CN115193436A - 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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- CN115193436A CN115193436A CN202211008244.5A CN202211008244A CN115193436A CN 115193436 A CN115193436 A CN 115193436A CN 202211008244 A CN202211008244 A CN 202211008244A CN 115193436 A CN115193436 A CN 115193436A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 83
- 239000002184 metal Substances 0.000 title claims abstract description 83
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 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 35
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000011949 solid catalyst Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 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 10
- 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
- 230000008569 process Effects 0.000 abstract description 13
- 238000010907 mechanical stirring Methods 0.000 description 14
- 238000009423 ventilation Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 238000010992 reflux 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
- 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
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 150000003335 secondary amines Chemical class 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
- 230000000694 effects Effects 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
- 239000000203 mixture Substances 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
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XPQIPUZPSLAZDV-UHFFFAOYSA-N 2-pyridylethylamine Chemical compound NCCC1=CC=CC=N1 XPQIPUZPSLAZDV-UHFFFAOYSA-N 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
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000008092 positive effect Effects 0.000 description 1
- 238000004321 preservation Methods 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
- 239000007858 starting material 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nickel-cobalt metal framework catalyst, which consists of 10-90% of nickel and 90-10% of cobalt by mass percent. The invention also discloses a preparation method of the nickel-cobalt metal framework catalyst, which comprises the following steps of S1, adding 50-80 mesh nickel-cobalt aluminum alloy powder into a container, then adding deionized water, stirring uniformly, adding a sodium hydroxide aqueous solution, and stirring; s2, washing the filtered nickel-cobalt metal framework solid catalyst with deionized water until the pH value is 7, then washing with absolute ethyl alcohol, and storing in the absolute ethyl alcohol; and S3, putting the nickel-cobalt metal framework solid catalyst into nitrogen or a reduction atmosphere for post-treatment. The prepared nickel-cobalt metal framework catalyst is applied to the preparation of organic amine from nitrile compounds. The nickel-cobalt metal framework catalyst can solve the problems of low yield and harsh process conditions of organic amine preparation by 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 organic amine is prepared by reducing a nitrile compound, which is an important means for industrially preparing the organic amine, the hydrogenation reduction is a clean and efficient reduction means, and conventional hydrogenation catalysts comprise palladium, platinum, rhodium, iridium, nickel, cobalt and the like, wherein the palladium, platinum, rhodium, iridium and other noble metals are mostly loaded on an inert carrier and used in the form of a loaded catalyst; cobalt and nickel are often used as porous metals (such as raney nickel and raney cobalt), or as a mixture with alumina and inorganic materials such as molecular sieves. Raney nickel, as a catalyst mature in a kind of process, plays an important role in the reduction of nitrile compounds, and can reduce nitrile groups into corresponding primary amines at a lower temperature and a lower hydrogen pressure. However, since enamine is involved in the reduction process, secondary and tertiary amines are inevitably produced as by-products in the reduction process. The Raney cobalt is used for catalyzing the reduction hydrogenation of nitrile compounds, so that the generation of byproducts such as primary amine, tertiary amine and the like can be effectively reduced, and good selectivity is shown. However, because of the low activity of Raney cobalt relative to Raney nickel, higher pressures are required for the catalytic hydrogenation of certain aliphatic nitriles.
Disclosure of Invention
The invention aims to provide a nickel-cobalt metal framework catalyst, which solves the problems of low yield and harsh process conditions of organic amine preparation by 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 purpose, the invention provides a nickel-cobalt metal framework catalyst which is composed of 10-90% of nickel and 90-10% of cobalt by mass percent.
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, then adding deionized water, uniformly stirring, then adding a sodium hydroxide aqueous solution, and completely reacting;
s2, filtering the reacted solution, washing the 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 combust in the air, so the nickel-cobalt metal framework catalyst is placed in alcohol for storage;
and 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 S1, the mass fraction of the sodium hydroxide aqueous solution is 30% to 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 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 a nitrogen gas for protection and sealed storage.
Preferably, in the step S3, the post-treatment is to place the nickel-cobalt metal skeleton solid catalyst into a hydrogen atmosphere with 1 to 4 atmospheres of pressure for activation, and the activation temperature is 20 ℃ to 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 have the advantages and positive effects 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 organic amine and reduce the generation of byproducts.
