CN111589464A - Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof - Google Patents
Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof Download PDFInfo
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- CN111589464A CN111589464A CN202010326710.9A CN202010326710A CN111589464A CN 111589464 A CN111589464 A CN 111589464A CN 202010326710 A CN202010326710 A CN 202010326710A CN 111589464 A CN111589464 A CN 111589464A
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- gallium
- rhodium
- boron nitride
- tin
- water
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 81
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 239000000956 alloy Substances 0.000 title claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 49
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 46
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 45
- 239000010948 rhodium Substances 0.000 claims abstract description 45
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052718 tin Inorganic materials 0.000 claims abstract description 40
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 claims abstract description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 42
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 8
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 3
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 3
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 claims description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 3
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 claims description 3
- 229940079864 sodium stannate Drugs 0.000 claims description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 claims description 3
- OTOHACXAQUCHJO-UHFFFAOYSA-H tripotassium;hexachlororhodium(3-) Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[K+].[Rh+3] OTOHACXAQUCHJO-UHFFFAOYSA-H 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 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 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 6
- 229910052737 gold Inorganic materials 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910005267 GaCl3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical group [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/27—
-
- 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
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- 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 boron nitride loaded rhodium-gallium-tin liquid alloy catalyst, and a preparation method and application thereof, and belongs to the technical field of catalysts. The boron nitride loaded rhodium-gallium-tin liquid alloy catalyst provided by the invention comprises boron nitride and an active component loaded on the surface of the boron nitride; the active component includes a rhodium gallium tin liquid alloy. The invention takes rhodium, gallium and tin as active components, takes boron nitride as a carrier, and forms a liquid stable structure of three metals among rhodium atoms, gallium atoms and tin atoms, so that the rhodium, the gallium and the tin cannot be agglomerated and have good dispersibility; the bonding force of rhodium, gallium and tin with the boron nitride carrier is strong, and the stability of the catalyst is high; and compared with the catalyst loaded with noble metals (Pd, Ag and Au), the cost of the catalyst is greatly reduced.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst and a preparation method and application thereof.
Background
Petroleum cracking is a process for producing ethylene that is commonly used in industry, but the ethylene obtained usually contains traces of acetylene. The content of acetylene seriously affects the ethylene polymerization reaction, so that the quality of polyethylene is obviously reduced, and therefore, acetylene removal is urgently needed in the industry to reduce the content of acetylene to be less than 5ppm, which is a hot point of research in recent years.
At present, the common methods for removing trace acetylene from ethylene are a partial oxidation steam conversion method and a catalytic hydrogenation reaction method. The catalytic hydrogenation reaction is a main method for industrially removing trace acetylene due to mild reaction conditions, low energy consumption and convenient operation. The choice of catalyst during the hydrogenation reaction is an important factor affecting the reaction result.
Because Pd has good adsorptivity for acetylene and can activate acetylene to promote the conversion of acetylene, the supported Pd catalyst is widely used in industry. However, Pd metal is expensive, and the activity and reaction selectivity for acetylene are still insufficient, and in order to improve the catalytic performance of Pd catalysts, Pd is often mixed with other metals such as Ag or Au, or Pd is supported on a carrier such as silica or alumina. However, the catalytic activity of the supported Pd catalyst is low.
Disclosure of Invention
The invention aims to provide a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst, which comprises boron nitride and an active component loaded on the surface of the boron nitride; the active component includes a rhodium gallium tin liquid alloy.
Preferably, the content of the active component in the boron nitride supported rhodium-gallium-tin liquid alloy catalyst is 0.8-8.5 wt%.
The invention provides a preparation method of a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst in the technical scheme, which comprises the following steps:
mixing a water-soluble rhodium source, a water-soluble gallium source, a water-soluble tin source and water, mixing the obtained mixed solution with boron nitride, standing, dipping and drying to obtain a catalyst precursor;
and sequentially carrying out calcination and reduction reaction on the catalyst precursor to obtain the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst.
Preferably, the mass ratios of the water-soluble rhodium source, the water-soluble gallium source, the water-soluble tin source and the boron nitride are respectively 0.002-0.015: 0.003 to 0.04: 0.003 to 0.04: 1.
preferably, the water-soluble rhodium source comprises rhodium chloride, rhodium nitrate, ammonium chlororhodate, rhodium sulfate, potassium hexachlororhodium (III) or rhodium (III) triacetylacetonate.
Preferably, the water-soluble gallium source comprises gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate or gallium triethylate.
