CN110560156A - supported ionic liquid-bimetallic palladium-based catalyst and preparation method and application thereof - Google Patents
supported ionic liquid-bimetallic palladium-based catalyst and preparation method and application thereof Download PDFInfo
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- CN110560156A CN110560156A CN201910814690.7A CN201910814690A CN110560156A CN 110560156 A CN110560156 A CN 110560156A CN 201910814690 A CN201910814690 A CN 201910814690A CN 110560156 A CN110560156 A CN 110560156A
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- palladium
- ionic liquid
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 46
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 13
- 238000005470 impregnation Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 imidazole cation Chemical class 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- GYTJXQRCNBRFGU-UHFFFAOYSA-N 1-methyl-3-propyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound Cl.CCCN1CN(C)C=C1 GYTJXQRCNBRFGU-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 16
- 239000005977 Ethylene Substances 0.000 abstract description 16
- 239000010949 copper Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical class CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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- B01J35/397—
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- 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
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- 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 supported ionic liquid-bimetallic palladium-based catalyst and a preparation method and application thereof, wherein the catalyst consists of an alumina carrier, an ionic liquid, a metal palladium compound and a second metal compound; the alumina supported ionic liquid-bimetallic palladium-based catalyst is applied to acetylene hydrogenation reaction, and has the advantages of high acetylene conversion rate, high ethylene selectivity and high stability.
Description
(I) technical field
the invention relates to a supported ionic liquid-bimetallic palladium-based catalyst, a preparation method thereof and application thereof in selective hydrogenation reaction of acetylene.
(II) background of the invention
Ethylene is one of the most important chemical products in the world, and is widely applied to various fields such as synthetic plastics, rubber, fibers, medicines, pesticides and dyes. Industrial ethylene is mainly produced by cracking naphtha, diesel oil and other raw materials, but about 0.3 to 3 percent of acetylene is often generated in the process of preparing ethylene gas; these traces of acetylene poison the Ziegler-Natta catalysts of downstream polyethylene processes, not only reducing the activity and lifetime of the catalyst, but also severely affecting the product quality of the polyethylene process. Therefore, the method has important industrial significance for removing trace acetylene in the raw material gas.
the method for removing acetylene commonly used in industry is a selective hydrogenation method, which has the advantages of no pollution, low energy consumption, simple process and the like and is widely applied. However, the palladium-based catalyst conventionally used in industry has a poor ethylene selectivity although it has a good catalytic activity, and may be excessively hydrogenated to ethane or oligomerized to green oil, thereby affecting the service life of the catalyst. Thus, the ethylene selectivity of palladium-based catalysts in acetylene hydrogenation is of great importance to the ethylene industry, and therefore, it is necessary to modify the catalysts to prevent the excessive hydrogenation of ethylene to ethane, thereby further improving the ethylene selectivity.
the ionic liquid is an electrolyte which is in a liquid state at room temperature or low temperature, and has the advantages of low vapor pressure, difficult combustion, low toxicity, excellent thermodynamics, excellent chemical stability and the like; the ionic liquid has special physical and chemical characteristics, so that the ionic liquid can be widely applied to catalytic reaction as a catalyst or a solvent;
based on the background, the invention provides an alumina-supported ionic liquid-bimetallic palladium-based catalyst to improve the selectivity of the palladium-based catalyst in selective hydrogenation of acetylene.
Disclosure of the invention
aiming at the defects in the prior art, the invention provides a supported ionic liquid-bimetallic palladium-based catalyst, a preparation method thereof and application thereof in selective hydrogenation reaction of acetylene. The preparation process is simple, and the prepared catalyst can greatly improve the ethylene selectivity in the selective hydrogenation reaction of acetylene.
the technical scheme of the invention is as follows:
A load type ionic liquid-bimetallic palladium-based catalyst is composed of an alumina carrier, an ionic liquid, a metal palladium compound and a second metal compound;
the specific surface area of the alumina carrier is 58-420 m2/g；
The metal palladium compound is chloropalladic acid, palladium nitrate, palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate or tetraamminepalladium nitrate, preferably palladium acetate;
The second metal compound is zinc chloride, copper chloride, chloroauric acid or stannic chloride, and copper chloride is preferred;
the ionic liquid is imidazole ionic liquid, cations of the ionic liquid are imidazole cations with different carbon chain lengths, and anions are chloride ions or bromide ions, and the specific examples are as follows: 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazolium tetrafluoroborate or 1-propyl-3-methylimidazole chloride, preferably 1-propyl-3-methylimidazole chloride; the ionic liquid forms an ionic liquid film on the inner surface of the carrier, so that a reaction environment is provided for active species;
in the catalyst, the loading amount of the metal palladium compound in terms of palladium is 0.01-0.5 wt% (preferably 0.01-0.1 wt%, more preferably 0.01-0.03 wt%), the loading amount of the second metal compound in terms of metal elements contained is 0.01-0.5 wt% (preferably 0.1-0.5 wt%, more preferably 0.5 wt%), and the loading amount of the ionic liquid is 10-40 wt% (preferably 10-30 wt%, more preferably 30 wt%), based on the mass of the carrier.
A preparation method of a supported ionic liquid-bimetallic palladium-based catalyst comprises the following steps:
(1) Dissolving a metal palladium compound in a solvent to prepare a palladium impregnation solution;
In the palladium impregnation liquid, the concentration of the metal palladium compound in terms of palladium is 0.001-0.01 g/mL;
The solvent depends on the kind of the metal palladium compound, and may be selected from, for example: deionized water, hydrochloric acid, ethanol, acetone and the like, and the invention has no special requirements for the method;
(2) Dissolving a second metal compound in a solvent to prepare a second metal impregnation liquid;
In the second metal impregnation liquid, the concentration of a second metal compound in terms of metal elements is 0.005-0.1 g/mL;
the solvent used is the same as the solvent in the palladium impregnation solution;
(3) Uniformly mixing the obtained palladium impregnation liquid with a second metal impregnation liquid, and then adding ionic liquid to uniformly mix to obtain an ionic liquid-bimetal compound impregnation liquid;
(4) Immersing an alumina carrier in an ionic liquid-bimetal compound impregnation liquid, dispersing uniformly, impregnating for 9-12 h at room temperature (20-30 ℃), and then drying for 9-12 h at 110-130 ℃, so as to obtain the supported ionic liquid-bimetal palladium-based catalyst;
In the invention, in the step (4), after the alumina carrier is immersed in the ionic liquid-bimetal compound impregnation liquid and impregnated for 9-12 hours, the system can be placed in a microwave reactor, the microwave is carried out for 20-80 min at the temperature of 110-130 ℃, the dispersion of metal components can be further promoted sufficiently, and then the sample is placed in an oven at the temperature of 110-130 ℃ and dried for 9-12 hours to obtain the final palladium-based catalyst;
In the preparation method of the catalyst of the present invention, the metal palladium compound, the second metal compound and the ionic liquid can be considered to be all supported, and the addition amount of the metal palladium compound, the second metal compound and the ionic liquid can be selected by those skilled in the art according to the required supported amount.
The supported ionic liquid-bimetallic palladium-based catalyst can be applied to acetylene hydrogenation reaction. Specifically, the application method comprises the following steps:
Before acetylene hydrogenation reaction, hydrogen is needed to reduce the catalyst, wherein the reduction temperature is 130-230 ℃ and the time is 1-3 h; and then the reduced catalyst is used for acetylene hydrogenation reaction, and the reaction conditions are as follows: the temperature is 100-210 ℃ (preferably 120-190 ℃), the pressure is 0.1-1 MPa (preferably 0.1-0.3 MPa, more preferably normal pressure), and the space velocity is 1000-10000 h-1(preferably 4000 to 8000 h)-1)；
In the acetylene hydrogenation reaction, the mixing composition proportion (volume fraction) of the initial reaction gas is as follows: 0.33% C2H2、0.66％H2、33.3％C2H4the balance N2。
compared with the prior art, the invention has the beneficial effects that:
(1) The aluminum oxide supported ionic liquid-bimetallic palladium-based catalyst firstly loads mixed solution of imidazole ionic liquid and bimetallic on an aluminum oxide carrier, wherein the imidazole ionic liquid forms a layer of liquid film on the surface of the carrier, and the ionic liquid film provides a stable reaction environment for an active center; on the other hand, the ionic liquid environment also provides certain energy for the migration of the second metal on the palladium active site, so that the second metal can more effectively promote the catalytic performance of palladium in the acetylene hydrogenation reaction. In addition, the alumina supported ionic liquid-bimetallic palladium-based catalyst prepared by the invention not only can further enhance the ethylene selectivity of the catalyst in the acetylene hydrogenation reaction, but also can increase the activity of the palladium-based catalyst by adding the second metal, thereby being better applied to the industry.
(2) The preparation method and the process of the alumina supported ionic liquid-bimetallic palladium-based catalyst are simple.
(3) The preparation method of the alumina supported ionic liquid-bimetallic palladium-based catalyst introduces the microwave treatment step, and can further promote the dispersion of bimetallic components and ionic liquid in a carrier, thereby further improving the selectivity of ethylene in the reaction.
(4) The alumina supported ionic liquid-bimetallic palladium-based catalyst is applied to acetylene hydrogenation reaction, and has the advantages of high acetylene conversion rate, high ethylene selectivity and high stability.
(IV) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Examples 1 to 5
weighing a certain amount of palladium acetate solid in a small beaker, adding a proper amount of deionized water for dissolving, transferring the solid to a volumetric flask after the palladium acetate is completely dissolved, and adding a certain amount of deionized water to corresponding scales to prepare the palladium chloride palladic acid solution with the mass concentration of palladium of 0.001 g/mL. Weighing a certain amount of copper chloride solid in a small beaker, adding a proper amount of deionized water for dissolving, transferring the copper chloride solid into a volumetric flask after the copper chloride solid is completely dissolved, and adding a certain amount of deionized water to corresponding scales to prepare a solution with the mass concentration of copper of 0.005 g/mL. According to the loading amount and the proportion thereof listed in the table 2, the metered palladium acetate solution, the metered copper chloride solution and the metered ionic liquid are mixed, a certain amount of deionized water is added, and after the mixture is uniformly stirred, the alumina carrier (with the specific surface area of 384 m) is uniformly mixed2/g) is poured into the impregnation solution and the catalyst is dispersed more homogeneously by ultrasound. And (3) soaking the wetted alumina at room temperature for 12h, and drying at 110 ℃ for 12h to obtain the supported ionic liquid-bimetallic palladium-based catalyst with good performance.
the texture properties of the alumina carrier before and after loading ionic liquid and Pd and Cu in the example 4 are compared in the following table 1:
TABLE 1 comparison of texture properties of supported ionic liquid-bimetallic palladium-based catalysts with supports
The data in Table 1 show that the supported ionic liquid is present in Al2O3the inner surface of the carrier forms a liquid film, i.e. an ionic liquid layer on the catalyst.
Example 6
with reference to the operation of example 5, the difference is only that the support is replaced by 58m having a smaller specific surface area2The supported ionic liquid-bimetallic palladium-based catalyst is prepared from the alumina per gram.
Example 7
with reference to the operation of example 5, the difference is only that the support is replaced by a support having a larger specific surface area of 420m2The supported ionic liquid-bimetallic palladium-based catalyst is prepared from the alumina per gram.
Example 8
the supported ionic liquid-bimetallic palladium-based catalyst prepared in example 2 was reacted in a microwave reactor at 110 ℃ for 80min to obtain a more dispersed supported ionic liquid-bimetallic palladium-based catalyst.
Example 9
The alumina supported ionic liquid-palladium catalyst prepared in example 5 was reacted in a microwave reactor at 120 ℃ for 70min to obtain a more dispersed supported ionic liquid-bimetallic palladium-based catalyst.