2. The nickel-cobalt-metal framework catalyst is prepared by taking nickel-cobalt-aluminum alloy as a starting material and then dissolving aluminum in the alloy by using a sodium hydroxide solution, and the preparation method is simple and easy to implement.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
A nickel-cobalt metal skeleton catalyst comprises 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 500 g of 50-80-mesh nickel-cobalt-aluminum alloy powder into a 10L three-neck round-bottom flask in a ventilation device with good ventilation, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50% sodium hydroxide aqueous solution through a separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the sodium hydroxide aqueous solution is dropped until no bubbles are generated.
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 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.
And S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter high-pressure kettle again, adding 2 liters of absolute ethyl alcohol, replacing air in the high-pressure kettle with nitrogen, replacing the nitrogen with hydrogen for three times, filling 1 atmosphere of hydrogen, preserving the heat at the temperature of 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealed storage after hydrogenation is finished.
Example 2
A nickel-cobalt metal skeleton catalyst comprises 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 500 g of 50-80 mesh nickel-cobalt-aluminum alloy powder into a 10L three-neck round-bottom flask in a well-ventilated ventilation device, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50 mass percent sodium hydroxide aqueous solution through the separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the dropping of the sodium hydroxide aqueous solution is finished until no bubbles are generated.
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 solution after reaction, washing the nickel-cobalt metal framework solid catalyst after filtration 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.
And S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter high-pressure kettle again, adding 2 liters of absolute ethyl alcohol, replacing air in the high-pressure kettle with nitrogen, replacing the nitrogen with hydrogen for three times, filling 2 atmospheric pressure hydrogen, preserving the heat at the temperature of 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealed storage after hydrogenation is finished.
Example 3
A nickel-cobalt metal skeleton catalyst comprises 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 500 g of 50-80-mesh nickel-cobalt-aluminum alloy powder into a 10L three-neck round-bottom flask in a ventilation device with good ventilation, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50% sodium hydroxide aqueous solution through a separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the sodium hydroxide aqueous solution is dropped until no bubbles are generated.
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 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.
And S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter high-pressure kettle again, adding 2 liters of absolute ethyl alcohol, replacing air in the high-pressure kettle with nitrogen, replacing the nitrogen with hydrogen for three times, filling 3 atmospheric pressure hydrogen, preserving the heat at the temperature of 20-80 ℃ for 4 hours, and placing the solid catalyst into the absolute ethyl alcohol for sealed storage after hydrogenation is finished.
Example 4
A nickel-cobalt metal skeleton catalyst comprises 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 500 g of 50-80-mesh nickel-cobalt-aluminum alloy powder into a 10L three-neck round-bottom flask in a ventilation device with good ventilation, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50% sodium hydroxide aqueous solution through a separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the sodium hydroxide aqueous solution is dropped until no bubbles are generated.
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 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.
And S3, adding the nickel-cobalt metal framework solid catalyst into a 5-liter high-pressure kettle again, adding 2 liters of absolute ethyl alcohol, replacing air in the high-pressure kettle with nitrogen, replacing the nitrogen with hydrogen for three times, filling 4 atmospheric-pressure hydrogen, preserving heat for 4 hours at the temperature of 20-80 ℃, and after hydrogenation is finished, placing the solid catalyst into the absolute ethyl alcohol for sealed preservation.
Example 5
A nickel-cobalt metal skeleton catalyst comprises 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 500 g of 50-80-mesh nickel-cobalt-aluminum alloy powder into a 10L three-neck round-bottom flask in a ventilation device with good ventilation, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50% sodium hydroxide aqueous solution through a separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the sodium hydroxide aqueous solution is dropped until no bubbles are generated.
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 framework catalyst with deionized water until the pH value is 7, washing the catalyst with absolute ethyl alcohol for 5 times, and storing the catalyst in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
And S3, sealing and storing the nickel-cobalt metal framework solid catalyst under the protection of 1 atmosphere of nitrogen.
Example 6
A nickel-cobalt metal skeleton catalyst comprises 11% by mass of nickel and 89% by mass of cobalt.
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 10L three-neck round-bottom flask in a ventilation device with good ventilation, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50% sodium hydroxide aqueous solution through a separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the sodium hydroxide aqueous solution is dropped until no bubbles are generated.
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 framework catalyst with deionized water until the pH value is 7, washing the catalyst with absolute ethyl alcohol for 5 times, and storing the catalyst in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
And S3, sealing and storing the nickel-cobalt metal framework solid catalyst under the protection of 1 atmosphere of nitrogen.
Example 7
A nickel-cobalt metal skeleton catalyst comprises 89% by mass of nickel and 11% by mass of cobalt.
