CN110560156A - supported ionic liquid-bimetallic palladium-based catalyst and preparation method and application thereof - Google Patents
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 45
- 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 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 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 14
- 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 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 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 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 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 3
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 150000001875 compounds Chemical class 0.000 claims 3
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 238000001035 drying Methods 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
- 239000000243 solution Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000012495 reaction gas Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 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
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 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
- 238000005516 engineering process 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000006384 oligomerization reaction Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- 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
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- 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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Abstract
本发明提供了一种负载型离子液体‑双金属钯基催化剂及其制备方法与应用，所述催化剂由氧化铝载体、离子液体、金属钯化合物、第二金属化合物组成；本发明的氧化铝负载型离子液体‑双金属钯基催化剂应用于乙炔加氢反应中，具有乙炔转化率高、乙烯选择性高和稳定性高的优点。The invention provides a supported ionic liquid-bimetallic palladium-based catalyst and its preparation method and application, wherein the catalyst is composed of an alumina carrier, an ionic liquid, a metal palladium compound, and a second metal compound; the alumina-supported catalyst of the present invention The type ionic liquid bimetallic palladium-based catalyst is applied in the hydrogenation reaction of acetylene, and has the advantages of high acetylene conversion rate, high ethylene selectivity and high stability.
Description
(一)技术领域(1) Technical field
本发明涉及一种负载型离子液体-双金属钯基催化剂及其制备方法，以及在乙炔选择性加氢反应中的应用。The invention relates to a supported ionic liquid-bimetallic palladium-based catalyst, a preparation method thereof, and an application in acetylene selective hydrogenation reaction.
(二)背景技术(2) Background technology
乙烯是世界范围内最重要的化工产品之一，被广泛的应用于合成塑料、橡胶、纤维、医药、农药和染料等各个领域。工业上的乙烯主要通过石脑油和柴油等原料裂解制得，但是在制备乙烯气的过程中往往会生成大约0.3％-3％的乙炔；这些微量乙炔会毒化下游聚乙烯工艺的Ziegler-Natta催化剂，不仅会降低催化剂的活性和使用寿命，并且也会严重影响聚乙烯工艺的产品质量。因此，脱除原料气中微量乙炔具有重要的工业意义。Ethylene is one of the most important chemical products in the world and is widely used in various fields such as synthetic plastics, rubber, fibers, medicine, pesticides and dyes. Industrial ethylene is mainly produced through the cracking of raw materials such as naphtha and diesel, but in the process of preparing ethylene gas, about 0.3%-3% of acetylene is often generated; these traces of acetylene will poison the Ziegler-Natta of the downstream polyethylene process The catalyst will not only reduce the activity and service life of the catalyst, but also seriously affect the product quality of the polyethylene process. Therefore, the removal of trace acetylene in raw gas has important industrial significance.
工业上常用脱除乙炔的方法是选择加氢法，其具有无污染、能耗低、工艺过程简单等优点而被广泛应用。然而，工业上传统用的钯基催化剂虽然拥有着较优的催化活性，但是却有着较差的乙烯选择性，会发生过度加氢生成乙烷或者是发生低聚反应生成绿油从而影响催化剂的使用寿命。于是钯基催化剂在乙炔加氢反应中的乙烯选择性对乙烯工业来说是至关重要的，因此需要对催化剂进行改性，防止乙烯发生过度加氢生成乙烷，从而进一步提高乙烯的选择性。The method commonly used in industry to remove acetylene is selective hydrogenation, which has the advantages of no pollution, low energy consumption, and simple process, so it is widely used. However, although the palladium-based catalysts traditionally used in industry have better catalytic activity, they have poor ethylene selectivity, which will cause excessive hydrogenation to generate ethane or oligomerization to generate green oil, which will affect the performance of the catalyst. service life. Therefore, the ethylene selectivity of palladium-based catalysts in the acetylene hydrogenation reaction is crucial to the ethylene industry, so it is necessary to modify the catalyst to prevent ethylene from excessive hydrogenation to ethane, thereby further improving the ethylene selectivity .