Preferably, the water-soluble tin source comprises stannous chloride dihydrate, stannic chloride, sodium stannate, tetraphenyltin, acetylacetonatostannic chloride, stannous sulfate or stannic acetate.
Preferably, the calcining temperature is 500-1000 ℃, and the time is 2-6 h.
Preferably, the reducing gas used in the reduction reaction comprises one or more of hydrogen, methane, hydrogen sulfide and ammonia gas;
the temperature of the reduction reaction is 200-600 ℃, and the time is 1-5 h.
The invention also provides the application of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared by the preparation method in the technical scheme in removing acetylene in ethylene by catalytic hydrogenation.
The invention provides a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst, which comprises boron nitride and an active component loaded on the surface of the boron nitride; the active component includes a rhodium gallium tin liquid alloy. The invention takes rhodium, gallium and tin as active components, and strong metal bonds are formed among rhodium atoms, gallium atoms and tin atoms, so that the stability is high, the bonding force with a boron nitride carrier is strong, rhodium, gallium and tin can not agglomerate, uniform active centers can be obtained, and the catalytic activity of the catalyst can be improved; and the cost is greatly reduced compared with the cost of noble metals (Pd, Ag and Au). The invention takes boron nitride as a carrier, can improve the dispersibility of rhodium, gallium and tin in the catalyst and the binding force with the rhodium, the gallium and the tin, and is beneficial to increasing the catalytic activity and the stability of the catalyst. The boron nitride loaded rhodium-gallium-tin liquid alloy catalyst provided by the invention forms a self-protection oxide layer liquid film in the process of removing acetylene in ethylene through catalytic hydrogenation, and can avoid secondary reaction of ethylene on the surface of the catalyst, so that the formation of ethane by-products through deep hydrogenation of acetylene is inhibited, and the catalytic activity on acetylene is high.
The invention provides a preparation method of the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst, which is simple to operate, low in raw material cost, free of secondary pollution and suitable for industrial production.
Drawings
FIG. 1 is a TEM image of a boron nitride supported rhodium gallium tin liquid alloy catalyst prepared in example 1;
FIG. 2 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in example 1 on the hydrogenation of acetylene;
FIG. 3 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in example 2 on the hydrogenation of acetylene;
FIG. 4 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in example 3 on the hydrogenation of acetylene;
FIG. 5 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in example 4 on the hydrogenation of acetylene;
FIG. 6 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in example 5 on the hydrogenation of acetylene;
FIG. 7 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in comparative example 1 on acetylene hydrogenation;
fig. 8 is a graph showing the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in comparative example 2 on acetylene hydrogenation.
Detailed Description
The invention provides a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst, which comprises boron nitride and an active component loaded on the surface of the boron nitride; the active component includes a rhodium gallium tin liquid alloy.
In the invention, the content of the active component in the boron nitride supported rhodium-gallium-tin liquid alloy catalyst is preferably 0.8-8.5 wt%, more preferably 1-8 wt%, and most preferably 2-7 wt%. In the invention, in the boron nitride supported rhodium-gallium-tin liquid alloy catalyst, the content of rhodium is preferably 0.2-1.5 wt%, more preferably 0.3-1.2 wt%, and most preferably 0.5-1 wt%; the content of gallium is preferably 0.3 to 4 wt%, more preferably 1 to 3 wt%, most preferably 1.5 to 2.5 wt%; the tin content is preferably 0.3 to 4 wt%, more preferably 1 to 3 wt%, most preferably 1.5 to 2.5 wt%. In the invention, a stable structure of the trimetal liquid alloy is formed among rhodium atoms in a rhodium elementary substance, gallium atoms in a gallium elementary substance and tin atoms in a tin elementary substance in the rhodium-gallium-tin liquid alloy, so that rhodium, gallium and tin are not aggregated, the bonding effect with a boron nitride carrier is strong, uniform active centers can be obtained, and the catalytic activity of the catalyst can be improved; and the cost is greatly reduced compared with the cost of noble metals (Pd, Ag and Au).
The invention provides a preparation method of a boron nitride loaded rhodium-gallium-tin liquid alloy catalyst in the technical scheme, which comprises the following steps:
mixing a water-soluble rhodium source, a water-soluble gallium source, a water-soluble tin source and water, mixing the obtained mixed solution with boron nitride, standing, dipping and drying to obtain a catalyst precursor;
and sequentially carrying out calcination and reduction reaction on the catalyst precursor to obtain the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of mixing a water-soluble rhodium source, a water-soluble gallium source, a water-soluble tin source and water, mixing the obtained mixed solution with boron nitride, standing, dipping and drying to obtain a catalyst precursor.
