CN113713840A - 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
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- CN113713840A CN113713840A CN202010449965.4A CN202010449965A CN113713840A CN 113713840 A CN113713840 A CN 113713840A CN 202010449965 A CN202010449965 A CN 202010449965A CN 113713840 A CN113713840 A CN 113713840A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 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 74
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 70
- 239000000956 alloy Substances 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 27
- -1 cobalt nitride Chemical class 0.000 claims abstract description 37
- 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 34
- 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 19
- 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 13
- 238000000034 method Methods 0.000 claims description 12
- 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 6
- 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
- 238000002791 soaking Methods 0.000 claims description 5
- 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 claims description 3
- UUYMIMCMTZVNDI-UHFFFAOYSA-N 2-chloro-3,4,5-trihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1Cl UUYMIMCMTZVNDI-UHFFFAOYSA-N 0.000 claims description 3
- 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
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 3
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005977 Ethylene Substances 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 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 15
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 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
- 229910005267 GaCl3 Inorganic materials 0.000 description 2
- 238000005034 decoration 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 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
- 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
- 238000000629 steam reforming Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 compound, ionic crystal and transition metal 3 substances, and can be used as a carrier and an auxiliary catalyst; the active component nickel gallium exists in the form of liquid alloy, and can be well combined with the carrier, so that a uniform active center can be obtained, and the catalytic activity and the stability of the catalyst are further improved. 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 more than 80% under the condition of omitting noble metal, and the selectivity of ethylene can reach 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 industrial product and is mainly used for producing polyethylene, but ethylene gas obtained by petroleum cracking contains acetylene with the volume fraction of 0.5-2.3%. The presence of acetylene not only reduces the catalyst activity but also affects the polymer properties when producing polyethylene. Therefore, it is necessary to carry out a dealkynization operation before the production of polyethylene products industrially.
In the dealkynation operation, a selective hydrogenation method and a partial oxidation steam reforming method are commonly used. Compared with 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 main core of the method for removing trace acetylene by catalytic selective hydrogenation lies in the selection of hydrogenation catalysts, but the catalyst commonly used in industry at present takes noble metal Pd as the main catalyst, and in addition, auxiliaries such as Ag, Au and the like need to be added, so that the cost of the catalyst is higher.
Disclosure of Invention
In view of this, the present invention aims to provide a cobalt nitride-nickel gallium liquid alloy composite catalyst, which has the characteristic of good catalytic activity without 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 a nickel gallium liquid alloy.
Preferably, the nickel content in the nickel-gallium liquid alloy is 2-10 wt%, and the gallium content in the nickel-gallium liquid alloy is 5-15 wt%.
Preferably, the nickel content in the nickel-gallium liquid alloy is 3-7 wt%, and the gallium content in the nickel-gallium liquid alloy is 8-12 wt%.
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 then drying to obtain cobalt nitride loaded with nickel salt and gallium salt;
(3) and (3) calcining the cobalt nitride loaded with nickel salt and 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, chlorogallic acid, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethyl.
Preferably, the calcining temperature in the step (3) is 200-600 ℃, and the calcining time is 1-6 h.
Preferably, the calcining temperature in the step (3) is 300-550 ℃, and the calcining time is 2-5 h.
Preferably, the reduction temperature in the step (3) is 100-600 ℃, and the reduction time is 1-5 h.
Preferably, the reduction temperature in the step (3) is 200-500 ℃, and the reduction time is 2-4 h.
The invention also provides the application of the cobalt nitride-nickel gallium liquid alloy composite catalyst or the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared by the preparation method according to the technical scheme 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 a 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 formation of ethane by deep hydrogenation of acetylene. The cobalt nitride selected by the invention has the properties of covalent compound, ionic crystal and transition metal 3 substances, not only can be used as a carrier, but also can be used as an auxiliary catalyst to exist, and the catalytic performance of the catalyst is improved. The active component nickel gallium exists in the form of liquid alloy, and can be well combined with the carrier, so that a uniform active center can be obtained, and the catalytic activity and the stability of the catalyst are further 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 reach more than 80% and the selectivity of ethylene can reach more than 70% under the condition of omitting the use of noble metals.
In addition, the preparation method provided by the invention is simple and easy to operate.
Drawings
FIG. 1 is a TEM image of a catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the acetylene conversion rate as a function of time in example 5 of the present invention;
FIG. 3 is a graph showing the acetylene conversion rate as a function of time in example 6 of the present invention;
FIG. 4 is a graph showing the acetylene conversion rate as a function of time in example 7 of the present invention;
FIG. 5 is a graph showing the time-dependent change of the 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 a 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 compound, ionic crystal and transition metal 3 substances, not only can be used as a carrier, but also can be used as an auxiliary catalyst, and the catalytic performance of the catalyst is improved.