离子液体是一类在室温或者低温下呈现液体状态的电解质，具有低蒸汽压、不易燃烧、低毒性、优异的热力学、化学稳定性等优点；离子液体具有特殊的物理与化学特性，这使得离子液体本身就可以作为催化剂或者作为溶剂在催化反应中得到了广泛的应用；Ionic liquids are a class of electrolytes that are in a liquid state at room temperature or low temperature, and have the advantages of low vapor pressure, non-flammability, low toxicity, excellent thermodynamics, and chemical stability; ionic liquids have special physical and chemical properties, which make ions The liquid itself can be used as a catalyst or as a solvent in catalytic reactions and has been widely used;
基于以上背景，本发明提出了一种氧化铝负载的离子液体-双金属钯基催化剂，以提高钯基催化剂在乙炔选择性加氢的选择性。Based on the above background, the present invention proposes an alumina-supported ionic liquid-bimetallic palladium-based catalyst to improve the selectivity of the palladium-based catalyst in the selective hydrogenation of acetylene.
(三)发明内容(3) Contents of the invention
针对现有技术中存在的不足，本发明提供了一种负载型离子液体-双金属钯基催化剂及其制备方法，以及在乙炔选择性加氢反应中的应用。本发明制备工艺简单，制得的催化剂能极大程度上提高乙炔选择性加氢反应中的乙烯选择性。Aiming at the deficiencies in the prior art, the invention provides a supported ionic liquid-bimetallic palladium-based catalyst and its preparation method, as well as its application in the selective hydrogenation reaction of acetylene. The preparation process of the invention is simple, and the prepared catalyst can greatly improve the ethylene selectivity in the acetylene selective hydrogenation reaction.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种负载型离子液体-双金属钯基催化剂，由氧化铝载体、离子液体、金属钯化合物、第二金属化合物组成；A supported ionic liquid-bimetallic palladium-based catalyst, consisting of an alumina carrier, an ionic liquid, a metal palladium compound, and a second metal compound;
所述氧化铝载体的比表面积为58～420m2/g；The specific surface area of the alumina support is 58-420m 2 /g;
所述金属钯化合物为氯钯酸、硝酸钯、醋酸钯、乙酰丙酮钯、二氯二氨钯、四氯钯酸铵、氯钯酸钠或硝酸四氨合钯，优选醋酸钯；The metal palladium compound is chloropalladium acid, palladium nitrate, palladium acetate, palladium acetylacetonate, dichlorodiammine palladium, ammonium tetrachloropalladate, sodium chloropalladate or tetraammine palladium nitrate, preferably palladium acetate;
所述第二金属化合物为氯化锌、氯化铜、氯金酸或氯化锡，优选氯化铜；The second metal compound is zinc chloride, copper chloride, chloroauric acid or tin chloride, preferably copper chloride;
所述离子液体为咪唑类离子液体，其阳离子为不同碳链长度的咪唑阳离子，阴离子为氯离子或溴离子，具体例如：氯化1-丁基-3甲基咪唑、1-丁基-3甲基咪唑四氟硼酸盐或氯化1-丙基-3甲基咪唑，优选氯化1-丙基-3-甲基咪唑；所述离子液体在载体内表面形成一层离子液体膜，为活性物种提供了反应环境；The ionic liquid is an imidazole ionic liquid, the cations are imidazolium cations with different carbon chain lengths, and the anions are chloride ions or bromide ions, for example: 1-butyl-3 methylimidazole chloride, 1-butyl-3 Methylimidazole 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, Provides a reactive environment for active species;
所述催化剂中，基于载体的质量，金属钯化合物以钯计的负载量为0.01～0.5wt％(优选0.01～0.1wt％，更优选0.01～0.03wt％)，第二金属化合物以所含金属元素计的负载量为0.01～0.5wt％(优选0.1～0.5wt％，更优选0.5wt％)，离子液体的负载量为10～40wt％(优选10～30wt％，更优选30wt％)。In the catalyst, based on the mass of the carrier, the metal palladium compound is loaded in an amount of 0.01 to 0.5 wt% (preferably 0.01 to 0.1 wt%, more preferably 0.01 to 0.03 wt%), and the second metal compound is loaded in the amount of metal The loading amount in terms of elements is 0.01-0.5wt% (preferably 0.1-0.5wt%, more preferably 0.5wt%), and the loading amount of the ionic liquid is 10-40wt% (preferably 10-30wt%, more preferably 30wt%).