In the present invention, the water-soluble rhodium source preferably includes rhodium chloride, rhodium nitrate, ammonium chlororhodate, rhodium sulfate, potassium hexachlororhodium (III) or rhodium (III) triacetylacetonate, and more preferably is rhodium chloride. In the present invention, the water-soluble gallium source preferably includes gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate or gallium triethylate, and more preferably gallium chloride. In the present invention, the water-soluble tin source preferably includes stannous chloride dihydrate, stannic chloride, sodium stannate, tetraphenyltin, acetylacetonatostannic chloride, stannous sulfate or stannic ethoxide, more preferably stannous chloride dihydrate.
In the invention, the mass of the water-soluble rhodium source, the mass of the water-soluble gallium source and the mass of the water-soluble tin source are respectively calculated according to the mass of rhodium, gallium and tin, and the mass ratio of the water-soluble rhodium source, the water-soluble gallium source, the water-soluble tin source and boron nitride is preferably 0.002-0.015: 0.003 to 0.04: 0.003 to 0.04: 1, more preferably 0.003 to 0.012: 0.01-0.03: 0.01-0.03: 1, most preferably 0.005 to 0.01: 0.015 to 0.025: 0.015 to 0.025: 1.
in the invention, the mixing of the water-soluble rhodium source, the water-soluble gallium source, the water-soluble tin source and the water preferably comprises the steps of firstly mixing the water-soluble rhodium source and the first part of water to obtain a rhodium source solution; secondly, mixing the water-soluble gallium source with second part of water to obtain a gallium source solution; thirdly mixing the water-soluble tin source with the third part of water to obtain a tin source solution; and fourthly, mixing the rhodium source solution, the gallium source solution, the tin source solution and the residual water to obtain a mixed solution. The dosage of the first part of water, the second part of water and the third part of water is not particularly limited, and the concentrations of the rhodium source solution, the gallium source solution and the tin source solution can be ensured to be 5-15 mg/mL independently, more preferably 8-12 mg/mL, and even more preferably 10 mg/mL. The using amount of the residual water is not particularly limited, and the mass volume ratio of the boron nitride to the mixed solution is ensured to be 1 g: 20 mL. In the present invention, the first mixing, the second mixing, the third mixing and the fourth mixing are all preferably stirring mixing, and the speed of the stirring mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed. In the present invention, the time for the first mixing, the second mixing, and the third mixing is not particularly limited, and the water-soluble rhodium source, the water-soluble gallium source, or the water-soluble tin source may be dissolved in water. In the invention, the time for the fourth mixing is preferably 0.5-1 h.
In the present invention, when gallium chloride (GaCl) is used3) In the case of a water-soluble gallium source, the GaCl is preferably used3Dissolving in strong acid, and then mixing with the second part of water to obtain chloropalladate solution; the strong acid preferably comprises hydrochloric acid, nitric acid or sulfuric acid; the concentration of the strong acid is preferably 10-12 mol/L, and more preferably 12 mol/L; the mass-to-volume ratio of the palladium chloride to the strong acid is preferably 1 g: 1-3 mL, more preferably 1 g: 3 mL. The invention firstly prepares GaCl3Dissolving in concentrated hydrochloric acid to make trivalent gallium ion form Ga3 +The form exists.
In the invention, when the stannous chloride dihydrate is used as the water-soluble tin source, the stannous chloride dihydrate is preferably dissolved in strong acid and then mixed with the third part of water to obtain the acid solution of the stannous chloride; the strong acid preferably comprises hydrochloric acid, nitric acid or sulfuric acid; the concentration of the strong acid is 10-12 mol/L, and more preferably 12 mol/L; the mass volume ratio of the stannous chloride to the strong acid is preferably 1 g: 1-3 mL, more preferably 1 g: 3mL, can avoid the stannous chloride dihydrate to decompose in neutral aqueous solution to generate precipitate.
In the present invention, the mixing of the mixed solution and boron nitride is preferably performed by stirring, and the stirring and mixing speed is not particularly limited, and the raw materials may be uniformly mixed. In the invention, the mixing time is preferably 0.5-1 h.
In the invention, the standing impregnation is preferably carried out under a standing condition, and the standing time is preferably 6-12 hours, and more preferably 8-10 hours. In the invention, in the standing dipping process, the water-soluble rhodium source, the water-soluble gallium source and the water-soluble tin source are loaded on the surface of the boron nitride.
