CN109174177B - Alumina-supported ionic liquid-palladium catalyst, preparation thereof and application thereof in acetylene hydrogenation reaction - Google Patents
Alumina-supported ionic liquid-palladium catalyst, preparation thereof and application thereof in acetylene hydrogenation reaction Download PDFInfo
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- CN109174177B CN109174177B CN201810923803.2A CN201810923803A CN109174177B CN 109174177 B CN109174177 B CN 109174177B CN 201810923803 A CN201810923803 A CN 201810923803A CN 109174177 B CN109174177 B CN 109174177B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 56
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 47
- 239000002608 ionic liquid Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 21
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 13
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 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 abstract description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims abstract description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 3
- 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 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims description 19
- -1 imidazole cations Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 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 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 2
- HDXFBBSZRMZTFF-UHFFFAOYSA-N 1-methyl-3-pentyl-2h-imidazole Chemical compound CCCCCN1CN(C)C=C1 HDXFBBSZRMZTFF-UHFFFAOYSA-N 0.000 claims description 2
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical compound CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 24
- 239000005977 Ethylene Substances 0.000 abstract description 24
- 238000003795 desorption Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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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
- B01J31/0284—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 of an aromatic ring, e.g. pyridinium
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses an alumina supported ionic liquid-palladium catalyst, a preparation method thereof and application thereof in acetylene hydrogenation reaction. The catalyst comprises an alumina carrier, and ionic liquid and a palladium compound which are loaded on the surface of the carrier, wherein the palladium compound is selected from one of chloropalladic acid, palladium nitrate, palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate and tetraammine palladium nitrate; the positive ions of the ionic liquid are imidazole positive ions with different carbon chain lengths, and the negative ions are chloride ions, bromide ions, hexafluorophosphate radicals, tetrafluorophosphate radicals or tetrafluoroborate radicals; wherein the ionic liquid forms a layer of liquid film on the surface of the carrier, and the ionic liquid and the palladium compound form a carbene structure; in the catalyst, the load of palladium is 0.03-1wt%, and the load of ionic liquid is 8-40 wt%. The catalyst of the invention is used for selective hydrogenation of acetylene, and can promote ethylene desorption, thereby greatly improving the selectivity of ethylene in the reaction.
Description
(I) technical field
The invention relates to an alumina supported ionic liquid-palladium catalyst, a preparation method thereof and application thereof in reaction for preparing ethylene by selective hydrogenation of acetylene.
(II) technical background
Ethylene is widely used in various fields as an important organic chemical raw material. The ethylene raw material gas obtained by industrial production often contains 1% of acetylene. Trace amount of acetylene mixed in the raw material gas of ethylene can poison the catalyst of the subsequent ethylene polymerization reaction and reduce the quality of polyethylene products. Therefore, the acetylene in the raw material gas is removed to be below 5ppm, which has important significance.
In the ethylene plant, acetylene in the ethylene raw material is usually removed by a solvent absorption method and a selective hydrogenation method. Compared with a solvent absorption method, the catalytic selective hydrogenation method has less pollution, and can improve the yield of ethylene while removing acetylene impurities. However, the conventional catalysts used in industry have low ethylene selectivity at high acetylene conversion. This is due to the over-hydrogenation, which is caused by the fact that ethylene is not desorbed in time during the reaction.
Based on the above background, designing a suitable catalyst to improve the selectivity of ethylene in the selective hydrogenation reaction of acetylene is of great significance to the industrial production of ethylene.
Disclosure of the invention
The invention aims to provide an alumina supported ionic liquid-palladium catalyst for selective hydrogenation of acetylene, which can greatly improve the selectivity of ethylene in the selective hydrogenation reaction of acetylene.
The second purpose of the invention is to provide a method for preparing the alumina supported ionic liquid-palladium catalyst with simple process.
The third purpose of the invention is to provide the application of the alumina supported ionic liquid-palladium catalyst in the selective hydrogenation reaction of acetylene, which has the advantages of high acetylene conversion rate, high ethylene selectivity and good catalyst stability.
The technical solution used in the present invention is specifically described below.