The catalyst activity and selectivity of the prepared catalyst were evaluated according to the following methods:
placing 0.3g of catalyst in a small quartz tube reactor, and placing the quartz tube in a heatable heating jacket; before reaction evaluation, reducing for 1h at 190 ℃ under the atmosphere of pure hydrogen gas, wherein the flow rate of the reducing gas is 10 mL/min; after completion of the reduction, the reaction was carried out at the temperature shown in Table 2. Wherein the reaction gas composition is (volume fraction): 0.33% acetylene, 33.3% ethylene, 0.66% H2the balance of nitrogen, and the flow rate of the reaction gas is 50 mL/min; the reaction pressure is normal pressure, the reaction gas outlet is connected with gas chromatography for on-line detection, and the evaluation result of the catalyst is shown in the following table 2.
TABLE 2 evaluation results of acetylene selective hydrogenation reaction of alumina-supported ionic liquid-bimetallic palladium-based catalyst
Examples 10 to 15
Referring to the preparation methods of the catalysts of examples 1 to 5, ionic liquids, loadings and ratios are shown in table 3, alumina-supported ionic liquid-bimetallic palladium-based catalysts were prepared.
The catalyst activity and selectivity were evaluated as above, with the reaction temperature being 170 ℃, while the mass percent of copper in the catalyst composition was varied, and the catalyst evaluation results are shown in table 3 below.
TABLE 3 evaluation results of acetylene selective hydrogenation reaction of supported ionic liquid-bimetallic palladium-based catalyst
| Examples | Load capacity wt% | Ionic Liquid (IL) species | Conversion of acetylene/% | Ethylene selectivity/%) |
| Example 10 | Pd＝0.03，IL＝30，Cu＝0.3 | Chlorinated 1-butyl-3-methylimidazole | ≥99.0 | 92.2 |
| Example 11 | Pd＝0.03，IL＝30，Cu＝0.4 | Chlorinated 1-butyl-3-methylimidazole | 99.2 | 92.8 |
| example 12 | Pd＝0.03，IL＝30，Cu＝0.1 | Chlorinated 1-propyl-3-methylimidazole | ≥99.5 | 93.3 |
| example 13 | Pd＝0.03，IL＝30，Cu＝0.2 | Chlorinated 1-propyl-3-methylimidazole | ≥99.2 | 94.1 |
| example 14 | Pd＝0.03，IL＝30，Cu＝0.3 | Chlorinated 1-propyl-3-methylimidazole | 98.4 | 94.5 |
| Example 15 | Pd＝0.03，IL＝30，Cu＝0.4 | Chlorinated 1-propyl-3-methylimidazole | 96.2 | 95.0 |
Examples 16 to 19
Referring to the preparation methods of the catalysts of examples 1 to 5, ionic liquids, loadings and ratios are shown in table 4, alumina-supported ionic liquid-bimetallic palladium-based catalysts were prepared.
the catalyst activity and selectivity were evaluated as above, the reaction temperature was still 170 ℃, only the reduction temperature of the catalyst was changed, and the catalyst evaluation results are shown in table 4 below.
TABLE 4 evaluation results of acetylene selective hydrogenation reaction of supported ionic liquid-bimetallic palladium-based catalyst
| Examples | load capacity wt% | Species of ionic liquids | Reduction temperature/. degree.C | Conversion of acetylene/% | Ethylene selectivity/%) |
| Example 16 | Pd＝0.3，IL＝30，Cu＝0.1 | Chlorinated 1-butyl-3-methylimidazole | 130 | 78 | 91.1 |
| Example 17 | Pd＝0.3，IL＝30，Cu＝0.1 | Chlorinated 1-butyl-3-methylimidazole | 170 | ≥99.5 | 91.6 |
| Example 18 | Pd＝0.3，IL＝30，Cu＝0.1 | Chlorinated 1-butyl-3-methylimidazole | 190 | ≥99.9 | 91.3 |
| Example 19 | Pd＝0.3，IL＝30，Cu＝0.1 | Chlorinated 1-butyl-3-methylimidazole | 230 | 40.3 | 91.6 |
Comparative examples 1 to 2
The invention Pd-Cu-IL/Al2O3Catalyst and Pd-IL/Al previously reported2O3The preparation methods of the catalysts are almost the same, but the catalysts have a large difference in acetylene hydrogenation reaction performance.