In the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 70-100 ℃, and more preferably 80 ℃; the vacuum drying time is preferably 6-15 hours, and more preferably 8-12 hours.
After the catalyst precursor is obtained, the catalyst precursor is sequentially subjected to calcination and reduction reaction to obtain the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst.
In the invention, the calcining temperature is preferably 500-1000 ℃, and more preferably 600-800 ℃; the calcination time is preferably 2-6 h, and more preferably 3-5 h. In the present invention, the calcination is preferably carried out in a protective atmosphere, which is preferably nitrogen or argon. In the calcining process, the water-soluble rhodium source, the water-soluble gallium source and the water-soluble tin source are subjected to in-situ thermal decomposition on the surface of boron nitride to respectively obtain rhodium oxide, gallium oxide and tin oxide.
In the present invention, the reducing gas used in the reduction reaction preferably includes one or more of hydrogen, methane, hydrogen sulfide and ammonia gas, more preferably includes hydrogen, methane, hydrogen sulfide or ammonia gas, and most preferably hydrogen. When the reducing gases used in the present invention are two or more, the ratio of the reducing gases used in the present invention is not particularly limited, and may be any ratio. In the present invention, the ratio of the flow rate of the calcined product to the reducing gas is preferably 0.5 g: 30-50 mL/min, more preferably 0.5 g: 40 mL/min.
In the invention, the temperature of the reduction reaction is preferably 200-600 ℃, and more preferably 300-500 ℃; the time of the reduction reaction is preferably 1-5 h, and more preferably 2-4 h. In the invention, in the reduction reaction process, rhodium oxide, gallium oxide and tin oxide are respectively reduced into elementary rhodium, elementary gallium and elementary tin, and simultaneously, active components rhodium, gallium and tin interact to form a liquid stable structure of three metals, so that rhodium, gallium and tin cannot agglomerate, and the combination effect of rhodium, gallium and tin with a boron nitride carrier is strong, thereby being beneficial to increasing the catalytic activity and stability of the catalyst.
The preparation method provided by the invention is simple to operate, low in raw material cost, free of secondary pollution due to the fact that water is used as a solvent, and suitable for industrial production.
The invention also provides the application of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared by the preparation method in the technical scheme in removing acetylene in ethylene by catalytic hydrogenation.
In the invention, the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst is preferably subjected to activation treatment before application. In the invention, the activation treatment is preferably reduction activation of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst by using hydrogen; the ratio of the mass of the boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst to the volume of hydrogen is preferably 1 g: (200-6000) mL, more preferably 1 g: (1000-3000) mL; the temperature of the activation treatment is preferably 100-300 ℃, and is preferably 150-250 ℃; the time of the activation treatment is preferably 0.5-2 h, and more preferably 1 h.
In the invention, the reaction conditions of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst for removing acetylene in ethylene by catalytic hydrogenation preferably comprise: the reaction gas is preferably C2H2/H2/C2H4Mixing the gas; c in the reaction gas2H2、H2And C2H4Is preferably 1: 2-10: 60-100, more preferably 1: 3-8: 70-90, most preferably 1: 4-6: 70-80, and the volume space velocity of the reaction gas is 1000-36000 h-1More preferably 1100 to 10000h-1More preferably 1200 to 5000 hours-1(ii) a The ratio of the mass of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst to the reaction gas pressure is preferably 0.2g (0.05-0.2) MPa, and more preferably 0.2g (0.05-0.1) MPa; the reaction temperature is preferably 30-210 ℃, more preferably 50-180 ℃, and most preferably 80-120 ℃; the reaction time is preferably 30 to 60 hours, and more preferably 40 to 50 hours.
In the invention, the preparation of ethylene by acetylene hydrogenation is preferably carried out in a fixed bed reactor, more preferably a fixed bed microreactor; the fixed bed micro-reactor has a fixed bed cavity inner diameter of preferably 2cm and a constant temperature heating zone length of preferably 10 cm.
In the embodiment of the invention, the catalytic effect of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst is preferably analyzed by using a gas chromatograph of a FID detector, wherein the sampling interval time is preferably 0.5 h.
The boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst forms a self-protection oxide layer liquid film in the process of preparing ethylene by catalyzing acetylene hydrogenation, and can avoid secondary reaction of ethylene on the surface of the catalyst, so that the formation of ethane byproducts by deep hydrogenation of acetylene is inhibited, and the catalyst has high selectivity and catalytic activity on ethylene.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dissolving 1g of rhodium chloride in deionized water, transferring the solution to a 100mL volumetric flask, adding deionized water to the scale of the volumetric flask, and shaking up to obtain a rhodium chloride solution with the concentration of 10 mg/mL;
dissolving 1g of gallium chloride in 3mL of concentrated hydrochloric acid (12mol/L), transferring the solution to a 100mL volumetric flask, adding deionized water to the scale of the volumetric flask, and shaking up to obtain an acid solution of gallium chloride with the concentration of 10 mg/mL;
dissolving 1g of stannous chloride dihydrate in 3mL of concentrated hydrochloric acid (12mol/L), transferring the solution to a 100mL volumetric flask, adding deionized water to the scale of the volumetric flask, and shaking up to obtain an acid solution of stannous chloride with the concentration of 10 mg/mL;
transferring 4.01mL of rhodium chloride solution, 2.52mL of gallium chloride solution and 1.46mL of stannous chloride solution by using a 1mL liquid transferring gun respectively, adding deionized water until the total volume is 20mL, and stirring and mixing for 0.5h to obtain a mixed solution;
(2) and adding the mixed solution into 1g of boron nitride, stirring and mixing for 1h, standing and soaking for 6h, and then placing in a vacuum drying oven to dry for 8h at the temperature of 80 ℃ to obtain a catalyst precursor.
(3) Calcining the catalyst precursor for 4 hours at 500 ℃ under the protection of argon, and then reducing for 2 hours at 200 ℃ in a hydrogen atmosphere to obtain the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst.
A TEM image of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in this embodiment is shown in fig. 1, and as can be seen from fig. 1, rhodium-gallium-tin liquid alloy particles in the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared in the present invention are uniformly distributed, which indicates that no metal agglomeration occurs in the boron nitride supported rhodium-gallium-tin liquid alloy catalyst provided in the present invention, and the catalyst dispersibility is good.
Examples 2 to 5
A boron nitride supported rhodium-gallium-tin liquid alloy catalyst was prepared according to the method of example 1, and the preparation conditions of examples 2 to 5 are shown in Table 1.
Comparative examples 1 to 2
A catalyst was prepared according to the method of example 1, and the preparation conditions of comparative examples 1 to 2 are shown in Table 1.
TABLE 1 amount of each raw material used in examples 1 to 5 and comparative examples 1 to 2
Application example
The catalysts prepared in examples 1-5 and comparative examples 1-2 are used as catalysts for preparing ethylene by acetylene hydrogenation, and are used for preparing ethylene by acetylene hydrogenation.
Wherein, the reaction conditions for preparing ethylene by acetylene hydrogenation are as follows: 200mg of catalyst is filled on a fixed bed microreactor, and the reaction gas is C2H2/H2/C2H4Mixed gas (C)2H2、H2And C2H4The molar ratio of (1: 2:100) and the volume space velocity of the reaction gas is 1200h-1The reaction pressure is 0.05MPa, the reaction temperature is 100 ℃, and the reaction time is 100 h; analyzing by using a gas chromatograph of an FID detector, wherein the sampling interval time is preferably 0.5 h; the fixed bed micro-reactor has a fixed bed cavity inner diameter of preferably 2cm and a constant temperature heating zone length of preferably 10 cm.
The catalytic effects of the catalysts prepared in examples 1 to 5 and comparative examples 1 to 2 in different reaction times are shown in fig. 2 to 8 and table 2, wherein fig. 2 is example 1, fig. 3 is example 2, fig. 4 is example 3, fig. 5 is example 4, fig. 6 is example 5, fig. 7 is comparative example 1, and fig. 8 is comparative example 2.
TABLE 2 catalytic Effect of catalysts prepared in examples 1 to 5 and comparative examples 1 to 2
| Conversion of acetylene/%) | Selectivity of ethylene/%) | |
| Example 1 | 98.9 | 99.6 |
| Example 2 | 97.4 | 94.3 |
| Example 3 | 88.8 | 88.4 |
| Example 4 | 95.4 | 92.2 |
| Example 5 | 93.4 | 90.1 |
| Comparative example 1 | 50.4 | 47.4 |
| Comparative example 2 | 46.9 | 42.1 |
As can be seen from fig. 2 to 6, the boron nitride supported rhodium-gallium-tin liquid alloy catalysts prepared in embodiments 1 to 5 of the present invention have increased acetylene conversion rates by increasing the reaction time within 0 to 5 hours, the acetylene conversion rates are sequentially maintained at about 98.9%, 97.4%, 88.8%, 95.4%, and 93.4% within 5 to 90 hours, and the activity of the catalysts starts to slightly decrease after the reaction time exceeds 90 hours, which indicates that the boron nitride supported rhodium-gallium-tin liquid alloy catalysts provided by the present invention have a long service life. As can be seen from Table 2, the boron nitride supported rhodium-gallium-tin liquid alloy catalysts prepared in examples 1 to 5 have a conversion rate of 88.8 to 98.9% to acetylene and a selectivity of 88.4 to 99.6% to ethylene, which indicates that the catalysts provided by the invention have high conversion rate to acetylene, high selectivity to ethylene and excellent catalytic effect.