一种负载型离子液体-双金属钯基催化剂的制备方法，所述制备方法包括以下步骤：A preparation method of supported ionic liquid-bimetallic palladium-based catalyst, said preparation method comprising the following steps:
(1)将金属钯化合物溶解于溶剂中，制得钯浸渍液；(1) metal palladium compound is dissolved in solvent, makes palladium impregnation solution;
所述钯浸渍液中，金属钯化合物以钯计的浓度为0.001～0.01g/mL；In the palladium impregnation solution, the concentration of the metal palladium compound in terms of palladium is 0.001 to 0.01 g/mL;
所述溶剂根据金属钯化合物的种类而定，例如可选自：去离子水、盐酸、乙醇、丙酮等，本发明对此没有特殊要求；The solvent depends on the type of metal palladium compound, for example, it can be selected from: deionized water, hydrochloric acid, ethanol, acetone, etc., the present invention has no special requirements on this;
(2)将第二金属化合物溶解于溶剂中，制得第二金属浸渍液；(2) dissolving the second metal compound in a solvent to obtain a second metal impregnation solution;
所述第二金属浸渍液中，第二金属化合物以所含金属元素计的浓度为0.005～0.1g/mL；In the second metal impregnating solution, the concentration of the second metal compound in terms of contained metal elements is 0.005-0.1 g/mL;
所用的溶剂与钯浸渍液中的溶剂相同；The solvent used is the same as in the palladium impregnation solution;
(3)将所得钯浸渍液与第二金属浸渍液混合均匀，然后加入离子液体混合均匀，得到离子液体-双金属复合物浸渍液；(3) Mix the obtained palladium impregnating solution with the second metal impregnating solution, then add the ionic liquid and mix uniformly to obtain the ionic liquid-bimetallic composite impregnating solution;
(4)将氧化铝载体浸没于离子液体-双金属复合物浸渍液中，分散均匀，室温(20～30℃)下浸渍9～12h，之后于110～130℃下干燥9～12h，即得所述负载型离子液体-双金属钯基催化剂；(4) Immerse the alumina carrier in the ionic liquid-bimetallic composite impregnation solution, disperse evenly, immerse at room temperature (20-30°C) for 9-12h, and then dry at 110-130°C for 9-12h to obtain The supported ionic liquid-bimetallic palladium-based catalyst;
本发明中，步骤(4)中将氧化铝载体浸没于离子液体-双金属复合物浸渍液并浸渍9～12h后，可将体系置于微波反应器中，在110～130℃下微波20～80min，可进一步充分促进金属组分的分散，然后再将样品放入110～130℃烘箱中干燥9～12h后得到最终的钯基催化剂；In the present invention, in step (4), after immersing the alumina carrier in the ionic liquid-bimetallic composite impregnation solution for 9 to 12 hours, the system can be placed in a microwave reactor and microwaved at 110 to 130°C for 20 to 20 hours. 80min, can further fully promote the dispersion of the metal component, and then put the sample in an oven at 110-130℃ to dry for 9-12h to obtain the final palladium-based catalyst;
本发明所述催化剂的制备方法中，金属钯化合物和第二金属化合物和离子液体可认为是全部负载，本领域技术人员可以根据需要的负载量选择金属钯化合物和第二金属化合物和离子液体的加入量。In the preparation method of catalyst described in the present invention, metal palladium compound and the second metal compound and ionic liquid can be considered as all loads, and those skilled in the art can select metal palladium compound and the second metal compound and ionic liquid according to the load of need. Amount added.
本发明所述负载型离子液体-双金属钯基催化剂可应用于乙炔加氢反应中。具体的，所述应用的方法为：The supported ionic liquid-bimetallic palladium-based catalyst of the invention can be applied to the hydrogenation reaction of acetylene. Specifically, the method of the application is:
在乙炔加氢反应前，需要先用氢气对所述催化剂进行还原，还原温度为130～230℃、时间为1～3h；再将还原后的催化剂用于乙炔加氢反应，反应条件为：温度100～210℃(优选120～190℃)、压力0.1～1MPa(优选0.1～0.3MPa，更优选常压)、空速1000～10000h-1(优选4000～8000h-1)；Before the acetylene hydrogenation reaction, the catalyst needs to be reduced with hydrogen, the reduction temperature is 130-230°C, and the time is 1-3h; then the reduced catalyst is used for the acetylene hydrogenation reaction, and the reaction conditions are: temperature 100-210°C (preferably 120-190°C), pressure 0.1-1MPa (preferably 0.1-0.3MPa, more preferably normal pressure), space velocity 1000-10000h -1 (preferably 4000-8000h -1 );
所述乙炔加氢反应中，反应初始气体的混合组成比例(体积分数)为：0.33％C2H2、0.66％H2、33.3％C2H4、余量N2。In the acetylene hydrogenation reaction, the mixing composition ratio (volume fraction) of the reaction initial gas is: 0.33% C 2 H 2 , 0.66% H 2 , 33.3% C 2 H 4 , and the balance N 2 .
与现有技术相比，本发明的有益效果在于：Compared with prior art, the beneficial effect of the present invention is:
(1)本发明的氧化铝负载型离子液体-双金属钯基催化剂，首先将咪唑类离子液体和双金属的混合液负载于氧化铝载体上，其中咪唑类离子液体在载体表面上形成一层液膜，这种离子液体液膜一方面为活性中心提供了稳定的反应环境；另一方面，这种离子液体环境也为第二金属在钯活性位点上的迁移提供了一定的能量，使得第二金属能够更加有效的促进钯在乙炔加氢反应的催化性能。此外，本发明制成的氧化铝负载型离子液体-双金属钯基催化剂不仅可以进一步增强催化剂在乙炔加氢反应中的乙烯选择性，并且第二金属的加入可以增加钯基催化剂的活性，从而更好的应用于工业上。(1) Alumina-supported ionic liquid-bimetallic palladium-based catalyst of the present invention, first the mixed solution of imidazoles ionic liquid and bimetal is loaded on the alumina carrier, wherein the imidazoles ionic liquid forms a layer on the surface of the carrier On the one hand, this ionic liquid liquid film provides a stable reaction environment for the active center; on the other hand, this ionic liquid environment also provides a certain amount of energy for the migration of the second metal on the palladium active site, making The second metal can more effectively promote the catalytic performance of palladium in the hydrogenation reaction of acetylene. In addition, the alumina-supported ionic liquid-bimetallic palladium-based catalyst made in the present invention can not only further enhance the ethylene selectivity of the catalyst in the hydrogenation reaction of acetylene, but the addition of the second metal can increase the activity of the palladium-based catalyst, thereby better applied in industry.
(2)本发明的氧化铝负载型离子液体-双金属钯基催化剂的制备方法和工艺简单。(2) The preparation method and process of the alumina-supported ionic liquid-bimetallic palladium-based catalyst of the present invention are simple.
(3)本发明的氧化铝负载型离子液体-双金属钯基催化剂的制备方法引入微波处理步骤，可以进一步促进双金属组分和离子液体在载体的分散，从而进一步提高反应中乙烯选择性。(3) The preparation method of the alumina-supported ionic liquid-bimetallic palladium-based catalyst of the present invention introduces a microwave treatment step, which can further promote the dispersion of the bimetallic component and the ionic liquid on the carrier, thereby further improving the ethylene selectivity in the reaction.
(4)本发明的氧化铝负载型离子液体-双金属钯基催化剂应用于乙炔加氢反应中，具有乙炔转化率高、乙烯选择性高和稳定性高的优点。(4) The alumina-supported ionic liquid-bimetallic palladium-based catalyst of the present invention is applied in the hydrogenation reaction of acetylene, and has the advantages of high acetylene conversion rate, high ethylene selectivity and high stability.
(四)具体实施方式(4) Specific implementation methods
下面通过具体实施例对本发明作进一步的说明，但本发明的保护范围并不仅限于此。The present invention will be further described below through specific examples, but the protection scope of the present invention is not limited thereto.