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 a nickel gallium liquid alloy. The active component nickel-gallium of the catalyst provided by the invention exists in the form of liquid alloy, can be well combined with a carrier, can obtain a uniform active center, and further improves the catalytic activity and stability of the catalyst.
In the invention, the content of nickel in the nickel-gallium liquid alloy is preferably 2-10 wt%, more preferably 3-7 wt%, and most preferably 3.5-6.5 wt%. The content of gallium in the nickel-gallium liquid alloy is preferably 5-15 wt%, more preferably 8-12 wt%, and most preferably 8.5-11.5 wt%. In the present invention, the nickel and gallium contents are limited to the above range and are coordinated with each other as active components, and high-efficiency conversion of high acetylene can be achieved without using noble metals.
In the invention, the nickel-gallium liquid alloy is preferably distributed on the surface of the 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 compound, ionic crystal and transition metal 3 substances, can be used as a carrier and also used as an auxiliary catalyst, and improves the catalytic performance of the catalyst. The active component nickel gallium exists in the form of liquid alloy, and can be well combined with the carrier, so that a uniform active center can be obtained, and the catalytic activity and the stability of the catalyst are further 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 then drying to obtain cobalt nitride loaded with nickel salt and gallium salt;
(3) and (3) calcining the cobalt nitride loaded with nickel salt and 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 commercial products which are conventional in the art, unless otherwise specified.
In the present invention, the operation is carried out at room temperature unless otherwise specified.
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, the nickel chloride hexahydrate is selected as a nickel source to synthesize the catalyst, 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, chlorogallic acid, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate, and gallium triethylate, and is more preferably gallium chloride. In the invention, the impurity content of the catalyst synthesized by selecting gallium chloride as a gallium source is low, thereby improving the catalytic performance of the catalyst.
In the present invention, the water is preferably deionized water.
In the present invention, the mixing of the nickel salt, the gallium salt and the water is preferably: mixing nickel salt and gallium salt with part of water respectively to obtain a nickel salt solution and a gallium salt solution; and mixing the nickel salt solution and the gallium salt solution with the residual water to obtain a mixed solution.
In the invention, the concentration of the nickel salt solution is preferably 5-15 mg/mL, more preferably 6-12 mg/mL, and most preferably 10 mg/mL.
In the invention, the concentration of the gallium salt solution is preferably 5-15 mg/mL, more preferably 6-12 mg/mL, and most preferably 10 mg/mL.
In the present invention, the means for pipetting the nickel salt and gallium salt solution is preferably a pipetting gun. In the present invention, the pipette gauge is preferably 1 mL.
After the mixed solution is obtained, the cobalt nitride is soaked in the mixed solution and then dried to obtain the cobalt nitride loaded with nickel salt and gallium salt.
In the present invention, the cobalt nitride is preferably CoN (cubic) or Co2N (orthogonal) and Co3At least one of N (hexagonal), preferably in the present embodiment, CoN (cubic). The CoN selected by the invention not only can be used as a carrier, but also can be used as an auxiliary catalyst, so that the catalytic performance of the catalyst is improved.
In the present invention, the cobalt nitride is preferably soaked in the mixed solution in an equal volume or an excess volume, and more preferably in an equal volume. In the present invention, the mass ratio of the nickel element to the 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 the catalytic performance of the catalyst is ensured.
In the present invention, the soaking of the cobalt nitride in the mixed solution preferably includes stirring and standing in this order. In the present invention, the stirring method is not particularly limited, and a stirring method known to those skilled in the art may be used. In the invention, the stirring time is preferably 1-12 h, more preferably 3-8 h, and most preferably 6 h. In the present invention, the standing method is not particularly limited, and a standing method known to those skilled in the art may be used. In the invention, the standing time is preferably 1-24 h, more preferably 6-18 h, and most preferably 8-14 h.
In the invention, the drying temperature of the cobalt nitride after soaking in the mixed solution is preferably 60-120 ℃, more preferably 70-100 ℃, and most preferably 80 ℃; the drying time is preferably 6-12 h, more preferably 7-10 h, and more preferably 8 h; the drying atmosphere is preferably vacuum drying.
After obtaining the cobalt nitride loaded with nickel salt and gallium salt, the invention carries out reduction after calcining the cobalt nitride loaded with nickel salt and gallium salt to obtain the cobalt nitride-nickel gallium liquid alloy composite catalyst.
In the invention, the calcination temperature is preferably 200-600 ℃, more preferably 400-550 ℃, and most preferably 500 ℃; the calcination time is preferably 1-6 h, more preferably 2-5 h, and most preferably 4 h. In the invention, the calcination temperature and the calcination time are adopted, which is beneficial to obtaining the nickel-gallium alloy with higher purity and improving the catalytic performance of the catalyst.
In the present invention, the condition of the calcination is preferably an air condition. In the invention, the nickel-gallium element is combined through a metal bond in the calcining process, so that the catalytic performance and the stability of the catalyst are improved.
In the invention, the reduction temperature is preferably 100-600 ℃, more preferably 200-500 ℃, and most preferably 400 ℃; the reduction time is preferably 1-5 h, more preferably 2-4 h, and more preferably 3 h. In the present invention, the reduced gas is preferably at least one of hydrogen, methane, hydrogen sulfide, and ammonia. In the invention, the nickel salt and the gallium salt finally form the nickel-gallium liquid alloy in the reduction process, and the active component nickel-gallium exists in the form of the liquid alloy, so that the nickel-gallium can be well combined with the carrier, uniform active centers can be obtained, and the catalytic activity and the stability of the catalyst are further improved.
The invention provides an application of the cobalt nitride-nickel gallium liquid alloy composite catalyst or the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared by the preparation method in the scheme in acetylene hydrogenation reaction.
In the present invention, the apparatus for the hydrogenation reaction of acetylene is preferably a reaction apparatus having a fixed bed. In the present invention, the catalyst is preferably used in a manner of being packed on a fixed bed. In the present invention, the contact manner of the catalyst and the reaction gas is preferably such that the reaction gas flows over the catalyst.
In the invention, the raw material H for acetylene hydrogenation reaction2And C2H2The molar volume ratio of (a) to (b) is not particularly limited, and may be adjusted according to the chemical reaction equation. In the examples of the invention, starting material H of the reaction2And C2H2Is preferably 2: 1.
in the invention, the volume space velocity of the acetylene hydrogenation reaction gas is preferably 1200-3600/h, more preferably 2000-3000/h, and more preferably 2400/h.
In the invention, the temperature of the acetylene hydrogenation reaction is preferably 30-210 ℃, more preferably 80-200 ℃, 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 present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of nickel salt and gallium salt solution
Nickel salt solution: weighing 1g of NiCl2·6H2O, putting the mixture into a beaker, adding deionized water to dissolve the mixture, wherein the adding amount of the deionized water is NiCl2·6H2And dissolving O, transferring the solution into a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a nickel chloride solution with the mass concentration of nickel chloride of 10 mg/mL.
Gallium salt solution: weighing 1g of GaCl3Putting the mixture into a beaker, adding concentrated hydrochloric acid (12mol/Ll) for dissolving, wherein the added amount of the concentrated hydrochloric acid is GaCl3And (3) transferring the solution to a 100mL volumetric flask, adding deionized water to corresponding scales, and preparing a gallium chloride solution with the mass concentration of 10 mg/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 transferred by a 1mL pipette, respectively, and added to a beaker filled with 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 the mixture was stirred for 0.5h to obtain a mixed solution.
2) And (3) adding the mixed solution obtained in the step (1) into 1g CoN (cubic), stirring for 6h, standing for 12h, and drying by a vacuum drying oven at the temperature of 80 ℃ for 8h to obtain the cobalt nitride loaded with nickel salt and gallium salt.
3) And (3) calcining the cobalt nitride loaded with nickel salt and gallium salt obtained in the step (2) for 4 hours in the air atmosphere of 500 ℃, and then carrying out high-temperature reduction in the hydrogen atmosphere at the reduction temperature of 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, from which it can be seen that the metal particles are uniformly distributed and 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 the operation of the embodiment 1, and the difference is only that 12.09mL of nickel salt solution and 25.2mL of gallium salt solution are transferred.
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 the operation of the embodiment 1, and the difference is that 28.21mL of nickel salt solution and 25.2mL of gallium salt solution are transferred.
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 the operation of the embodiment 1, and the difference is only that 20.15mL of nickel salt solution and 30.24mL of gallium salt solution are transferred.
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 the operation of the example 1, and the difference is only 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 the gallium salt solution and the preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst are the same as the operation of the example 1, and the difference is that 25.2mL of the gallium salt solution is removed, and the addition of the nickel salt solution is omitted.
Example 5
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 1 was loaded in a fixed bed, and a reaction gas C was introduced2H2、H2And C2H4The molar ratio of the gases is 1: 2: 100, the volume space velocity of the reaction gas is 2400h-1The reaction was carried out at a reaction temperature of 130 ℃ and a pressure of 0.05MPa, the selectivity of ethylene was 95.2%, and the results of acetylene conversion are shown in FIG. 2.
Example 6
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 2 was filled in a fixed bed, and a reaction gas C was introduced2H2、H2And C2H4The molar ratio of the gases is 1: 2: 100, the volume space velocity of the reaction gas is 2400h-1The reaction was carried out at a reaction temperature of 130 ℃ and a pressure of 0.05MPa, the selectivity of ethylene was 80.6%, and the results of acetylene conversion are shown in FIG. 3.
Example 7
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 3 was loaded in a fixed bed, and a reaction gas C was introduced2H2、H2And C2H4The molar ratio of the gases is 1: 2: 100, the volume space velocity of the reaction gas is 2400h-1The reaction was carried out at a reaction temperature of 130 ℃ and a pressure of 0.05MPa, the selectivity of ethylene was 84.1%, and the results of acetylene conversion are shown in FIG. 3.
Example 8
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in example 4 was loaded in a fixed bed, and a reaction gas C was introduced2H2、H2And C2H4The molar ratio of the gases is 1: 2: 100, the volume space velocity of the reaction gas is 2400h-1The reaction was carried out at a reaction temperature of 130 ℃ and a pressure of 0.05MPa, the selectivity of ethylene was 70.7%, and the results of acetylene conversion are shown in FIG. 5.
Comparative example 3
200mg of cobalt-nickel nitride prepared in comparative example 1 was addedFilling the gallium liquid alloy composite catalyst in a fixed bed, and introducing reaction gas C2H2、H2And C2H4The molar ratio of the gases is 1: 2: 100, the volume space velocity of the reaction gas is 2400h-1The reaction is carried out at the reaction temperature of 130 ℃ and the pressure of 0.05MPa, and the catalyst has no obvious activity. (since the catalyst was inactive, no experimental data was provided)
Comparative example 4
200mg of the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared in the comparative example 2 was filled in a fixed bed, and a reaction gas C was introduced2H2、H2And C2H4The molar ratio of the gases is 1: 2: 100, the volume space velocity of the reaction gas is 2400h-1The reaction is carried out at the reaction temperature of 130 ℃ and the pressure of 0.05MPa, and the catalyst has no obvious activity. (since the catalyst was inactive, no experimental data was provided)
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 slightly decrease after 60 hours of operation; as can be seen in FIG. 3, the acetylene conversion of example 2 was 81.7%, and the activity began to drop slightly after 60h of operation; as can be seen in fig. 4, the conversion of acetylene in example 3 was 88.7%, and the activity began to drop slightly after 60h of operation; as can be seen in fig. 5, the conversion of acetylene in example 4 was 73.1% and the activity began to drop slightly after 60h of operation.
Experimental data of examples 5 to 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 reach more than 80% under the condition of omitting noble metal, and the selectivity of ethylene can reach more than 70%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
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 a nickel gallium liquid alloy.
2. The cobalt nitride-nickel gallium liquid alloy composite catalyst according to claim 1, wherein the nickel content in the nickel gallium liquid alloy is 2-10 wt%, and the gallium content in the nickel gallium liquid alloy is 5-15 wt%.
3. The cobalt nitride-nickel gallium liquid alloy composite catalyst according to claim 2, wherein the nickel content in the nickel gallium liquid alloy is 3 to 7 wt%, and the gallium content in the nickel gallium liquid alloy is 8 to 12 wt%.
4. The preparation method of the cobalt nitride-nickel gallium liquid alloy composite catalyst according to any one of claims 1 to 3, 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 then drying to obtain cobalt nitride loaded with nickel salt and gallium salt;
(3) and (3) calcining the cobalt nitride loaded with nickel salt and gallium salt obtained in the step (2) and then reducing to obtain the cobalt nitride-nickel gallium liquid alloy composite catalyst.
5. The method according to claim 4, 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, chlorogallic acid, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethyl.
6. The preparation method according to claim 4, wherein the calcining temperature in the step (3) is 200-600 ℃, and the calcining time is 1-6 h.
7. The preparation method of claim 6, wherein the calcining temperature in the step (3) is 300-550 ℃, and the calcining time is 2-5 h.
8. The preparation method according to claim 4, 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.
9. The preparation method according to claim 8, wherein the temperature of the reduction in the step (3) is 200-500 ℃ and the time of the reduction is 2-4 h.
10. The cobalt nitride-nickel gallium liquid alloy composite catalyst according to any one of claims 1 to 3 or the cobalt nitride-nickel gallium liquid alloy composite catalyst prepared by the preparation method according to any one of claims 4 to 9 is used in acetylene hydrogenation reaction.
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