CN113713840B - Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof - Google Patents
Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113713840B CN113713840B CN202010449965.4A CN202010449965A CN113713840B CN 113713840 B CN113713840 B CN 113713840B CN 202010449965 A CN202010449965 A CN 202010449965A CN 113713840 B CN113713840 B CN 113713840B
- Authority
- CN
- China
- Prior art keywords
- nickel
- gallium
- liquid alloy
- cobalt nitride
- salt
- 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.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 78
- 239000010941 cobalt Substances 0.000 title claims abstract description 78
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 68
- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 239000007788 liquid Substances 0.000 title claims abstract description 68
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 23
- -1 cobalt nitride Chemical class 0.000 claims abstract description 41
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 150000002258 gallium Chemical class 0.000 claims description 37
- 150000002815 nickel Chemical class 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 3
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000005977 Ethylene Substances 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 239000012266 salt solution Substances 0.000 description 27
- 239000012495 reaction gas Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a cobalt nitride-nickel gallium liquid alloy composite catalyst, which comprises a carrier cobalt nitride and an active component nickel gallium liquid alloy loaded on the carrier. The cobalt nitride selected by the invention has the properties of covalent compounds, ionic crystals and transition metal 3 substances, and can be used as a carrier and an auxiliary catalyst at the same time; the active component nickel gallium exists in the form of liquid alloy, can be well combined with a carrier, and can obtain uniform active centers, so that the catalytic activity and stability of the catalyst are improved. When the cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention is used for acetylene hydrogenation reaction, under the condition that noble metal is omitted, the conversion rate of acetylene can be more than 80%, and the selectivity of ethylene can be more than 70%.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a cobalt nitride-nickel gallium liquid alloy composite catalyst and a preparation method and application thereof.
Background
Ethylene is an important petroleum industry product mainly used for producing polyethylene, but the ethylene gas obtained by petroleum cracking contains 0.5-2.3% of acetylene by volume. In the production of polyethylene, the presence of acetylene not only reduces the catalyst activity, but also affects the properties of the polymer. Therefore, a dealkylation operation is required industrially before the polyethylene product is produced.
In the alkyne removal operation, the common methods are a selective hydrogenation method and a partial oxidation steam conversion method. Compared with the partial oxidation steam conversion method, the catalytic selective hydrogenation method has the advantages of less pollution, low energy consumption and good acetylene removal effect. The method for removing trace acetylene by catalytic selective hydrogenation mainly has the key points that the hydrogenation catalyst is selected, the catalyst commonly used in the industry at present takes noble metal Pd as a main catalyst, and in addition, auxiliaries such as Ag, au and the like are needed to be added, so that the catalyst cost is high.
Disclosure of Invention
In view of the above, the invention aims to provide a cobalt nitride-nickel gallium liquid alloy composite catalyst, which has the characteristic of good catalytic activity under the condition of not using noble metals.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a cobalt nitride-nickel gallium liquid alloy composite catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is cobalt nitride, and the active component is nickel gallium liquid alloy.
Preferably, the nickel content in the nickel-gallium liquid alloy is 2-10wt%, and the gallium content in the nickel-gallium liquid alloy is 5-15wt%.
Preferably, the nickel content in the nickel-gallium liquid alloy is 3-7wt%, and the gallium content in the nickel-gallium liquid alloy is 8-12wt%.
The invention also provides a preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst, which comprises the following steps:
(1) Mixing nickel salt, gallium salt and water to obtain a mixed solution;
(2) Soaking cobalt nitride in the mixed solution obtained in the step (1), and drying to obtain cobalt nitride loaded with nickel salt and gallium salt;
(3) And (3) calcining the cobalt nitride loaded with the nickel salt and the gallium salt obtained in the step (2) and then reducing to obtain the cobalt nitride-nickel gallium liquid alloy composite catalyst.
Preferably, the nickel salt in the step (1) is at least one of nickel chloride hexahydrate, nickel formate, nickel carbonate, nickel ammonium sulfate, nickel perchlorate, nickel acetylacetonate and nickel nitrate hexahydrate;
the gallium salt in the step (1) is at least one of gallium nitrate, chlorogallate, ethanol gallium, isopropanol gallium, acetyl acetonate gallium and triethyl gallium.