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 10L three-neck round-bottom flask in a ventilation device with good ventilation, adding mechanical stirring, a reflux condenser tube and a constant-pressure dropping funnel, adding 500 ml of deionized water under the mechanical stirring, uniformly stirring, after the powder is completely wetted, adding 4 kg of 50% sodium hydroxide aqueous solution through a separating funnel, controlling the reaction temperature of the sodium hydroxide aqueous solution to be 0-80 ℃ through interlayer cooling water in the dropping process, and continuing stirring for 6 hours after the sodium hydroxide aqueous solution is dropped until no bubbles are generated.
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 framework catalyst with deionized water until the pH value is 7, washing the catalyst with absolute ethyl alcohol for 5 times, and storing the catalyst in the absolute ethyl alcohol; the obtained nickel-cobalt metal framework solid catalyst is black solid powder.
And S3, sealing and storing the nickel-cobalt metal framework solid catalyst under the protection of nitrogen at 1 atmosphere.
Catalytic testing of nickel cobalt metal skeletal catalysts
0.5 g of the nickel-cobalt metal skeletal catalyst prepared in examples 1 to 5 and 50 g of 2- (cyanoethyl) pyridine were placed in an autoclave having a volume of 1 liter, and 300 ml of diethylene glycol dimethyl ether was added as a solvent, and the reaction temperature was 100 to 120 ℃, the hydrogen pressure was 20 atm, the ammonia pressure was 4 atm, and the reaction time was 4 hours.
Comparative example 1
The catalyst was Raney nickel of the same weight and the other catalytic test procedures were the same as in examples 1-5.
Comparative example 2
The catalyst was Raney cobalt of the same weight 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: raney cobalt =1:1 and the other catalytic test processes were the same as in examples 1-5.
Performing high performance liquid chromatography detection on the reaction product, wherein the liquid chromatograph model is Waters 2695, and the detection Column model is Atlantis dC18 Column (C: (C))
3 μm,2.1mm × 150 mm), eluting with acetonitrile and deionized water at a volume ratio of V (acetonitrile): v (water) =2:1.
The conversion of nitrile compound, the yield of primary amine product, the ratio of secondary amine by-product, and the ratio of tertiary amine by-product in examples 1 to 7 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 conversion of nitrile compound, primary amine product yield, secondary amine by-product ratio, and tertiary amine by-product ratio in examples 1 to 7 and comparative examples 1 to 3
As can be seen from Table 1, the nickel-cobalt metal framework catalyst shows better balance of reaction activity and selectivity in the process of hydrogenating and reducing 2- (cyanoethyl) pyridine into 2- (aminoethyl) pyridine, and effectively reduces the generation of secondary amine, tertiary amine and other byproducts while ensuring better yield of primary amine products.
Therefore, the nickel-cobalt metal framework catalyst can solve the problems of low yield and harsh process conditions of organic amine preparation by nitrile compounds; 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 solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (8)
1. A nickel-cobalt metal skeletal catalyst, characterized in that: consists of 10 to 90 mass percent of nickel and 90 to 10 mass percent of cobalt.
2. The method of claim 1, comprising the steps of:
s1, adding 50-80 mesh nickel-cobalt-aluminum alloy powder into a container, then adding deionized water, uniformly stirring, then adding a sodium hydroxide aqueous solution, and completely reacting;
s2, filtering the reacted solution, washing the 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;
and S3, putting the nickel-cobalt metal framework solid catalyst into nitrogen or a reduction atmosphere for post-treatment.
3. The method of claim 2, wherein the nickel cobalt metal skeletal catalyst is prepared by: in the S1, the weight percentage of aluminum in the nickel-cobalt-aluminum alloy powder is 50%.
4. The method of claim 2, wherein the nickel cobalt metal skeletal catalyst is prepared by: 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.
5. the method of claim 2, wherein the nickel cobalt metal skeletal catalyst is formed by: in the S1, the reaction temperature is 0-80 ℃, and the reaction time is 4-8 hours.
6. The method of claim 2, wherein the nickel cobalt metal skeletal catalyst is formed by: and in the S3, the post-treatment is to put the nickel-cobalt metal framework solid catalyst into nitrogen protection for sealed storage.
7. The method of claim 2, wherein the nickel cobalt metal skeletal catalyst is prepared by: in S3, the post-treatment is to place the nickel-cobalt metal framework solid catalyst into a hydrogen atmosphere with 1-4 atmospheric pressures for activation, wherein the activation temperature is 20-80 ℃.
8. The nickel-cobalt metal skeleton catalyst is used in preparing organic amine with nitrile compound.
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