In one aspect, the invention provides an alumina-supported ionic liquid-palladium catalyst, which comprises an alumina carrier, and an ionic liquid and a palladium compound which are supported on the surface of the carrier, wherein the palladium compound is selected from one of chloropalladic acid, palladium nitrate, palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate and tetraammine palladium nitrate; the ionic liquid is selected from imidazole ionic liquid, cations of the ionic liquid are selected from imidazole cations with different carbon chain lengths, and anions of the ionic liquid are chloride ions, bromide ions, hexafluorophosphate radicals, tetrafluorophosphate radicals or tetrafluoroborate radicals; wherein the ionic liquid forms a layer of liquid film on the surface of the carrier, and the ionic liquid and the palladium compound form a carbene structure; in the catalyst, the load of palladium is 0.03-1wt%, and the load of ionic liquid is 8-40 wt%.
In the present invention, the supported amount is defined as the mass percentage of the component relative to the carrier.
Furthermore, the specific surface area of the alumina carrier is 58-420m2/g。
Further, the palladium compound is preferably chloropalladite.
Further, the imidazole cations with different carbon chain lengths are cations formed by 1-ethyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-butyl-3-methylimidazole or 1-pentyl-3-methylimidazole.
Further, the ionic liquid is preferably 1-propyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-propyl-3-methylimidazole tetrafluoroborate or 1-propyl-3-methylimidazole hexafluorophosphate, which is liable to form a carbene structure with a palladium compound, and more preferably 1-propyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole chloride.
Further, the supported amount of palladium is preferably 0.05 to 0.1% by weight, more preferably 0.1% by weight; the loading of the ionic liquid is preferably 20 to 30wt%, more preferably 30 wt%.
In another aspect, the invention provides a preparation method of an alumina supported ionic liquid-palladium catalyst, comprising the following steps:
(1) preparing an impregnation liquid: dissolving a palladium compound by using a solvent to prepare a corresponding palladium compound impregnation liquid, wherein the mass concentration of palladium is 0.001-0.01 g/mL;
(2) preparation of ionic liquid-palladium complex: mixing the palladium compound impregnation liquid with the ionic liquid according to the proportion, and fully stirring and uniformly dispersing to obtain an ionic liquid-palladium compound impregnation liquid;
(3) uniformly pouring the alumina into the ionic liquid-palladium compound impregnation liquid to ensure that the alumina is completely immersed and fully dispersed by the impregnation liquid, impregnating the soaked carrier for 8-14h at room temperature, and then drying for 8-14h at the temperature of 110-130 ℃ to obtain the alumina supported ionic liquid-palladium catalyst.
In the preparation method of the catalyst of the present invention, the palladium compound and the ionic liquid can be considered as all supported, and the addition amount of the palladium compound and the ionic liquid can be selected by those skilled in the art according to the required supported amount.
In the step (1) of the present invention, the solvent may be water, hydrochloric acid solution, ethanol, etc., depending on the kind of the palladium compound, and the present invention does not particularly require this.
In the step (3) of the invention, if the impregnating solution can not immerse the added alumina, a certain amount of deionized water can be added to completely immerse the alumina.
In step (3) of the present invention, after the alumina is added, the alumina is uniformly dispersed in the impregnation solution, preferably by ultrasonic treatment.
Further, the preparation method also comprises the following step (4): and (4) placing the catalyst prepared in the step (3) in a microwave reactor, and carrying out microwave treatment at the temperature of 100-120 ℃ for 10-30min to obtain the finished catalyst. This step may further facilitate the formation of carbene structures.
In a third aspect, the invention provides an application of the alumina supported ionic liquid-palladium catalyst in selective hydrogenation reaction of acetylene. Before application, the catalyst is reduced by hydrogen at the temperature of 130 ℃ and 200 ℃ for 1-3 h.
Further, the conditions for selective hydrogenation of acetylene are: the reaction temperature is 60-210 ℃, the reaction pressure is 0.1-1MPa, and the space velocity is 4000--1。
In the selective hydrogenation of acetylene, the higher the reaction temperature is, the better the reaction activity is, but the selectivity is also reduced correspondingly. The preferred reaction temperature is 120-170 ℃. The reaction pressure is preferably 0.1 to 0.3MPa, and more preferably normal pressure. The preferred space velocity is 6000-10000h-1。
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the aluminum oxide supported ionic liquid-palladium catalyst, a mixed solution of imidazole ionic liquid and palladium is supported on an aluminum oxide carrier, on one hand, the imidazole ionic liquid forms a layer of liquid film on the surface of the carrier, and the relatively balanced hydrogen and acetylene ratio is formed on the surface of the catalyst by utilizing the characteristic of low solubility of hydrogen in the ionic liquid, so that excessive hydrogenation is prevented, and the ethylene selectivity of the reaction is improved; on the other hand, the imidazole ionic liquid and the active component palladium form a special carbene structure, the palladium is in an electron-rich state due to the electronic effect generated by the structure, and the desorption of ethylene from the surface of the palladium active component is promoted, so that the catalyst greatly improves the selectivity of ethylene in the reaction while keeping high acetylene conversion rate. In addition, the supported catalyst prepared by the method can reduce the dosage of expensive ionic liquid and reduce the cost; on the other hand, because the mass transfer effect of the ionic liquid is poor, the ionic liquid is loaded on the carrier to form a layer of liquid film, so that the mass transfer effect can be improved.
(2) The preparation method of the alumina supported ionic liquid-palladium catalyst has simple process.
(3) The preparation method of the alumina supported ionic liquid-palladium catalyst introduces a microwave treatment step, and can further promote the formation of a carbene structure, thereby further improving the selectivity of ethylene in the reaction.
(4) The alumina supported ionic liquid-palladium catalyst is applied to the preparation of ethylene by selective hydrogenation of acetylene, and has the advantages of high acetylene conversion rate, high ethylene selectivity and good stability.
(IV) description of the drawings
Fig. 1 is a schematic diagram of the selective hydrogenation of acetylene over an alumina supported ionic liquid-palladium catalyst having a carbene palladium structure.
FIGS. 2 and 3 are respectively Pd- [ Prmim ] prepared in example 7][Cl]/Al2O3The C1 s XPS spectrogram and the N1 s XPS spectrogram of the catalyst show that the position of Pd-NHC is the characteristic peak of carbene, which proves that the catalyst contains a carbene structure.
Fig. 4 and 5 are evaluation results of the selective hydrogenation of acetylene for a long time in example 11.
(V) detailed description of the preferred embodiments
The invention is illustrated by the following specific examples. It should be noted that the examples are only for further illustration of the present invention, but should not be construed as limiting the scope of the present invention.
Examples 1 to 9
Weighing a certain amount of PdCl2Dissolving in concentrated hydrochloric acid, transferring to a volumetric flask, adding a certain amount of deionized water to corresponding scales, and obtaining the chloropalladate solution with the mass concentration of palladium of 0.001 g/mL. According to the loading amount and the proportion thereof listed in the table 1, the metered chloropalladate solution and the ionic liquid are mixed, a certain amount of deionized water is added, and after uniform stirring, the alumina carrier (with the specific surface area of 384 m) is uniformly mixed2/g) pouring into the impregnation liquid, and performing ultrasonic treatment to uniformly disperse the impregnation liquid. And (3) soaking the wetted alumina at room temperature for 12h, and drying at 110 ℃ for 12h to obtain the alumina supported ionic liquid-palladium catalyst capable of forming a special carbene palladium structure.
FIGS. 2 and 3 are respectively Pd- [ Prmim ] prepared in example 7][Cl]/Al2O3The C1 s XPS spectrogram and the N1 s XPS spectrogram of the catalyst show that the position of Pd-NHC is the characteristic peak of carbene, which proves that the catalyst contains a carbene structure.
The texture properties of the alumina support before and after loading ionic liquid and Pd in example 7 are compared in table 1:
TABLE 1 comparison of texture properties of supports before and after loading with ionic liquids
The data in Table 1 show that the supported ionic liquid is present in Al2O3A liquid film is formed on the surface of the carrier.
Example 10
With reference to the operation of example 9, the only difference is that the support is exchanged for a support having a specific surface area of 58m2The alumina supported ionic liquid-palladium catalyst which can form a special carbene palladium structure is prepared by the alumina per gram.
Example 11
With reference to the operation of example 9, the only difference is that the support is replaced by a support having a specific surface area of 420m2The alumina supported ionic liquid-palladium catalyst which can form a special carbene palladium structure is prepared by the alumina per gram.