From fig. 7 to 8, it can be seen that the conversion of acetylene increases with the reaction time of the catalysts prepared in comparative examples 1 to 2 being prolonged within 0 to 5 hours, the conversion of acetylene is maintained at about 50.4% and 46.9% in the 5 to 90 hours, and the activity of the catalysts starts to slightly decrease after the reaction time exceeds 90 hours. As can be seen from Table 2, the conversion of acetylene to ethylene of the catalysts prepared in comparative examples 1-2 is only 46.9-50.4%, and the selectivity to ethylene is only 42.1-47.4%, which indicates that the catalysts obtained by loading two metals in rhodium, gallium and tin have low conversion rate to acetylene, low selectivity to ethylene, and poor catalytic effect.
As can be seen from comparison of the catalytic effects of the catalysts prepared in example 1 and comparative examples 1 to 2, the catalyst obtained by supporting three metals, rhodium, gallium and tin, on boron nitride has an excellent catalytic effect on removal of acetylene from ethylene by catalytic hydrogenation, compared to the state alloy catalyst in which two metals, rhodium, gallium and tin, are supported on the surface of boron nitride.
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. A boron nitride supported rhodium-gallium-tin liquid alloy catalyst comprises boron nitride and an active component supported on the surface of the boron nitride; the active component includes a rhodium gallium tin liquid alloy.
2. The boron nitride supported rhodium-gallium-tin liquid alloy catalyst according to claim 1, wherein the content of active components in the boron nitride supported rhodium-gallium-tin liquid alloy catalyst is 0.8-8.5 wt%.
3. A method for preparing the boron nitride supported rhodium-gallium-tin liquid alloy catalyst as claimed in claim 1 or 2, characterized by comprising the following steps:
mixing a water-soluble rhodium source, a water-soluble gallium source, a water-soluble tin source and water, mixing the obtained mixed solution with boron nitride, standing, dipping and drying to obtain a catalyst precursor;
and sequentially carrying out calcination and reduction reaction on the catalyst precursor to obtain the boron nitride loaded rhodium-gallium-tin liquid alloy catalyst.
4. The preparation method according to claim 3, wherein the mass of the water-soluble rhodium source, the mass of the water-soluble gallium source and the mass of the water-soluble tin source are calculated according to the mass of rhodium, gallium and tin respectively, and the mass ratio of the water-soluble rhodium source to the water-soluble gallium source to the water-soluble tin source to boron nitride is 0.002-0.015: 0.003 to 0.04: 0.003 to 0.04: 1.
5. a method of manufacture as claimed in claim 3 or claim 4 wherein the water soluble source of rhodium comprises rhodium chloride, rhodium nitrate, ammonium chlororhodate, rhodium sulphate, potassium hexachlororhodium (III) or rhodium (III) triacetylacetonate.
6. The production method according to claim 3 or 4, characterized in that the water-soluble gallium source comprises gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate or gallium triethylate.
7. The method of claim 3 or 4, wherein the water-soluble tin source comprises stannous chloride dihydrate, stannic chloride, sodium stannate, tetraphenyltin, stannic acetylacetonate chloride, stannous sulfate, or stannic acetate.
8. The preparation method according to claim 3, wherein the calcination is carried out at a temperature of 500 to 1000 ℃ for 2 to 6 hours.
9. The preparation method according to claim 3, wherein the reducing gas used in the reduction reaction comprises one or more of hydrogen, methane, hydrogen sulfide and ammonia;
the temperature of the reduction reaction is 200-600 ℃, and the time is 1-5 h.
10. Use of the boron nitride supported rhodium-gallium-tin liquid alloy catalyst according to any one of claims 1 to 2 or the boron nitride supported rhodium-gallium-tin liquid alloy catalyst prepared by the preparation method according to any one of claims 3 to 9 in removing acetylene from ethylene by catalytic hydrogenation.
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