实施例1-5Example 1-5
称取一定量的醋酸钯固体于小烧杯中，加入适量的去离子水溶解，待醋酸钯完全溶解后转移至容量瓶中，加入一定量的去离子水到相应刻度，制得钯的质量浓度为0.001g/mL的氯钯酸溶液。称取一定量的氯化铜固体于小烧杯中，加入适量的去离子水溶解，完全溶解后转移至容量瓶中，加入一定量的去离子水到相应刻度，制得铜的质量浓度为0.005g/mL溶液。按照表2所列的负载量及其配比，将计量的醋酸钯溶液、氯化铜溶液和离子液体混合，并加入一定量的去离子水，搅拌均匀后，均匀地将氧化铝载体(比表面积为384m2/g)倒入浸渍液中，超声使催化剂分散地更加均匀。将润湿的氧化铝在室温浸渍12h，并在110℃下干燥12h，即制得性能良好的负载型离子液体-双金属钯基催化剂。Weigh a certain amount of palladium acetate solid in a small beaker, add an appropriate amount of deionized water to dissolve, transfer it to a volumetric flask after the palladium acetate is completely dissolved, add a certain amount of deionized water to the corresponding scale, and obtain the mass concentration of palladium It is a 0.001g/mL solution of chloropalladic acid. Weigh a certain amount of copper chloride solid in a small beaker, add an appropriate amount of deionized water to dissolve, transfer it to a volumetric flask after completely dissolving, add a certain amount of deionized water to the corresponding scale, and obtain a mass concentration of copper of 0.005 g/mL solution. According to the loading capacity listed in Table 2 and the proportion thereof, the metered palladium acetate solution, cupric chloride solution and ionic liquid are mixed, and a certain amount of deionized water is added, after stirring evenly, the alumina carrier (ratio The surface area is 384m 2 /g) is poured into the impregnation solution, and the catalyst is dispersed more uniformly by ultrasonication. Wet alumina was impregnated at room temperature for 12 hours, and dried at 110° C. for 12 hours to obtain a supported ionic liquid-bimetallic palladium-based catalyst with good performance.
实施例4中氧化铝载体在负载离子液体和Pd、Cu前后织构性质比较见表1：In Example 4, the comparison of the texture properties of the alumina carrier before and after loading ionic liquid, Pd, and Cu is shown in Table 1:
表1负载型离子液体-双金属钯基催化剂与载体织构性质比较Table 1 Comparison of texture properties between supported ionic liquid-bimetallic palladium-based catalysts and supports
表1的数据表明负载的离子液体在Al2O3载体内表面形成了液膜，也就是在催化剂上形成了离子液体层。The data in Table 1 shows that the supported ionic liquid forms a liquid film on the inner surface of the Al 2 O 3 carrier, that is, forms an ionic liquid layer on the catalyst.
实施例6Example 6
参照实施例5的操作，区别仅在于载体换成比表面积较小的58m2/g的氧化铝，制得负载型离子液体-双金属钯基催化剂。Referring to the operation of Example 5, the only difference is that the carrier is replaced by alumina with a smaller specific surface area of 58 m 2 /g to obtain a supported ionic liquid-bimetallic palladium-based catalyst.
实施例7Example 7
参照实施例5的操作，区别仅在于载体换成比表面积较大420m2/g的氧化铝，制得负载型离子液体-双金属钯基催化剂。Referring to the operation of Example 5, the only difference is that the carrier is replaced by alumina with a larger specific surface area of 420m 2 /g to obtain a supported ionic liquid-bimetallic palladium-based catalyst.
实施例8Example 8
将实施例2制备的负载型离子液体-双金属钯基催化剂在微波反应器中于110℃反应80min，得到更加分散的负载型离子液体-双金属钯基催化剂。The supported ionic liquid-bimetallic palladium-based catalyst prepared in Example 2 was reacted in a microwave reactor at 110° C. for 80 minutes to obtain a more dispersed supported ionic liquid-bimetallic palladium-based catalyst.
实施例9Example 9
将实施例5制备的氧化铝负载离子液体-钯催化剂在微波反应器中于120℃反应70min，得到更加分散的负载型离子液体-双金属钯基催化剂。The alumina-supported ionic liquid-palladium catalyst prepared in Example 5 was reacted in a microwave reactor at 120° C. for 70 minutes to obtain a more dispersed supported ionic liquid-bimetallic palladium-based catalyst.
制得的催化剂按照下面方法进行催化剂活性及选择性评价：The prepared catalyst carries out catalyst activity and selectivity evaluation according to the following method:
将0.3g催化剂置于小型石英管反应器中，将石英管放置于可加热的加热套中；在反应评价前，在纯氢气体气氛下190℃下还原1h，还原气流速为10mL/min；还原结束后，按表2所示温度下进行反应。其中反应气体组成为(体积分数)：0.33％乙炔，33.3％乙烯，0.66％H2，余量氮气，反应气的流速为50mL/min；反应压力为常压，反应气出口接气相色谱在线检测，催化剂的评价结果见下表2所示。Put 0.3g of catalyst in a small quartz tube reactor, and place the quartz tube in a heatable heating mantle; before the reaction evaluation, it was reduced at 190°C for 1h under a pure hydrogen gas atmosphere, and the reducing gas flow rate was 10mL/min; After reduction finishes, carry out reaction under the temperature shown in table 2. Wherein the reaction gas composition is (volume fraction): 0.33% acetylene, 33.3% ethylene, 0.66% H 2 , the balance of nitrogen, the flow rate of the reaction gas is 50mL/min; the reaction pressure is normal pressure, and the outlet of the reaction gas is connected to the gas chromatography for online detection , The evaluation results of the catalyst are shown in Table 2 below.
表2氧化铝负载型离子液体-双金属钯基催化剂的乙炔选择性加氢反应评价结果Table 2 Evaluation results of acetylene selective hydrogenation reaction of alumina-supported ionic liquid-bimetallic palladium-based catalyst
实施例10-15Examples 10-15
参照实施例1-5的催化剂的制备方法，离子液体、负载量和配比见表3，制备氧化铝负载型离子液体-双金属钯基催化剂。Referring to the preparation method of the catalyst in Examples 1-5, see Table 3 for the ionic liquid, loading capacity and proportion, to prepare an alumina-supported ionic liquid-bimetallic palladium-based catalyst.
催化剂活性和选择性的评价方法同上，反应温度为170℃，同时改变催化剂组成中铜的质量配比百分数，催化剂的评价结果见下表3所示。The evaluation method of catalyst activity and selectivity is the same as above, the reaction temperature is 170°C, and the mass proportion percentage of copper in the catalyst composition is changed at the same time. The evaluation results of the catalyst are shown in Table 3 below.
表3负载型离子液体-双金属钯基催化剂的乙炔选择性加氢反应评价结果Table 3 Evaluation results of the selective hydrogenation of acetylene over supported ionic liquid-bimetallic palladium-based catalysts
实施例16-19Examples 16-19
参照实施例1-5的催化剂的制备方法，离子液体、负载量和配比见表4，制备氧化铝负载型离子液体-双金属钯基催化剂。Referring to the preparation method of the catalyst in Examples 1-5, see Table 4 for the ionic liquid, loading capacity and proportion, to prepare an alumina-supported ionic liquid-bimetallic palladium-based catalyst.
催化剂活性和选择性的评价方法同上，反应温度仍为170℃，只改变催化剂的还原温度，催化剂的评价结果见下表4所示。The evaluation method of catalyst activity and selectivity is the same as above, the reaction temperature is still 170°C, only the reduction temperature of the catalyst is changed, and the evaluation results of the catalyst are shown in Table 4 below.
表4负载型离子液体-双金属钯基催化剂的乙炔选择性加氢反应评价结果Table 4 Evaluation results of acetylene selective hydrogenation reaction of supported ionic liquid-bimetallic palladium-based catalyst
对比例1-2Comparative example 1-2
本发明Pd-Cu-IL/Al2O3催化剂与先前报道的Pd-IL/Al2O3催化剂的制备方法几乎是相同的，但是其催化剂在乙炔加氢反应性能上存在很大差距。The preparation method of the Pd-Cu-IL/Al 2 O 3 catalyst of the present invention is almost the same as that of the previously reported Pd-IL/Al 2 O 3 catalyst, but there is a large gap in the performance of the catalyst in acetylene hydrogenation reaction.
催化剂活性和选择性评价方法同上，反应温度仍为170℃，两个催化剂的性能比较如下。The catalyst activity and selectivity evaluation methods are the same as above, and the reaction temperature is still 170°C. The performance comparison of the two catalysts is as follows.
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| 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 |
| CN112151815A (en) * | 2020-09-27 | 2020-12-29 | 江南大学 | A PdZn alloy nanocatalyst for ethanol fuel cells |
| CN112151815B (en) * | 2020-09-27 | 2022-02-15 | 江南大学 | A PdZn alloy nanocatalyst for ethanol fuel cells |
| CN114177937A (en) * | 2021-12-24 | 2022-03-15 | 天津大学 | Yttrium-based supported ionic liquid bimetallic catalyst and preparation method thereof |
| CN114471615A (en) * | 2022-02-24 | 2022-05-13 | 河南科技大学 | Preparation method and application of Pd-Cu alloy nano sea urchin |
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