Example 12
The alumina supported ionic liquid-palladium catalyst prepared in example 2 is reacted in a microwave reactor at 100 ℃ for 30min to obtain a finished catalyst, and the C1 s XPS spectrum and the N1 s XPS spectrum of the finished catalyst also show that the catalyst contains a carbene structure.
Example 13
The alumina supported ionic liquid-palladium catalyst prepared in example 9 was reacted in a microwave reactor at 120 ℃ for 10min to obtain a finished catalyst, and the C1 s XPS spectrum and the N1 s XPS spectrum also showed that the catalyst contained a carbene structure.
The catalyst activity and selectivity of the prepared catalyst were evaluated according to the following methods:
0.3g of catalyst was placed in a small quartz tube reactor, the quartz tube was placed in a temperature-controllable heating furnace, and pure H was introduced before the reaction2Reducing for 1h at 180 ℃, wherein the flow rate of the reducing gas is 10 mL/min; after the reduction, the reaction was carried out while controlling the temperature at 150 ℃. The reaction gas composition (volume fraction): 0.33% acetylene, 0.66% hydrogen, 33% ethylene, and the balance nitrogen. The flow rate of the reaction gas was 50mL/min, and the reaction pressure was normal pressure. The reaction gas outlet is connected with a 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-palladium catalyst
Note:athe solubility ratio of acetylene and ethylene in 1-propyl-3-methylimidazole chloride was 1.4: 1.
examples 14 to 18
Weighing oneQuantitative PdCl2Dissolving in concentrated hydrochloric acid, transferring to a volumetric flask, adding a certain amount of deionized water to corresponding scales, and obtaining the chloropalladate solution with the mass concentration of palladium of 0.1 g/mL. According to the loading amount and the proportion thereof listed in the table 1, the metered chloropalladate solution and the ionic liquid are mixed, a certain amount of deionized water is added, and after uniform stirring, the alumina carrier (with the specific surface area of 384 m) is uniformly mixed2/g) pouring into the impregnation liquid, and performing ultrasonic treatment to uniformly disperse the impregnation liquid. And (3) soaking the wetted alumina at room temperature for 12h, and drying at 110 ℃ for 12h to obtain the alumina supported ionic liquid-palladium catalyst capable of forming a special carbene palladium structure.
The catalyst activity and selectivity evaluation methods were the same as above, only the reaction temperature was changed, and the catalyst evaluation results are shown in table 3 below.
TABLE 3 evaluation results of acetylene selective hydrogenation reaction of alumina-supported ionic liquid-palladium catalyst
Examples 19 to 23
Weighing a certain amount of PdCl2Dissolving in concentrated hydrochloric acid, transferring to a volumetric flask, adding a certain amount of deionized water to corresponding scales, and obtaining the chloropalladate solution with the mass concentration of palladium of 0.01 g/mL. According to the loading amount and the proportion thereof listed in the table 1, the metered chloropalladate solution and the ionic liquid are mixed, a certain amount of deionized water is added, and after uniform stirring, the alumina carrier (with the specific surface area of 384 m) is uniformly mixed2/g) pouring into the impregnation liquid, and performing ultrasonic treatment to uniformly disperse the impregnation liquid. And (3) soaking the wetted alumina at room temperature for 12h, and drying at 110 ℃ for 12h to obtain the alumina supported ionic liquid-palladium catalyst capable of forming a special carbene palladium structure.
The catalyst activity and selectivity evaluation methods were the same as above, the reaction temperature was kept constant at 150 ℃, the inlet flow rate of the reaction gas was varied, and the catalyst evaluation results are shown in table 4 below.
TABLE 4 evaluation results of acetylene selective hydrogenation reaction of alumina-supported ionic liquid-palladium catalyst
Example 24: stability test
The catalyst was evaluated for its selective hydrogenation performance for acetylene over a long period of time under the reaction conditions of example 11, and the results are shown in FIGS. 4 and 5, indicating that the catalyst had good stability.