The catalyst activity and selectivity were evaluated as above, the reaction temperature was still 170 ℃, and the performance of the two catalysts was compared as follows.
Claims (8)
1. A load type ionic liquid-bimetallic palladium-based catalyst is characterized by comprising an alumina carrier, an ionic liquid, a metal palladium compound and a second metal compound;
the metal palladium compound is chloropalladic acid, palladium nitrate, palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate or tetraamminepalladium nitrate;
The second metal compound is zinc chloride, copper chloride, chloroauric acid or stannic chloride;
The ionic liquid is imidazole ionic liquid, the cation of the ionic liquid is imidazole cation, and the anion of the ionic liquid is chloride ion or bromide ion;
In the catalyst, based on the mass of the carrier, the loading amount of the metal palladium compound calculated by palladium is 0.01-0.5 wt%, the loading amount of the second metal compound calculated by the contained metal element is 0.01-0.5 wt%, and the loading amount of the ionic liquid is 10-40 wt%.
2. The supported ionic liquid-bimetallic palladium-based catalyst of claim 1, wherein the ionic liquid is: 1-butyl-3 methylimidazole chloride, 1-butyl-3 methylimidazolium tetrafluoroborate or 1-propyl-3 methylimidazole chloride.
3. The method of preparing the supported ionic liquid-bimetallic palladium-based catalyst as described in claim 1, wherein the method of preparing comprises the steps of:
(1) Dissolving a metal palladium compound in a solvent to prepare a palladium impregnation solution;
(2) Dissolving a second metal compound in a solvent to prepare a second metal impregnation liquid;
(3) Uniformly mixing the obtained palladium impregnation liquid with a second metal impregnation liquid, and then adding ionic liquid to uniformly mix to obtain an ionic liquid-bimetal compound impregnation liquid;
(4) Immersing an alumina carrier in an ionic liquid-bimetal compound impregnation liquid, dispersing uniformly, impregnating for 9-12 h at room temperature, and drying for 9-12 h at 110-130 ℃ to obtain the supported ionic liquid-bimetal palladium-based catalyst.
4. The method according to claim 3, wherein in the step (1), the concentration of the metal palladium compound in terms of palladium in the palladium-impregnated solution is 0.001 to 0.01 g/mL.
5. The method according to claim 3, wherein in the step (2), the concentration of the second metal compound in terms of the metal element contained in the second metal-impregnated solution is 0.005 to 0.1 g/mL.
6. The preparation method of claim 3, wherein in the step (4), the alumina carrier is immersed in the ionic liquid-bimetal compound impregnation liquid for 9-12 hours, then the system is placed in a microwave reactor, the microwave is carried out for 20-80 min at 110-130 ℃, and then the sample is placed in an oven at 110-130 ℃ and dried for 9-12 hours to obtain the final palladium-based catalyst.
7. Use of the supported ionic liquid-bimetallic palladium-based catalyst according to claim 1 in acetylene hydrogenation reactions.
8. The application of claim 7, wherein the method of applying is:
Before the acetylene hydrogenation reaction, reducing the catalyst by hydrogen at the temperature of 130-230 ℃ for 1-3 h; and then the reduced catalyst is used for acetylene hydrogenation reaction, and the reaction conditions are as follows: the temperature is 100-210 ℃, the pressure is 0.1-1 MPa, and the space velocity is 1000-10000 h-1；
In the acetylene hydrogenation reaction, the mixing composition proportion of reaction initial gas is as follows: 0.33% C2H2、0.66％H2、33.3％C2H4the balance N2。
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| CN114177937A (en) * | 2021-12-24 | 2022-03-15 | 天津大学 | Yttrium-based supported ionic liquid bimetallic catalyst and preparation method thereof |
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