CN115193436B - Nickel-cobalt metal framework catalyst, preparation method and application thereof - Google Patents
Nickel-cobalt metal framework catalyst, preparation method and application thereof Download PDFInfo
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- CN115193436B CN115193436B CN202211008244.5A CN202211008244A CN115193436B CN 115193436 B CN115193436 B CN 115193436B CN 202211008244 A CN202211008244 A CN 202211008244A CN 115193436 B CN115193436 B CN 115193436B
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- -1 nickel-cobalt-aluminum Chemical compound 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000011949 solid catalyst Substances 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 238000010907 mechanical stirring Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000009423 ventilation Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- KWGZNYCFTYOQHV-UHFFFAOYSA-N 3-pyridin-2-ylpropanenitrile Chemical compound N#CCCC1=CC=CC=N1 KWGZNYCFTYOQHV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- XPQIPUZPSLAZDV-UHFFFAOYSA-N 2-pyridylethylamine Chemical compound NCCC1=CC=CC=N1 XPQIPUZPSLAZDV-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nickel-cobalt metal skeleton catalyst, which consists of 10-90% by mass of nickel and 90-10% by mass of cobalt. The invention also discloses a preparation method of the nickel-cobalt metal skeleton catalyst, which comprises the steps of S1, adding 50-80 mesh nickel-cobalt-aluminum alloy powder into a container, adding deionized water, uniformly stirring, and adding sodium hydroxide aqueous solution for stirring; s2, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol, and storing in the absolute ethyl alcohol; s3, putting the nickel-cobalt metal framework solid catalyst into nitrogen or a reduction atmosphere for post-treatment. The prepared nickel-cobalt metal skeleton catalyst is applied to the preparation of organic amine from nitrile compounds. The nickel-cobalt metal skeleton catalyst can solve the problems of low yield and harsh process conditions of preparing organic amine from nitrile compounds; the preparation method of the nickel-cobalt metal framework catalyst is simple and easy to realize.
Description
Technical Field
The invention relates to the technical field of nickel cobalt catalysts, in particular to a nickel cobalt metal framework catalyst, a preparation method and application thereof.
Background
The preparation of organic amine by reduction of nitrile compounds is an important means for preparing organic amine industrially, hydrogenation reduction is a clean and efficient reduction means, and conventional hydrogenation catalysts comprise palladium, platinum, rhodium, iridium, nickel, cobalt and the like, wherein noble metals such as palladium, platinum, rhodium, iridium and the like are supported on inert carriers and are used in the form of supported catalysts; cobalt, nickel and other porous metals (such as Raney nickel and Raney cobalt) or mixed with alumina, molecular sieve and other inorganic materials. Raney nickel, which is a mature catalyst in the process, plays an important role in the reduction of nitrile compounds, and can reduce nitrile groups to the corresponding primary amines at lower temperatures and hydrogen pressures. However, since enamine is subjected to the reduction process, secondary and tertiary amine byproducts are inevitably produced in the reduction process. The Raney cobalt is used for catalyzing the reduction hydrogenation of the nitrile compound, so that the generation of byproducts such as primary amine, tertiary amine and the like can be effectively reduced, and better selectivity is shown. However, since Raney cobalt is relatively less active than Raney nickel, higher pressures are required in the catalytic hydrogenation of certain aliphatic nitriles.
Disclosure of Invention
The invention aims to provide a nickel-cobalt metal skeleton catalyst, which solves the problems of low yield and harsh process conditions of preparing organic amine from nitrile compounds. The invention also aims to provide a preparation method and application of the nickel-cobalt metal framework catalyst.
In order to achieve the aim, the invention provides a nickel-cobalt metal skeleton catalyst which consists of 10-90% by mass of nickel and 90-10% by mass of cobalt.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 50-80 mesh nickel-cobalt-aluminum alloy powder into a container, adding deionized water, uniformly stirring, adding sodium hydroxide aqueous solution, and stirring to react completely;
s2, filtering the reacted solution, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol, and storing in the absolute ethyl alcohol; the nickel-cobalt metal framework catalyst is easy to spontaneously ignite in the air, so that the nickel-cobalt metal framework catalyst is put into alcohol for preservation;
s3, putting the nickel-cobalt metal framework solid catalyst into nitrogen or a reduction atmosphere for post-treatment.
