherein the nitrile compound of aromatic or aliphatic series and ammonia water are added to n-hexane, and after stirring, the multimetal oxide supported nickel catalyst Ni is added 0.5 /Zn 1.5 Al 1 Adding Ox into a reaction kettle, replacing air with hydrogen, introducing hydrogen with a certain pressure, stirring and reacting at a certain temperature, and centrifugally separating the catalyst after the reaction is finished to obtain a corresponding primary amine product.
7. The method according to claim 6, wherein the molar ratio of ammonia to nitrile compound is 5-30: 1, preferably 10-20: 1, more preferably 13: 1.
8. The method according to claim 6, wherein 10 to 80mg of catalyst, preferably 30 to 50mg of catalyst, more preferably 40mg of catalyst is added per 1mmol of nitrile compound.
9. The process according to claim 6, wherein the hydrogen used for the hydrogenation is at a pressure of 1 to 40bar, preferably 5 to 20bar, more preferably 10 bar.
10. The process according to claim 6, wherein the hydrogenation reaction temperature is 30 to 80 ℃, preferably 30 to 60 ℃, more preferably 30 ℃; the hydrogenation reaction time is 10-48 h, preferably 12-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210860171.6A CN115041175B (en) | 2022-07-21 | 2022-07-21 | 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210860171.6A CN115041175B (en) | 2022-07-21 | 2022-07-21 | 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115041175A true CN115041175A (en) | 2022-09-13 |
| CN115041175B CN115041175B (en) | 2024-05-10 |
Family
ID=83167750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210860171.6A Active CN115041175B (en) | 2022-07-21 | 2022-07-21 | 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115041175B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277072A (en) * | 2016-08-24 | 2017-01-04 | 合肥学院 | A kind of graphene/nickel cobalt aluminum layered double-hydroxide composite and preparation method thereof |
| CN111072490A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine from hexamethylene dialdehyde based on Ni-based catalyst |
| CN113304750A (en) * | 2021-05-28 | 2021-08-27 | 宁夏大学 | Preparation method and application of petal-shaped catalyst |
-
2022
- 2022-07-21 CN CN202210860171.6A patent/CN115041175B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277072A (en) * | 2016-08-24 | 2017-01-04 | 合肥学院 | A kind of graphene/nickel cobalt aluminum layered double-hydroxide composite and preparation method thereof |
| CN111072490A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine from hexamethylene dialdehyde based on Ni-based catalyst |
| CN113304750A (en) * | 2021-05-28 | 2021-08-27 | 宁夏大学 | Preparation method and application of petal-shaped catalyst |
Non-Patent Citations (1)
| Title |
|---|
| DONG, LS 等: "Promoting hydrogen production and minimizing catalyst deactivation from the pyrolysis-catalytic steam reforming of biomass on nanosized NiZnAlOx catalysts", FUEL, pages 610 - 620 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115041175B (en) | 2024-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kita et al. | Effects of ruthenium hydride species on primary amine synthesis by direct amination of alcohols over a heterogeneous Ru catalyst | |
| CN102633649A (en) | Method for synthesizing cyclohexylamine with aniline by means of gas-phase catalytic hydrogenation | |
| CN110449189B (en) | Catalyst for synthesizing dimethyl carbonate and preparation method thereof | |
| CN102105435B (en) | 5-isopropyl-3-aminomethyl-2-methyl-1-amino-cyclohexane (carvone diamine), and method for the production thereof | |
| KR100502606B1 (en) | Catalysts Suitable for Preparing Aliphatic Alpha-, Omega-aminonitriles by Partial Hydrogenation of Aliphatic Dinitriles | |
| Tumma et al. | A facile method for the N-formylation of primary and secondary amines by liquid phase oxidation of methanol in the presence of hydrogen peroxide over basic copper hydroxyl salts | |
| CN105771964A (en) | Catalyst used in ammoxidation of methanol for preparation of hydrocyanic acid, and application thereof | |
| CN115028537A (en) | Preparation method of aminopropyl alicyclic secondary amine | |
| CN1587244A (en) | Process for producing isononyl aldehyde from mixed octene and synthetic gas | |
| Adhikary et al. | Heterogenization of three homogeneous catalysts: a comparative study as epoxidation catalyst | |
| CN106732725B (en) | The preparation and its application of the carbon-based transition-metal catalyst of MgO-Supported N doping | |
| CN115041175A (en) | Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound with multi-metal oxide supported nickel catalyst | |
| CA2385597A1 (en) | Method for activating passivated iron | |
| US11760718B2 (en) | Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol | |
| CN114797983B (en) | Nickel catalyst, preparation method and application | |
| CN113214146B (en) | Process for the N-alkylation of aminopyridines | |
| CN107628957A (en) | A kind of new method research of the direct ammonification synthesizing cyclohexane 1 amine of cyclohexene | |
| CN114426503A (en) | Process for the preparation of dinitrile compounds | |
| CN106391123A (en) | A catalyst used for cyclohexane catalytic oxidation and a using method thereof | |
| CN112961130B (en) | Two-dimensional MoS 2 Application of catalyst in preparation of succinic anhydride by catalyzing selective hydrogenation of maleic anhydride | |
| CN115672376B (en) | High-carbon olefin hydroformylation carbon-loaded single-atom cobalt catalyst and preparation and application methods thereof | |
| CN113289662B (en) | Catalyst for preparing cyclohexylamine by aniline hydrogenation, preparation method and application | |
| CN116535322B (en) | Preparation method of tricyclodecane dimethylamine | |
| CN117143009B (en) | Synthesis method of N, N' -bis- (2, 6-tetramethyl-4-piperidinyl) 1, 6-hexamethylenediamine | |
| CN110294690A (en) | To methylbenzyl alcohol through ammoxidation preparation to the method for methyl cyanophenyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |