CN115608414B - Supported ionic liquid nano metal catalyst and preparation method and application thereof - Google Patents
Supported ionic liquid nano metal catalyst and preparation method and application thereof Download PDFInfo
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- CN115608414B CN115608414B CN202110808825.6A CN202110808825A CN115608414B CN 115608414 B CN115608414 B CN 115608414B CN 202110808825 A CN202110808825 A CN 202110808825A CN 115608414 B CN115608414 B CN 115608414B
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 title abstract description 18
- 239000002184 metal Substances 0.000 title abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 107
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 11
- 239000011343 solid material Substances 0.000 claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 10
- 150000004056 anthraquinones Chemical class 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- IYHLUGVVUPPBEJ-UHFFFAOYSA-N 1-butyl-3-ethenyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCC[NH+]1CN(C=C)C=C1 IYHLUGVVUPPBEJ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- WIEZTXFTOIBIOC-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.Cl[Pd]Cl WIEZTXFTOIBIOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 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
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 23
- -1 imidazole cation Chemical class 0.000 abstract description 22
- 150000001450 anions Chemical class 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 229940006460 bromide ion Drugs 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 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 description 10
- 239000002082 metal nanoparticle Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- AKIOUZFROHTEEN-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium chloride Chemical compound [Cl-].CCCC[NH+]1C=CN(C)C1C AKIOUZFROHTEEN-UHFFFAOYSA-N 0.000 description 2
- XUHHZNLAPUWRHH-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCCCN1CN(C)C=C1 XUHHZNLAPUWRHH-UHFFFAOYSA-N 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000002633 protecting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- NCKNEUYMXRAPNR-UHFFFAOYSA-N 1-ethyl-10h-anthracen-9-one Chemical compound C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC NCKNEUYMXRAPNR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- KBOGIATXPIINBP-UHFFFAOYSA-N [Br].C(=C)N1CN(C=C1)CCCC Chemical compound [Br].C(=C)N1CN(C=C1)CCCC KBOGIATXPIINBP-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B01J35/23—
-
- 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
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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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 discloses a supported ionic liquid nano metal catalyst, a preparation method and application thereof, which consists of a porous solid material carrier, imidazole ionic liquid and Pd metal compound supported on the carrier; the porous solid material is gamma-Al 2 O 3 The cation of the imidazole ionic liquid is imidazole cation, the anion is hydrogen sulfate ion, methane sulfonate ion, dihydrogen phosphate, acetate ion, chloride ion or bromide ion, and the imidazole cation is 1-butyl-3-methylimidazole cation, 1-butyl-2, 3-dimethylimidazole cation or 1-vinyl-3-butylimidazole cation. The ionic liquid plays a role of 'bridging' to strengthen interaction between palladium nano metal and a catalyst carrier, reduce the problem that active components of the catalyst are easy to run away in the use process, and improve the stability of the palladium metal catalyst.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a supported ionic liquid nano metal catalyst and a preparation method and application thereof.
Background
Ionic liquids are a class of salts consisting of anions and cations, typically organic cations, and inorganic or organic anions. The ionic liquid has the characteristics of good solubility, high thermal stability, low vapor pressure, small volatility, adjustable structure and the like, and is widely applied to the related fields of catalysis, adsorption, separation, purification and the like. The environment provided by the ionic liquid microphase can be used for stabilizing metal nano ions, so that the dispersity of metal nano particles can be improved, and meanwhile, the unique functional group structure of the ionic liquid and the metal particles form coordination action to stabilize the metal nano particles.
Chinese patent application publication No. CN110496645a discloses a supported ionic liquid-bimetallic palladium-based catalyst for use in selective hydrogenation of acetylene. The ionic liquid adopts imidazole ionic liquid, cations are imidazole cations with different carbon chain lengths, anions are chloride ions or bromide ions, and alumina is used as a carrier to prepare a series of palladium-based bimetallic catalysts, and the ionic liquid can provide stable reaction environment for active centers and provide energy for migration of second metals, so that the ethylene selectivity of the catalysts in acetylene hydrogenation reaction is improved. However, the method has the problems of complicated catalyst preparation process, complex components and the like.
Disclosure of Invention
The invention aims at overcoming the technical defects in the prior art and provides a supported ionic liquid nano metal catalyst.
The invention further aims at providing a preparation method of the supported ionic liquid nano metal catalyst.
The invention also aims to provide application of the supported ionic liquid nano metal catalyst.
The technical scheme adopted for realizing the purpose of the invention is as follows:
an alumina-supported imidazole ionic liquid-Pd-based catalyst comprises a porous solid material carrier and imidazole ion supported on the carrierA sub-liquid and a Pd metal compound; the porous solid material is gamma-Al 2 O 3 。
In the above technical solution, the gamma-Al 2 O 3 Has a specific surface area of 100 to 500m 2 And/g, pore diameter is 5-18 nm.
In the above technical solution, the gamma-Al 2 O 3 The preparation method comprises the steps of preparing precursor pseudo-boehmite (AlOOH.nH) 2 O) heating to 400-800 ℃ from room temperature at a heating rate of 1-10 ℃/min, and calcining for 2-8 h.
In the above technical solution, the Pd metal compound is sodium chloropalladate, palladium nitrate, palladium acetate, palladium acetylacetonate, diamminedichloropalladium, ammonium tetrachloropalladate or tetraamminepalladium nitrate, and more preferably sodium chloropalladate.
In the above technical scheme, the imidazole ionic liquid has an imidazole cation, and the anion is hydrogen sulfate ion, methane sulfonate ion, dihydrogen phosphate, acetate ion, chloride ion or bromide ion, and the imidazole cation is 1-butyl-3-methylimidazole cation, 1-butyl-2, 3-dimethylimidazole cation or 1-vinyl-3-butylimidazole cation.
In the imidazole ionic liquid, the cations contain a long chain radical side chain, and the cations on or near the surfaces of the nanoparticles can provide space force by stretching the side chains of the nanoparticles, so that the nanoparticles are prevented from approaching each other and agglomeration of the metal nanoparticles is prevented.
Hydrogen sulfate ion, methane sulfonate ion, acetate ion, and dihydrogen phosphate as acidityThe anions of the ionic liquid can directly provide proton hydrogen, the acid strength is adjustable, the acid is not easy to run off, and the water stability is good.
In the technical scheme, the load of the Pd metal compound in terms of Pd is 0.05-10wt%, preferably 2-4wt%, and the load of the ionic liquid is 1-20wt%, preferably 1-6wt%. In the invention, the load refers to the mass percent of the substance to the carrier.
In another aspect of the invention, a method for preparing an alumina-supported imidazole ionic liquid-Pd-based catalyst comprises the following steps:
step 1, dissolving a Pd metal compound in a deionized water solvent, and fully dispersing by ultrasonic to obtain a Pd impregnation liquid; in the Pd impregnating solution, the concentration of Pd metal compounds is 0.1-5 mg/mL;
step 2, dissolving the ionic liquid in deionized water solvent, and fully dispersing by ultrasonic waves to obtain ionic liquid impregnating solution; in the ionic liquid impregnating solution, the concentration of the ionic liquid is 0.5-8 mg/mL;
step 3, uniformly mixing the obtained Pd impregnating solution and the ionic liquid impregnating solution at 20-60 ℃ to obtain ionic liquid-Pd impregnating solution;
and 4, adding 0.5-5 g of carrier into the ionic liquid-Pd impregnating solution, stirring for 0.5-5 h at 20-60 ℃, uniformly dispersing, aging at 20-60 ℃ and standing for 1-12 h, filtering and washing, and drying for 9-24 h in a baking oven at 60-150 ℃.
In another aspect, the invention includes the use of the alumina-supported imidazole ionic liquid-Pd-based catalyst.
In the technical scheme, when the ionic liquid is 1-vinyl-3-butyl imidazole bromide or 1-butyl-3-methyl imidazole acetate, the alumina-supported imidazole ionic liquid-Pd-based catalyst is directly applied to hydrogenation reaction;
when the ionic liquid is 1-butyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole methane sulfonate or 1-butyl-2, 3-dimethylimidazole chloride, the catalyst is reduced by a reducing agent and then is applied to hydrogenation reaction.
In the above technical solution, the reduction method is as follows: reducing by hydrogen or sodium borohydride, heating to 25-230 ℃ from room temperature at a heating rate of 1-10 ℃/min, and preserving heat for 0-6 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, through the unique space limiting action and electrostatic action of the ionic liquid and the coordination action between the ionic liquid and the palladium nano metal, the size of the nano particles is limited in the formation process of the palladium nano particles, meanwhile, the palladium nano particles are stabilized, the dispersity of the palladium nano particles is improved, the aggregation phenomenon is reduced, and the catalytic efficiency of the palladium nano particles is improved.
2. According to the invention, on one hand, ionic liquid is adsorbed on the surface of a carrier through electrostatic action, on the other hand, the ionic liquid provides a layer of protective film for an active component and is distributed around palladium nano particles, the purpose of stabilizing and dispersing palladium is achieved through electrostatic action and steric hindrance, the ionic liquid plays a role in strengthening interaction between palladium nano metal and a catalyst carrier, the problem that the active component is easy to run off in the use process of the catalyst is reduced, and the stability of the palladium metal catalyst is improved.
3. The catalyst of the invention is used in an anthraquinone hydrogenation reaction system, improves the catalytic hydrogenation activity and selectivity, and improves the product H 2 O 2 Is a mass of (3).
4. The preparation method is simple, the reduction condition is mild, the catalyst precursor is decomposed into oxides by high-temperature roasting before the reduction of the traditional catalyst, volatile components are removed, certain chemical composition is reserved, the mechanical strength of the catalyst is enhanced, active components are anchored on a carrier, and the combination fastness of the active components and the carrier is improved; the catalyst does not undergo a high-temperature roasting process, so that the ionic liquid is introduced to strengthen the interaction between palladium nano metal and the catalyst carrier, and the loss of active components of the catalyst in the use process is reduced. On the other hand, the decomposition temperature of the ionic liquid is lower, and the ionic liquid can be decomposed by high-temperature roasting to damage the structure of the ionic liquid, so that the structure and the catalytic activity of the catalyst are affected.
5. The size of the metal nano particles is limited by the unique domain limiting effect of the ionic liquid, the dispersibility of the metal is improved, and the size of the metal nano particles is limited in the nucleation and growth processes of the metal nano ions in a microphase environment provided by the ionic liquid. The metal nano particles have high surface free energy due to small size, are in an unstable state and are easy to aggregate. The ionic liquid is composed of anions and cations, and a certain 'macromolecular network structure' can be formed in space, so that the ionic liquid has an electronic effect and a steric effect to stabilize the metal nano particles, and can effectively prevent agglomeration of the metal nano particles.
Drawings
FIG. 1 shows STEM diagram (a) and elemental distribution diagram (b-i) of supported ionic liquid palladium-based catalyst.
In order to observe the distribution of elements on the supported ionic liquid catalyst, scanning electron microscope (STEM) analysis is carried out, mapping analysis is carried out on each element on a catalyst sample, the ionic liquid is 1-butyl-3-methylimidazole bisulfate ionic liquid, and the carrier is gamma-Al 2 O 3 As shown in fig. 1. From the elemental distribution pattern, the main elements constituting the catalyst were Al and O elements, since the support was Al 2 O 3 For this reason, it was also found that C, N, S, pd elements, which are derived from the imidazole-based ionic liquid and the catalyst precursor Na, are distributed to varying degrees 2 PdCl 4 Wherein the N element is derived from ionic liquid cations and the S element is derived from ionic liquid anions. The N element and the Pd element are distributed and overlapped, and the N element and the Pd element are found to be uniformly distributed around each other, so that the Pd species are uniformly surrounded by the ionic liquid, the dispersity of the prepared catalyst Pd is good to a certain extent, and the ionic liquid has the stabilizing and protecting effects on the Pd species.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Examples 1 to 4
Pseudo-boehmite (AlOOH.nH) 2 O) calcining in a muffle furnace at 600 ℃ for 4 hours at a heating rate of 5 ℃/min to obtain gamma-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the According to the load amount listed in table 1, the metered sodium chloropalladate and the imidazole ionic liquid are mixed in a scattered manner to obtain an ionic liquid-palladium impregnating solution; gamma-Al 2 O 3 Adding the carrier into the mixed soaking solution, stirring at 45deg.C for 1.5 hr, aging at 45deg.CStanding for 3h, filtering, washing, and drying in an oven at 80 ℃ for 12h to obtain the alumina-supported ionic liquid-palladium-based catalyst.
Reducing with hydrogen at 150 deg.c for 4 hr at 5 deg.c/min; obtaining the final alumina-supported ionic liquid Pd-based catalyst.
The alumina-supported ionic liquid-Pd-based catalyst can be applied to anthraquinone hydrogenation reaction, the concentration of an anthraquinone working solution is 120g/L, the hydrogen pressure is 0.3Mpa, the rotating speed is 1000rpm, the temperature is 60 ℃, and 0.6g of the catalyst and 60mL of the working solution are reacted in a reaction kettle for 15min to evaluate hydrogenation performance.
The evaluation results of the catalyst are shown in Table 1.
TABLE 1 preparation of alumina Supported ionic liquid-Palladium-based catalyst and evaluation results of Activity in anthraquinone hydrogenation reactions
Examples | Load wt% | Ionic liquid species | Hydrogenation efficiency (g/L) |
Example 1 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole bisulfate | 6.7 |
Example 2 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole chloride | 7.5 |
Example 3 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole methane sulfonate | 7.2 |
Example 4 | Pd=0.3,IL=3 | 1-butyl-2, 3-dimethylimidazole chloride salt | 5.8 |
Comparative example 1 | Pd=0.3,IL=3 | 1-vinyl-3-butylimidazole bromide | 4.2 |
Comparative example 2 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole dicyandiamide salt | 0.8 |
In comparative example 1, during the reduction of the catalyst, not only the active component Pd was added 2+ Reduction to Pd 0 The vinyl in the 1-vinyl-3-butyl imidazole bromine salt is reduced, so that the structure of the ionic liquid is changed, the ionic liquid is influenced to play a role, and the catalytic activity of the catalyst is reduced.
In comparative example 2, 1-butyl-3-methylimidazole dicyandiamide salt ionic liquid was poorly soluble in water, floating on the upper layer, causing Na 2 PdCl 4 Agglomeration does not result in a homogeneously dispersed impregnating solution. The hydrogen salt and the bromine salt have high stability to water, and can form a uniformly dispersed impregnating solution.
Examples 5 to 6
In addition to the 1-vinyl-3-butylimidazole bromide salt of comparative example 1, the same problems exist with 1-butyl-3-methylimidazole acetate as an ionic liquid, and the catalyst is directly applied to hydrogenation reaction, so that the hydrogenation efficiency is higher than that of the reduced catalyst. This is because the imidazole ionic liquid is a mild reducing agent, the reducing capability of which is related to the cationic substituent and the anionic species, and the catalyst loaded with the 1-vinyl-3-butyl imidazole bromide or 1-butyl-3-methyl imidazole acetate ionic liquid is not added with an exogenous reducing agent (such as H 2 ,NaBH 4 Sodium citrate, etc.), the hydrogenation efficiency is higher than that of the catalyst obtained by H 2 And (3) reducing. May be H 2 Will not only lead the active component Pd 2+ Reduction to Pd 0 The ionic liquid is reduced, so that the structure of the ionic liquid is changed, the ionic liquid is influenced to play a role, and the catalytic activity of the catalyst is reduced.
The evaluation results of the catalyst are shown in Table 2.
TABLE 2 hydrogenation efficiency before and after reduction
The physicochemical properties of the alumina carrier in example 1 before and after loading the ionic liquid and Pd are compared in Table 3.
Table 3 comparison of supported ionic liquid metal catalysts with support texture properties
Specific surface area (m) 2 /g) | Pore volume (cm) 3 /g) | Average pore diameter (nm) | |
Al 2 O 3 Carrier body | 277 | 0.75 | 9.27 |
EXAMPLE 1 preparation of Al 2 O 3 Pd/IL catalyst | 212 | 0.53 | 9.27 |
Therefore, ionic liquid and Pd metal nano particles occupy part of pore channels of the carrier, and the ionic liquid plays a role in stabilizing and protecting Pd species.
Examples 7 to 10
With reference to the operation of example 1,2, except for the ionic liquid loadings, see in particular table 3, alumina-supported ionic liquid-Pd-based catalysts were prepared. The evaluation results of the catalyst are shown in table 3.
TABLE 3 preparation of alumina Supported ionic liquid-Palladium-based catalyst and evaluation results of Activity in anthraquinone hydrogenation reactions
Examples | Load amount | Ionic liquid species | Hydrogenation efficiency (g/L) |
Example 7 | Pd=0.3,IL=1 | 1-butyl-3-methylimidazole bisulfate | 5.8 |
Example 1 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole bisulfate | 6.7 |
Example 8 | Pd=0.3,IL=6 | 1-butyl-3-methylimidazole bisulfate | 5.9 |
Example 9 | Pd=0.3,IL=1 | 1-butyl-3-methylimidazole chloride | 5.0 |
Example 2 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole chloride | 7.5 |
Example 10 | Pd=0.3,IL=6 | 1-butyl-3-methylimidazole chloride | 8.0 |
When the ionic liquid is 1-butyl-3-methylimidazoleWhen il=1 to 6, the hydrogenation efficiency increases and decreases with the increase of the loading of the ionic liquid when the hydrogen sulfate salt and the 1-butyl-3-methylimidazole chloride salt are added, because of Al 2 O 3 The acidity of the surface of the carrier can directly influence the electronic characteristics of Pd nano particles, thereby influencing the catalytic performance of the catalyst. Loaded acidityThe ionic liquid 1-butyl-3-methylimidazole bisulfate can regulate and control the acidity of the surface of a carrier, on one hand, the acidity site of a catalyst can participate in the reaction through adsorbing anthraquinone molecules, and as the loading amount of the 1-butyl-3-methylimidazole ionic liquid is increased, the weak acidity site on the surface of the catalyst is increased, the hydrogenation efficiency of the catalyst is higher, on the other hand, the acidic ionic liquid is excessively loaded to increase the strong acid site on the surface of the carrier, so that a reaction product is not easy to fall off from an active site, the possibility of excessive hydrogenation is improved, and byproducts such as ethylanthrone and the like are easy to generate.
The catalyst activity of the N-butyl pyridine tetrafluoroborate-containing ionic liquid is relatively high, mainly negative ion tetrafluoroborate ions act, and because tetrafluoroborate ions are hydrophilic and are easy to dissolve in water, uniform impregnating liquid can be formed with Pd, the high solvent and weak coordination effect of polar catalyst complex are combined, loss of active components can be effectively reduced, and meanwhile, tetrafluoroborate ions can influence the acid-base property of a carrier, so that the hydrogenation efficiency of the reaction is influenced.
Examples 11 to 12
With reference to the procedure of example 1, except for the aging time of the support in the mixed impregnation liquid, see in particular table 4, an alumina-supported ionic liquid Pd-based catalyst was prepared. The evaluation results of the catalyst are shown in table 4.
TABLE 4 preparation of alumina Supported ionic liquid-Palladium-based catalyst and evaluation results of Activity in anthraquinone hydrogenation reactions
Examples | Load wt% | Ionic liquid species | Aging time (h) | Hydrogenation Activity (g/L) |
Example 11 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole chloride | 1h | 4.4 |
Example 12 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole chloride | 9h | 5.5 |
The aging time is too short, the palladium nano particles are not firmly combined with the carrier, active components of the catalyst are easy to run off in the using process, so that the hydrogenation activity is reduced, along with the prolongation of the aging time, the metal nano particles are uniformly dispersed on the surface of the carrier, the hydrogenation activity is gradually improved, but the aging time is too long, the palladium nano particles can enter the pore canal of the carrier, anthraquinone macromolecules cannot enter deep layers, and cannot be combined with metal active sites, so that the activity of the catalyst is reduced.
Examples 13 to 14
The procedure of example 2 was followed, except that the reduction conditions of the catalyst, specifically shown in Table 5, were used to prepare an alumina-supported ionic liquid Pd-based catalyst. The evaluation results of the catalyst are shown in table 5.
TABLE 5 preparation of alumina Supported ionic liquid-Palladium-based catalyst and evaluation results of Activity in anthraquinone hydrogenation reactions
Examples | Load wt% | Ionic liquid species | Reduction conditions | Hydrogenation Activity (g/L) |
Example 13 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole chloride | 10%H 2 Reducing with Ar of 90% at 150 ℃ for 2h | 5.7 |
Example 14 | Pd=0.3,IL=3 | 1-butyl-3-methylimidazole chloride | 10%H 2 Reducing with Ar of 90% at 100deg.C for 4 hr | 6.7 |
Comparative examples
When no ionic liquid is added, the carrier is added into the sodium chloropalladate impregnating solution, the mixture is stirred for 1.5 hours at 45 ℃, aged and kept stand for 3 hours at 45 ℃, filtered and washed, and the mixture is put into an oven at 80 ℃ for drying for 12 hours, and the obtained catalyst is reduced for 4 hours by hydrogen at 150 ℃, and the type and activity evaluation results of the carrier are shown in the following table 5:
table 5 comparative example catalyst evaluation results
Examples | Carrier species | Load wt% | Hydrogenation Activity (g/L) |
Comparative examples | γ-Al 2 O 3 | Pd=0.3 | 4.8 |
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The application of the alumina-supported imidazole ionic liquid-Pd-based catalyst in catalyzing anthraquinone hydrogenation reaction is characterized in that the alumina-supported imidazole ionic liquid-Pd-based catalyst consists of a porous solid material carrier, imidazole ionic liquid and Pd metal compound which are supported on the carrier; the porous solid material is gamma-Al 2 O 3 ;
The Pd metal compound has a Pd-based load of 0.05-10wt% and the imidazole ionic liquid has a Pd-based load of 1-6wt%;
the imidazole ionic liquid is 1-vinyl-3-butyl imidazole bromide or 1-butyl-3-methyl imidazole acetate, and the alumina-supported imidazole ionic liquid-Pd-based catalyst is directly applied to hydrogenation reaction.
2. The use according to claim 1, wherein the γ -Al 2 O 3 Has a specific surface area of 100-500 m 2 And/g, pore diameter is 5-18 nm.
3. The use according to claim 1, wherein the γ -Al 2 O 3 The preparation method comprises the steps of heating precursor pseudo-boehmite to 400-800 ℃ from room temperature at a heating rate of 1-10 ℃/min, and calcining for 2-8 h.
4. The use according to claim 1, wherein the Pd metal compound is sodium chloropalladate, palladium nitrate, palladium acetate, palladium acetylacetonate, diamminedichloropalladium, ammonium tetrachloropalladate or tetraamminepalladium nitrate.
5. Use according to claim 1, prepared by the following method:
step 1, dissolving a Pd metal compound in a deionized water solvent, and fully dispersing by ultrasonic to obtain a Pd impregnation liquid; in the Pd impregnation liquid, the concentration of Pd metal compounds is 0.1-5 mg/mL;
step 2, dissolving the ionic liquid in deionized water solvent, and fully dispersing by ultrasonic waves to obtain ionic liquid impregnating solution; in the ionic liquid impregnating solution, the concentration of the ionic liquid is 0.5-8 mg/mL;
step 3, uniformly mixing the Pd impregnating solution and the ionic liquid impregnating solution at 20-60 ℃ to obtain ionic liquid-Pd impregnating solution;
and 4, adding 0.5-5 g of carrier into the ionic liquid-Pd impregnating solution, stirring at 20-60 ℃ for 0.5-5 h, uniformly dispersing, aging at 20-60 ℃ and standing for 1-12 h, filtering and washing, and drying in a 60-150 ℃ oven for 9-24 h.
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