Claims (13)
1. An alumina supported ionic liquid-palladium catalyst comprises an alumina carrier, and an ionic liquid and a palladium compound which are supported on the surface of the carrier, wherein the palladium compound is selected from one of chloropalladic acid, palladium nitrate, palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladite and tetraammine palladium nitrate; the ionic liquid is selected from imidazole ionic liquid, cations of the ionic liquid are selected from imidazole cations with different carbon chain lengths, and anions of the ionic liquid are chloride ions, bromide ions, hexafluorophosphate radicals, tetrafluorophosphate radicals or tetrafluoroborate radicals; wherein the ionic liquid forms a layer of liquid film on the surface of the carrier, and the ionic liquid and the palladium compound form a carbene structure; in the catalyst, the load of palladium is 0.03-1wt%, and the load of ionic liquid is 8-40 wt%.
2. The alumina-supported ionic liquid-palladium catalyst of claim 1, wherein: the specific surface area of the alumina carrier is 58-420m2/g。
3. The alumina-supported ionic liquid-palladium catalyst of claim 1, wherein: the palladium compound is palladium chloride acid.
4. The alumina-supported ionic liquid-palladium catalyst according to any one of claims 1 to 3, wherein: the imidazole cations with different carbon chain lengths are cations formed by 1-ethyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-butyl-3-methylimidazole or 1-pentyl-3-methylimidazole.
5. The alumina-supported ionic liquid-palladium catalyst of claim 4 wherein: the ionic liquid is selected from one of the following: 1-propyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-propyl-3-methylimidazole tetrafluoroborate and 1-propyl-3-methylimidazole hexafluorophosphate.
6. The alumina-supported ionic liquid-palladium catalyst according to any one of claims 1 to 3 or 5, wherein: the loading amount of palladium is 0.05-0.1 wt%; the loading of the ionic liquid is 20-30 wt%.
7. The alumina-supported ionic liquid-palladium catalyst of claim 6 wherein: the loading of palladium was 0.1 wt%.
8. The alumina-supported ionic liquid-palladium catalyst of claim 6 wherein: the loading of ionic liquid was 30 wt%.
9. A method of preparing the alumina-supported ionic liquid-palladium catalyst of claim 1, comprising the steps of:
(1) preparing an impregnation liquid: dissolving a palladium compound by using a solvent to prepare a corresponding palladium compound impregnation liquid, wherein the mass concentration of palladium is 0.001-0.01 g/mL;
(2) preparation of ionic liquid-palladium complex: mixing the palladium compound impregnation liquid with the ionic liquid according to the proportion, and fully stirring and uniformly dispersing to obtain an ionic liquid-palladium compound impregnation liquid;
(3) uniformly pouring the alumina into the ionic liquid-palladium compound impregnation liquid to ensure that the alumina is completely immersed and fully dispersed by the impregnation liquid, impregnating the soaked carrier for 8-14h at room temperature, and then drying for 8-14h at the temperature of 110-130 ℃ to obtain the alumina supported ionic liquid-palladium catalyst.
10. The method according to claim 9, further comprising the step (4) of: and (4) placing the catalyst prepared in the step (3) in a microwave reactor, and carrying out microwave treatment at the temperature of 100-120 ℃ for 10-30min to obtain the finished catalyst.
11. The application of the alumina supported ionic liquid-palladium catalyst in the selective hydrogenation reaction of acetylene as claimed in claim 1, wherein before the application, hydrogen is firstly used to reduce the catalyst, the reduction temperature is 130-200 ℃, and the reduction time is 1-3 h.
12. The use of claim 11, wherein: the conditions of the acetylene selective hydrogenation reaction are as follows: the reaction temperature is 60-210 ℃; the reaction pressure is 0.1-1 MPa; the airspeed is 4000-15000h-1。
13. The use of claim 11, wherein: the conditions of the acetylene selective hydrogenation reaction are as follows: the reaction temperature is 120-170 ℃; the reaction pressure is 0.1-0.3 MPa; the airspeed is 6000-10000h-1。
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| CN112191268B (en) * | 2020-08-31 | 2023-05-23 | 浙江工业大学 | Ni-IL/mesoporous aluminum oxide catalyst and preparation and application thereof |
| CN112191269A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Alumina-supported ionic liquid-copper catalyst, preparation thereof and application thereof in acetylene hydrogenation reaction |
| CN112473744B (en) * | 2020-11-27 | 2021-11-30 | 浙江工业大学 | Front-rear stage two-section type combined catalyst and application thereof |
| CN115608414B (en) * | 2021-07-16 | 2024-01-26 | 天津大学 | Supported ionic liquid nano metal catalyst and preparation method and application thereof |
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