Preferably, the calcination temperature in the step (3) is 200-600 ℃, and the calcination time is 1-6 h.
Preferably, the calcination temperature in the step (3) is 300-550 ℃ and the calcination time is 2-5 h.
Preferably, the temperature of the reduction in the step (3) is 100-600 ℃, and the time of the reduction is 1-5 h.
Preferably, the temperature of the reduction in the step (3) is 200-500 ℃, and the time of the reduction is 2-4 h.
The invention also provides an application of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared by the technical scheme or the preparation method in acetylene hydrogenation reaction.
The invention provides a cobalt nitride-nickel gallium liquid alloy composite catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is cobalt nitride, and the active component is nickel gallium liquid alloy. The existence of the nickel-gallium liquid alloy can avoid the secondary reaction of reactants on the surface of the catalyst, and inhibit or reduce the deep hydrogenation of acetylene to form ethane. The cobalt nitride selected by the invention has the properties of covalent compounds, ionic crystals and transition metal 3 substances, can be used as a carrier and an auxiliary catalyst, and improves the catalytic performance of the catalyst. The active component nickel gallium exists in the form of liquid alloy, can be well combined with a carrier, and can obtain uniform active centers, so that the catalytic activity and stability of the catalyst are improved. The results of the examples show that when the cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention is used for acetylene hydrogenation reaction, the conversion rate of acetylene can be more than 80% and the selectivity of ethylene can be more than 70% under the condition that noble metal is omitted.
In addition, the preparation method provided by the invention is simple and easy to operate.
Drawings
FIG. 1 is a TEM image of the catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the time course of acetylene conversion in example 5 of the present invention;
FIG. 3 is a graph showing the time course of acetylene conversion in example 6 of the present invention;
FIG. 4 is a graph showing the acetylene conversion over time in example 7 of the present invention;
FIG. 5 is a graph showing the time course of acetylene conversion in example 8 of the present invention.
Detailed Description
The invention provides a cobalt nitride-nickel gallium liquid alloy composite catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is cobalt nitride, and the active component is nickel gallium liquid alloy.
The cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention comprises a carrier, wherein the carrier is cobalt nitride. In the invention, the cobalt nitride has the properties of covalent compounds, ionic crystals and transition metal 3 substances, and can be used as a carrier and an auxiliary catalyst at the same time, thereby improving the catalytic performance of the catalyst.
The cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention comprises an active component loaded on the carrier, wherein the active component is nickel gallium liquid alloy. The nickel gallium serving as the active component of the catalyst provided by the invention can be well combined with the carrier because of the existence of the liquid alloy, so that a uniform active center can be obtained, further the catalytic activity and stability of the catalyst are improved, the conversion rate of acetylene and the selectivity of ethylene are improved under the combined action of the nickel gallium liquid alloy and cobalt nitride serving as a carrier and an auxiliary catalyst, and the use of noble metals is omitted.
In the present invention, the nickel content in the nickel gallium liquid alloy is preferably 2 to 10wt%, more preferably 3 to 7wt%, and most preferably 3.5 to 6.5wt%. The content of gallium in the nickel gallium liquid alloy is preferably 5 to 15wt%, more preferably 8 to 12wt%, and most preferably 8.5 to 11.5wt%. In the invention, the content of nickel and gallium is limited in the above range, nickel and gallium are matched with each other, and high-efficiency conversion of high acetylene can be realized without using noble metal as an active component.
In the invention, the nickel-gallium liquid alloy is preferably distributed on the surface of cobalt nitride.
The cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention takes cobalt nitride as a carrier, has the properties of covalent compounds, ionic crystals and transition metal 3 substances, can be used as a carrier and an auxiliary catalyst, and improves the catalytic performance of the catalyst. The active component nickel gallium exists in the form of liquid alloy, can be well combined with a carrier, and can obtain uniform active centers, so that the catalytic activity and stability of the catalyst are improved.
The invention also provides a preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst, which comprises the following steps:
(1) Mixing nickel salt, gallium salt and water to obtain a mixed solution;
(2) Soaking cobalt nitride in the mixed solution obtained in the step (1), and drying to obtain cobalt nitride loaded with nickel salt and gallium salt;
(3) And (3) calcining the cobalt nitride loaded with the nickel salt and the gallium salt obtained in the step (2) and then reducing to obtain the cobalt nitride-nickel gallium liquid alloy composite catalyst.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
In the present invention, unless otherwise specified, the operations performed are all room temperature conditions.
The invention mixes nickel salt, gallium salt and water to obtain mixed solution.
In the present invention, the nickel salt is preferably at least one of nickel chloride hexahydrate, nickel formate, nickel carbonate, nickel ammonium sulfate, nickel perchlorate, nickel acetylacetonate, and nickel nitrate hexahydrate, and more preferably nickel chloride hexahydrate. In the invention, nickel chloride hexahydrate is selected as a catalyst for synthesizing a nickel source, so that the impurity content is low, and the catalytic performance of the catalyst is improved.
In the present invention, the gallium salt is preferably at least one of gallium nitrate, chlorogallate, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethylide, more preferably gallium chloride. In the invention, the catalyst synthesized by using gallium chloride as a gallium source has low impurity content, so that the catalytic performance of the catalyst is improved.
In the present invention, the water is preferably deionized water.
In the present invention, the mixture of nickel salt, gallium salt and water is preferably: mixing nickel salt and gallium salt with partial water respectively to obtain nickel salt solution and gallium salt solution; and mixing the nickel salt solution and the gallium salt solution with the rest water to obtain a mixed solution.
In the present invention, the concentration of the nickel salt solution is preferably 5 to 15mg/mL, more preferably 6 to 12mg/mL, and most preferably 10mg/mL.
In the present invention, the concentration of the gallium salt solution is preferably 5 to 15mg/mL, more preferably 6 to 12mg/mL, and most preferably 10mg/mL.
In the present invention, the means for removing the nickel salt and gallium salt solutions is preferably a pipette gun. In the present invention, the specification of the pipette is preferably 1mL.
After the mixed solution is obtained, the cobalt nitride is soaked in the mixed solution and then dried, so that the cobalt nitride loaded with nickel salt and gallium salt is obtained.
In the present invention, the cobalt nitride is preferably CoN (cubic), co 2 N (orthogonal) and Co 3 At least one of N (hexagonal) is preferably CoN (cubic) in the embodiment of the present invention. The CoN selected by the invention can be used as a carrier and an auxiliary catalyst, so that the catalytic performance of the catalyst is improved.
In the present invention, the means for immersing the cobalt nitride in the mixed solution is preferably equal volume immersion or excessive volume immersion, more preferably equal volume immersion. In the present invention, the mass ratio of nickel element to cobalt nitride in the mixed solution is preferably 1.0 to 12.0%, more preferably 2.0 to 10.0%, and most preferably 3.0 to 7.0%. The mass ratio of the gallium element to the cobalt nitride is preferably 1.0 to 20.0%, more preferably 5.0 to 15.0%, and still more preferably 8.0 to 12.0%. In the present invention, the content of nickel and gallium is limited to the above range, so that the amount of metal used can be reduced while ensuring the catalytic performance of the catalyst.
In the present invention, the immersing of the cobalt nitride in the mixed solution preferably includes stirring and standing in order. The stirring method is not particularly limited, and stirring methods well known to those skilled in the art may be employed. In the present invention, the stirring time is preferably 1 to 12 hours, more preferably 3 to 8 hours, and most preferably 6 hours. The method of standing in the present invention is not particularly limited, and a standing method known to those skilled in the art may be used. In the present invention, the time for the standing is preferably 1 to 24 hours, more preferably 6 to 18 hours, and most preferably 8 to 14 hours.
In the invention, the drying temperature of the cobalt nitride after being soaked in the mixed solution is preferably 60-120 ℃, more preferably 70-100 ℃ and most preferably 80 ℃; the drying time is preferably 6 to 12 hours, more preferably 7 to 10 hours, and even more preferably 8 hours; the atmosphere for drying is preferably vacuum drying.
After cobalt nitride loaded with nickel salt and gallium salt is obtained, the cobalt nitride loaded with nickel salt and gallium salt is calcined and then reduced, so that the cobalt nitride-nickel gallium liquid alloy composite catalyst is obtained.
In the present invention, the temperature of the calcination is preferably 200 to 600 ℃, more preferably 400 to 550 ℃, and most preferably 500 ℃; the calcination time is preferably 1 to 6 hours, more preferably 2 to 5 hours, most preferably 4 hours. In the invention, the adoption of the calcination temperature and the calcination time is beneficial to obtaining nickel-gallium alloy with higher purity and improving the catalytic performance of the catalyst.
In the present invention, the conditions for the calcination are preferably air conditions. In the invention, nickel gallium is combined through metal bond in the calcination process, so that the catalytic performance and stability of the catalyst are improved.
In the present invention, the temperature of the reduction is preferably 100 to 600 ℃, more preferably 200 to 500 ℃, and most preferably 400 ℃; the time for the reduction is preferably 1 to 5 hours, more preferably 2 to 4 hours, and still more preferably 3 hours. In the present invention, the reduced gas is preferably at least one of hydrogen, methane, hydrogen sulfide, and ammonia. In the invention, nickel salt and gallium salt finally form nickel-gallium liquid alloy in the reduction process, and active component nickel-gallium can be well combined with a carrier due to the existence of the liquid alloy, so that a uniform active center can be obtained, and the catalytic activity and stability of the catalyst are further improved.
The invention provides an application of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared by the scheme or the preparation method in acetylene hydrogenation reaction.
In the present invention, the apparatus for hydrogenation of acetylene is preferably a reaction apparatus having a fixed bed. In the present invention, the catalyst is preferably used in a form packed on a fixed bed. In the present invention, the catalyst and the reaction gas are preferably contacted in such a manner that the reaction gas flows over the catalyst.
In the invention, the raw material H for acetylene hydrogenation reaction 2 And C 2 H 2 The molar volume ratio of (2) is not particularly limited, and may be adjusted according to a chemical reaction equation. In an embodiment of the invention, the starting material H for the reaction 2 And C 2 H 2 Preferably 2:1.
in the present invention, the volume space velocity of the gas for the acetylene hydrogenation reaction is preferably 1200 to 3600/h, more preferably 2000 to 3000/h, and still more preferably 2400/h.
In the present invention, the temperature of the acetylene hydrogenation reaction is preferably 30 to 210 ℃, more preferably 80 to 200 ℃, and most preferably 130 ℃.
In the present invention, the pressure of the acetylene hydrogenation reaction is preferably 0.01 to 0.2MPa, more preferably 0.03 to 0.1MPa, and most preferably 0.05MPa.
When the cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention is used for acetylene hydrogenation reaction, the conversion rate of acetylene can reach 99.4%, and the selectivity of ethylene can reach 95.2%.
The cobalt nitride-nickel gallium liquid alloy composite catalyst, the preparation method and the application thereof provided by the invention are described in detail below with reference to examples, but are not to be construed as limiting the scope of the invention.
Example 1
Preparation of Nickel salt and gallium salt solutions
Nickel salt solution: weigh 1g of NiCl 2 ·6H 2 O is put into a beaker and added with deionized water for dissolution, and the addition amount of the deionized water is used for dissolving NiCl 2 ·6H 2 O is dissolved, the solution is transferred to a 100mL volumetric flask, deionized water is added to corresponding scales, and the nickel chloride solution with the mass concentration of 10mg/mL of nickel chloride is prepared.
Gallium salt solution: 1g of GaCl is weighed 3 Putting into a beaker, adding concentrated hydrochloric acid (12 mol/L) for dissolution, wherein the adding amount of the concentrated hydrochloric acid is GaCl 3 Dissolving, transferring the solution into a 100mL volumetric flask, and adding deionized water to corresponding scales to obtain gallium chloride solution with the mass concentration of gallium chloride of 10mg/mL.
Preparation of cobalt nitride-nickel gallium liquid alloy composite catalyst
1) 20.15mL of the nickel salt solution and 25.2mL of the gallium salt solution were respectively removed by a 1mL pipette, and added to a beaker containing water, the volume of which was determined by the volume of the cobalt nitride carrier (metal component loading by an equal volume standing method), and stirred for 0.5h to obtain a mixed solution.
2) And (3) adding the mixed solution in the step (1) into 1g CoN (cubic), stirring for 6h, standing for 12h, and drying by a vacuum drying oven at 80 ℃ for 8h to obtain the cobalt nitride loaded with nickel salt and gallium salt.
3) Calcining the cobalt nitride loaded with nickel salt and gallium salt obtained in the step 2 for 4 hours in an air atmosphere at 500 ℃, and then carrying out high-temperature reduction in a hydrogen atmosphere at 400 ℃ for 3 hours to obtain the cobalt nitride-nickel gallium liquid alloy composite catalyst. The TEM of the catalyst is shown in fig. 1, and it can be seen from fig. 1 that the metal particles are uniformly distributed and the particles are smaller.
Example 2
The preparation of nickel salt and gallium salt solution and the preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst are the same as those of example 1, except that 12.09mL of nickel salt solution and 25.2mL of gallium salt solution are removed.
Example 3
The preparation of nickel salt and gallium salt solution and the preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst are the same as those of example 1, except that 28.21mL of nickel salt solution and 25.2mL of gallium salt solution are removed.
Example 4
The preparation of nickel salt and gallium salt solution and the preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst are the same as those of example 1, except that 20.15mL of nickel salt solution and 30.24mL of gallium salt solution are removed.
Comparative example 1
The preparation of the nickel salt solution and the preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst are the same as those of the example 1, except that 20.15mL of the nickel salt solution is removed, and the addition of the gallium salt solution is omitted.
Comparative example 2
The preparation of gallium salt solution and the preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst are the same as those of the example 1, except that 25.2mL of gallium salt solution is removed, and the addition of nickel salt solution is omitted.
Example 5
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 1 is filled in a fixed bed, and reaction gas C is introduced 2 H 2 、H 2 And C 2 H 4 The molar ratio of the gases is 1:2:100, the volume space velocity of the reaction gas is 2400h -1 The reaction was carried out at 130℃and 0.05MPa, with an ethylene selectivity of 95.2% and an acetylene conversion as shown in FIG. 2.
Example 6
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 2 is filled in a fixed bed and is introduced into the reactionGas C 2 H 2 、H 2 And C 2 H 4 The molar ratio of the gases is 1:2:100, the volume space velocity of the reaction gas is 2400h -1 The reaction was carried out at 130℃and 0.05MPa, with an ethylene selectivity of 80.6% and an acetylene conversion as shown in FIG. 3.
Example 7
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 3 is filled in a fixed bed, and reaction gas C is introduced 2 H 2 、H 2 And C 2 H 4 The molar ratio of the gases is 1:2:100, the volume space velocity of the reaction gas is 2400h -1 The reaction was carried out at 130℃and 0.05MPa, with an ethylene selectivity of 84.1% and an acetylene conversion as shown in FIG. 3.
Example 8
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 4 is filled in a fixed bed, and reaction gas C is introduced 2 H 2 、H 2 And C 2 H 4 The molar ratio of the gases is 1:2:100, the volume space velocity of the reaction gas is 2400h -1 The reaction was carried out at 130℃and 0.05MPa, with an ethylene selectivity of 70.7% and an acetylene conversion as shown in FIG. 5.
Comparative example 3
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in comparative example 1 is filled in a fixed bed, and reaction gas C is introduced 2 H 2 、H 2 And C 2 H 4 The molar ratio of the gases is 1:2:100, the volume space velocity of the reaction gas is 2400h -1 The reaction is carried out at the reaction temperature of 130 ℃ and the pressure of 0.05MPa, and no obvious activity of the catalyst is found. (no experimental results data are provided because the catalyst is inactive)
Comparative example 4
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in comparative example 2 is filled in a fixed bed, and reaction gas C is introduced 2 H 2 、H 2 And C 2 H 4 The molar ratio of the gases is 1:2:100, the volume space velocity of the reaction gas is 2400h -1 The reaction is carried out at the reaction temperature of 130 ℃ and the pressure of 0.05MPa, and no obvious activity of the catalyst is found. (no experimental results data are provided because the catalyst is inactive)
As can be seen from fig. 2, the conversion rate of acetylene of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 1 is 93.5%, and the activity starts to be slightly reduced after 60 hours of operation; as can be seen in fig. 3, the conversion of acetylene was 81.7% in example 2, and the activity began to slightly decrease after 60 hours of operation; as can be seen in fig. 4, the conversion of acetylene was 88.7% in example 3, and the activity began to slightly decrease after 60 hours of operation; as can be seen in FIG. 5, the conversion of acetylene was 73.1% in example 4 and the activity began to slightly decrease after 60 hours of operation.
Experimental data in examples 5-8 show that when the cobalt nitride-nickel gallium liquid alloy composite catalyst provided by the invention is used for acetylene hydrogenation reaction, the conversion rate of acetylene can be more than 80% and the selectivity of ethylene can be more than 70% under the condition that noble metal is omitted.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The cobalt nitride-nickel gallium liquid alloy composite catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is cobalt nitride, and the active component is nickel gallium liquid alloy;
the content of nickel in the nickel-gallium liquid alloy is 2-10wt% relative to the mass of the carrier cobalt nitride, and the content of gallium in the nickel-gallium liquid alloy is 5-15wt%.
2. The cobalt nitride-nickel gallium liquid alloy composite catalyst according to claim 1, wherein the content of nickel in the nickel gallium liquid alloy is 3-7wt% and the content of gallium in the nickel gallium liquid alloy is 8-12wt%.
3. The method for preparing the cobalt nitride-nickel gallium liquid alloy composite catalyst according to any one of claims 1-2, comprising the following steps:
(1) Mixing nickel salt, gallium salt and water to obtain a mixed solution;
(2) Soaking cobalt nitride in the mixed solution obtained in the step (1), and drying to obtain cobalt nitride loaded with nickel salt and gallium salt;
(3) And (3) calcining the cobalt nitride loaded with the nickel salt and the gallium salt obtained in the step (2) and then reducing to obtain the cobalt nitride-nickel gallium liquid alloy composite catalyst.
4. The method according to claim 3, wherein the nickel salt in the step (1) is at least one of nickel chloride hexahydrate, nickel formate, nickel carbonate, nickel ammonium sulfate, nickel perchlorate, nickel acetylacetonate and nickel nitrate hexahydrate;
the gallium salt in the step (1) is at least one of gallium nitrate, chlorogallate, ethanol gallium, isopropanol gallium, acetyl acetonate gallium and triethyl gallium.
5. The method according to claim 3, wherein the calcination temperature in the step (3) is 200 to 600 ℃ and the calcination time is 1 to 6 hours.
6. The method according to claim 5, wherein the calcination temperature in the step (3) is 300-550 ℃ and the calcination time is 2-5 hours.
7. The method according to claim 3, wherein the temperature of the reduction in the step (3) is 100 to 600 ℃, and the time of the reduction is 1 to 5 hours.
8. The preparation method according to claim 7, wherein the reduction temperature in the step (3) is 200-500 ℃ and the reduction time is 2-4 hours.
9. Use of the cobalt nitride-nickel gallium liquid alloy composite catalyst according to any one of claims 1-2 or the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared by the preparation method according to any one of claims 3-8 in acetylene hydrogenation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010449965.4A CN113713840B (en) | 2020-05-25 | 2020-05-25 | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010449965.4A CN113713840B (en) | 2020-05-25 | 2020-05-25 | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113713840A CN113713840A (en) | 2021-11-30 |
| CN113713840B true CN113713840B (en) | 2023-07-25 |
Family
ID=78671684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010449965.4A Active CN113713840B (en) | 2020-05-25 | 2020-05-25 | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113713840B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247876A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Method for preparing ethylene with acetylene selective catalytic hydrogenation |
| WO2013186474A1 (en) * | 2012-06-11 | 2013-12-19 | Universite Pierre Et Marie Curie (Paris 6) | Method for producing a nickel supported catalyst, and use of said catalyst for the production of hydrogen |
| CN106861715A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of application of nickeliferous alloy catalyst in selective acetylene hydrocarbon hydrogenation reaction |
| CN109675569A (en) * | 2019-01-28 | 2019-04-26 | 华东师范大学 | A kind of load-type nickel based alloy catalyst and its preparation method and application |
| CN109718762A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | It is the method for the selective hydrogenation of catalyst of ethylene and preparation method thereof and acetylene for selective hydrogenation of acetylene |
| CN110038614A (en) * | 2019-05-20 | 2019-07-23 | 中国科学院长春应用化学研究所 | A kind of nitrogen-doped carbon material and preparation method thereof of cobalt nitride load |