Preferably, in S1, the weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%.
Preferably, in the step S1, the mass fraction of the sodium hydroxide aqueous solution is 30% -70%, and the mass ratio of the sodium hydroxide aqueous solution to the nickel-cobalt-aluminum alloy powder is 6-10:1.
preferably, in the step S1, the reaction temperature is 0-80 ℃ and the reaction time is 4-8 hours.
Preferably, in the step S3, the post-treatment is to put the nickel-cobalt metal framework solid catalyst into nitrogen protection for sealing and preserving.
Preferably, in the step S3, the post-treatment is to put the nickel-cobalt metal framework solid catalyst into a hydrogen atmosphere with the pressure of 1-4 atmospheres for activation, and the activation temperature is 20-80 ℃.
The nickel-cobalt metal skeleton catalyst is used in preparing organic amine with nitrile compound.
The nickel-cobalt metal framework catalyst, the preparation method and the application thereof have the advantages that:
1. the invention provides a nickel-cobalt metal skeleton catalyst for preparing organic amine from nitrile compounds, which can improve the conversion rate of the organic amine and reduce the generation of byproducts.
2. The nickel-cobalt metal skeleton catalyst is prepared by taking the nickel-cobalt-aluminum alloy as the initial raw material and then dissolving aluminum in the alloy by using a sodium hydroxide solution, and has simple preparation method and easy realization.
Detailed Description
The technical scheme of the invention is further described below by examples.
Example 1
A nickel-cobalt metal skeleton catalyst consists of 50% nickel by mass and 50% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter autoclave again, adding 2 liters of absolute ethyl alcohol, replacing air in the autoclave with nitrogen, replacing nitrogen with hydrogen for three times, filling 1 atmosphere hydrogen, preserving the temperature at 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealing and preserving after hydrogenation is finished.
Example 2
A nickel-cobalt metal skeleton catalyst consists of 50% nickel by mass and 50% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter autoclave again, adding 2 liters of absolute ethyl alcohol, replacing air in the autoclave with nitrogen, replacing nitrogen with hydrogen for three times, filling 2 atmospheric pressure hydrogen, preserving the temperature at 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealing and preserving after hydrogenation is finished.
Example 3
A nickel-cobalt metal skeleton catalyst consists of 50% nickel by mass and 50% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter autoclave again, adding 2 liters of absolute ethyl alcohol, replacing air in the autoclave with nitrogen, replacing nitrogen with hydrogen for three times, filling 3 atmospheric pressure hydrogen, preserving the temperature at 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealing and preserving after hydrogenation is finished.
Example 4
A nickel-cobalt metal skeleton catalyst consists of 50% nickel by mass and 50% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter autoclave again, adding 2 liters of absolute ethyl alcohol, replacing air in the autoclave with nitrogen, replacing nitrogen with hydrogen for three times, filling 4 atmospheric pressure hydrogen, preserving the temperature at 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealing and preserving after hydrogenation is finished.
Example 5
A nickel-cobalt metal skeleton catalyst consists of 50% nickel by mass and 50% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered solid nickel-cobalt metal skeleton catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, sealing and storing the nickel-cobalt metal framework solid catalyst under the protection of nitrogen at 1 atmosphere.
Example 6
A nickel-cobalt metal skeleton catalyst consists of 11% nickel by mass and 89% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered solid nickel-cobalt metal skeleton catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, sealing and storing the nickel-cobalt metal framework solid catalyst under the protection of nitrogen at 1 atmosphere.
Example 7
A nickel-cobalt metal skeleton catalyst consists of 89% nickel by mass and 11% cobalt by mass.
The preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10-liter three-neck round bottom flask in a well-ventilated ventilation device, adding a mechanical stirring device, a reflux condenser pipe and a constant pressure dropping funnel, adding 500 ml of deionized water under mechanical stirring, uniformly stirring, adding 4 kg of 50% sodium hydroxide aqueous solution by mass fraction through the dropping funnel after the powder is completely wetted, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuously stirring for 6 hours until no bubbles are generated after the sodium hydroxide aqueous solution is completely dropped.
The weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%, and the yield of the nickel-cobalt metal framework catalyst is 50%.
S2, filtering the reacted solution, washing the filtered solid nickel-cobalt metal skeleton catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol for 5 times, and storing in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
S3, sealing and storing the nickel-cobalt metal framework solid catalyst under the protection of nitrogen at 1 atmosphere.
Catalytic test of nickel cobalt metal framework catalyst
0.5 g of the nickel cobalt metal skeleton catalyst prepared in the above examples 1 to 5, 50 g of 2- (cyanoethyl) pyridine, and 300 ml of di-polyethylene glycol dimethyl ether as a solvent were added to a 1 liter autoclave at a reaction temperature of 100 to 120℃under a hydrogen pressure of 20 atmospheres and an ammonia pressure of 4 atmospheres for a reaction time of 4 hours.
Comparative example 1
The catalyst was Raney nickel in the same weight and the other catalytic test procedures were the same as in examples 1-5.
Comparative example 2
The catalyst was the same weight of Raney cobalt and the other catalytic test procedures were the same as in examples 1-5.
Comparative example 3
The catalyst is a mixture of Raney nickel and Raney cobalt with the same weight, wherein the weight ratio of Raney nickel is as follows: raney cobalt=1:1, other catalytic test procedures were identical to examples 1-5.
High performance liquid chromatography detection is carried out on the reaction product, the model of a liquid chromatograph is Waters 2695, and the model of a detection Column is Atlantis dC18 Column%3 μm,2.1mm×150 mm), eluting with acetonitrile and deionized water, eluent volume ratio V (acetonitrile): v (water) =2:1.
The conversion of nitrile compound, primary amine product yield, secondary amine by-product ratio, tertiary amine by-product ratio in examples 1 to 7 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 conversion of nitrile compounds, primary amine product yield, secondary amine by-product ratio, tertiary amine by-product ratio in examples 1-7, comparative examples 1-3
As can be seen from the table 1, the nickel-cobalt metal skeleton catalyst shows better balance of reactivity and selectivity in the hydrogenation reduction of 2- (cyanoethyl) pyridine to 2- (aminoethyl) pyridine, and can effectively reduce the generation of secondary amine, tertiary amine and other byproducts while ensuring better primary amine product yield.
Therefore, the nickel-cobalt metal framework catalyst can solve the problems of low yield and harsh process conditions of the preparation of the organic amine from the nitrile compound; the preparation method of the nickel-cobalt metal framework catalyst is simple and easy to realize.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (4)
1. The application of a nickel-cobalt metal framework catalyst in the preparation of organic amine from nitrile compounds is characterized in that: the nickel-cobalt metal skeleton catalyst consists of 50% by mass of nickel and 50% by mass of cobalt;
the preparation method of the nickel-cobalt metal framework catalyst comprises the following steps:
s1, adding 50-80 mesh nickel-cobalt-aluminum alloy powder into a container, adding deionized water, uniformly stirring, adding sodium hydroxide aqueous solution, and stirring to react completely;
s2, filtering the reacted solution, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, washing with absolute ethyl alcohol, and storing in the absolute ethyl alcohol;
s3, putting the nickel-cobalt metal framework solid catalyst into a reduction atmosphere for post-treatment;
in the step S3, the post-treatment is to put the nickel-cobalt metal framework solid catalyst into a hydrogen atmosphere with the pressure of 1-4 atmospheres for activation, and the activation temperature is 20-80 ℃.
2. The use of a nickel cobalt metal framework catalyst according to claim 1 in the preparation of organic amines from nitrile compounds, characterized in that: in the S1, the weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%.
3. The use of a nickel cobalt metal framework catalyst according to claim 1 in the preparation of organic amines from nitrile compounds, characterized in that: in the S1, the mass fraction of the sodium hydroxide aqueous solution is 30% -70%, and the mass ratio of the sodium hydroxide aqueous solution to the nickel-cobalt-aluminum alloy powder is 6-10:1.
4. the use of a nickel cobalt metal framework catalyst according to claim 1 in the preparation of organic amines from nitrile compounds, characterized in that: in the step S1, the reaction temperature is 0-80 ℃ and the reaction time is 4-8 hours.
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