| CN110548499A (en) * | 2019-08-16 | 2019-12-10 | 西安凯立新材料股份有限公司 | Composite carrier catalyst for acetylene hydrochlorination and application thereof |
-
2020
- 2020-05-25 CN CN202010449965.4A patent/CN113713840B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247876A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Method for preparing ethylene with acetylene selective catalytic hydrogenation |
| WO2013186474A1 (en) * | 2012-06-11 | 2013-12-19 | Universite Pierre Et Marie Curie (Paris 6) | Method for producing a nickel supported catalyst, and use of said catalyst for the production of hydrogen |
| CN106861715A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of application of nickeliferous alloy catalyst in selective acetylene hydrocarbon hydrogenation reaction |
| CN109718762A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | It is the method for the selective hydrogenation of catalyst of ethylene and preparation method thereof and acetylene for selective hydrogenation of acetylene |
| CN109675569A (en) * | 2019-01-28 | 2019-04-26 | 华东师范大学 | A kind of load-type nickel based alloy catalyst and its preparation method and application |
| CN110038614A (en) * | 2019-05-20 | 2019-07-23 | 中国科学院长春应用化学研究所 | A kind of nitrogen-doped carbon material and preparation method thereof of cobalt nitride load |
| CN110548499A (en) * | 2019-08-16 | 2019-12-10 | 西安凯立新材料股份有限公司 | Composite carrier catalyst for acetylene hydrochlorination and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Selective hydrogenation of acetylene on SiO2-supported Ni-Ga alloy and intermetallic compound";Lei Wang et al.;《Journal of Energy Chemistry》;第29卷;40-49 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113713840A (en) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0169188B1 (en) | Method of preparing hydrocarbon | |
| CN110368933B (en) | Ruthenium-based ammonia synthesis catalyst with Ce-Ti composite oxide as carrier and preparation method thereof | |
| CN111229213A (en) | Preparation method of ruthenium-based catalyst | |
| CN112774674A (en) | Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof | |
| CN111644197A (en) | Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application | |
| CN114160143B (en) | CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof | |
| CN111250080A (en) | Pd/MgO-Al2O3Catalyst, preparation method and application thereof | |
| CN112808295B (en) | Preparation method and application of single-site Co (II) catalyst | |
| CN109569712A (en) | One kind being used for CO2The catalyst and its preparation method and purposes of hydrogenating reduction production ethyl alcohol | |
| CN113713840B (en) | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof | |
| CN112403475A (en) | Preparation method of catalyst for preparing synthesis gas by reforming carbon dioxide | |
| CN110404558B (en) | NiPt-Ni (OH) for hydrogen production by hydrazine decomposition 2 /La(OH) 3 Catalyst and preparation method thereof | |
| CN112827501A (en) | Controllable synthesis of alpha-MoC supported indium and modified catalyst thereof and application of alpha-MoC supported indium in reaction for preparing methanol by carbon dioxide hydrogenation | |
| CN110038591B (en) | Copper-iridium composite oxide catalyst for preparing methanol by methane oxidation | |
| CN113713810B (en) | Aluminum oxide-ruthenium gallium indium liquid alloy composite catalyst and preparation method and application thereof | |
| CN110038563A (en) | A kind of charcoal@alumina load ruthenium-based ammonia synthetic catalyst and preparation method thereof | |
| CN113713811B (en) | Aluminum oxide-iridium gallium liquid alloy composite catalyst and preparation method and application thereof | |
| CN114100653B (en) | Nitride supported palladium catalyst and preparation method and application thereof | |
| CN112723973B (en) | Process for producing styrene | |
| US11318446B2 (en) | Activated carbon/Pd-Ga liquid alloy composite catalyst, preparation method and use thereof | |
| CN111116377B (en) | Method for preparing hexamethylene diamine | |
| CN112694907B (en) | Method for preparing hydrocarbon compound from methane | |
| CN111589464B (en) | Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof | |
| CN115475637B (en) | Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof | |
| CN114471744B (en) | Pretreatment method of iron-based catalyst and application thereof |
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 |