CN111068669B - Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof - Google Patents
Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof Download PDFInfo
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- CN111068669B CN111068669B CN202010037567.1A CN202010037567A CN111068669B CN 111068669 B CN111068669 B CN 111068669B CN 202010037567 A CN202010037567 A CN 202010037567A CN 111068669 B CN111068669 B CN 111068669B
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 47
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 117
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 57
- 150000003248 quinolines Chemical class 0.000 claims abstract description 37
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000002923 metal particle Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000008247 solid mixture Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229940111121 antirheumatic drug quinolines Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 239000012694 precious metal precursor Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 54
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- -1 quinoline compound Chemical class 0.000 abstract description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 43
- 239000000463 material Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 24
- 229910001220 stainless steel Inorganic materials 0.000 description 24
- 239000010935 stainless steel Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PASUADIMFGAUDB-UHFFFAOYSA-N 6-chloro-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(Cl)=CC=C21 PASUADIMFGAUDB-UHFFFAOYSA-N 0.000 description 1
- GKJSZXGYFJBYRQ-UHFFFAOYSA-N 6-chloroquinoline Chemical compound N1=CC=CC2=CC(Cl)=CC=C21 GKJSZXGYFJBYRQ-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 238000005406 washing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/18—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof, wherein the heterogeneous catalyst comprises 1-10 wt% of noble metal particles and 9-90 wt% of titanium dioxide with oxygen vacancies, and the noble metal particles are loaded on the titanium dioxide with oxygen vacancies. Compared with the common titanium dioxide supported noble metal catalyst, the heterogeneous catalyst of the invention is applied to the selective hydrogenation reaction of the catalytic quinoline compound, because the noble metal in the heterogeneous catalyst of the invention and the oxygen vacancy of the titanium dioxide act together, electrons are transferred, so that the noble metal is rich in charge, thereby improving the catalytic activity of the heterogeneous catalyst.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof.
Background
The synthesis of functionalized 1,2,3, 4-tetrahydroquinoline (py-THQ) is receiving increasing attention due to its great utility in the production of pharmaceuticals, alkaloids, pesticides and other fine chemicals. High reaction temperatures are required for the hydrogenation of N-heteroarenes catalyzed by transition metal and metal-free catalysts: (>120 ℃ and long reaction times: (>24 H) because they have a low H 2 And (4) activating ability. The noble metal (such as Ir, ru, rh, pd and Pt) catalytic system has higher catalytic activity for the hydrogenation reaction of quinoline compounds. However, whether or notWhether it is a heterogeneous catalyst or a homogeneous catalyst, in the presence of other reducible functional groups (Cl, OH, CHO, etc.), the substrate applicability of the catalyst is generally poor, leading to a decrease in its chemoselectivity. In addition, strong adsorption of quinoline and hydrogenated quinoline may result in catalyst poisoning. Therefore, the development of a quinoline compound hydrogenation catalyst with high activity and high selectivity is of great significance.
For a long time, efforts have been made to develop catalysts with high activity, high selectivity and high stability for selective hydrogenation of quinolines to produce 1,2,3, 4-tetrahydroquinolines. TiO 2 2 As a common metal oxide, it has attracted much attention as a carrier due to its strong interaction with metals. For example, using high specific surface area TiO 2 The supported nano Au catalyst can be used for preparing a catalyst at 60 ℃ and 2MPa H 2 Under the reaction conditions of (1), 6-chloroquinoline is quantitatively converted into 6-chlorotetrahydroquinoline within 3h, and no dehalogenation reaction occurs (j.am. Chem. Soc. 2012, 134, 17592.). The catalytic system has very good substrate universality, and can obtain better yield for quinoline substrates substituted by some reducible groups (acetyl, vinyl and the like) or other nitrogen-containing aromatic compounds (such as isoquinoline, 7, 8-benzoquinoline, acridine and the like). At the same time, rutile phase TiO 2 The supported nano-gold catalyst can also be used for selectively hydrogenating quinoline compounds by taking formic acid as a hydrogen source at 130 ℃ (Adv Synth. Catal. 2015, 357, 753). However, these catalysts are either complicated to prepare or the reaction conditions are severe.
The defect of the metal oxide is one of important factors influencing the performance of the metal oxide, the oxygen vacancy is one of the most important defects of the metal oxide, the electronic structure regulation and control of the metal and the influence research in the quinoline hydrogenation reaction are less, and the invention is to use the oxygen vacancy TiO 2 The strong interaction with noble metals is applied to heterogeneous catalytic reactions.
Disclosure of Invention
In view of the above technical problems in the prior art, an object of the present invention is to provide a heterogeneous catalyst for selective hydrogenation of quinoline compounds, which is synthesized by a specific method and contains noble metal particles, and which is stable to air, water and heat, and exhibits excellent catalytic activity and selectivity when applied to selective hydrogenation of quinoline, and an application thereof.
The heterogeneous catalyst for the selective hydrogenation reaction of the quinoline compounds is characterized by comprising 1-10 wt% of noble metal particles and 9-90 wt% of titanium dioxide with oxygen vacancies, wherein the noble metal particles are loaded on the titanium dioxide with the oxygen vacancies.
The heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds is characterized in that the preparation method of the titanium dioxide with oxygen vacancies comprises the following steps: calcining titanium dioxide serving as a raw material at the temperature of 600-1200 ℃ for 0.5-6 h in an inert gas atmosphere to obtain the titanium dioxide with oxygen vacancies.
The heterogeneous catalyst for the selective hydrogenation reaction of the quinoline compounds is characterized in that in the method for preparing the titanium dioxide with the oxygen vacancy, the raw material of the titanium dioxide is TiO 2 (B) And the inert gas is nitrogen.
The heterogeneous catalyst for selective hydrogenation of quinoline compounds is characterized in that the preparation method of the heterogeneous catalyst comprises the following steps:
1) Adding the titanium dioxide with the oxygen vacancy into an aqueous solution of a noble metal precursor, stirring and mixing uniformly to enable the noble metal precursor to be adsorbed on the titanium dioxide, and then heating and stirring at 60-80 ℃ until the moisture is completely volatilized to obtain a solid mixture;
2) And (2) placing the solid mixture obtained in the step 1) in a tubular furnace, and roasting in an atmosphere of introducing hydrogen to reduce the precious metal precursor loaded on the titanium dioxide into precious metal particles, thus obtaining the heterogeneous catalyst.
The heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds is characterized in that the noble metal particles are Au, ag, rh, os, ir, ru, pt or Pd particles; the particle diameter of the noble metal particle is 1 to 50nm, preferably 1 to 15nm.
The heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds is characterized in that in the step 2), the roasting temperature is 200-600 ℃, and preferably 250-500 ℃.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the quinoline compounds and a solvent are mixed, and the mixed reaction liquid and hydrogen gas are subjected to selective hydrogenation reaction under the action of the heterogeneous catalyst to generate hydrogenated quinoline compounds; wherein the reaction temperature is 0-150 ℃, and the reaction pressure is 0.1-10 MPa; the solvent is water, ethanol, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, N-dimethylformamide, N-hexane or toluene.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the quinoline compounds are quinoline or substituted quinoline, the number of substituents on benzene rings or pyridine rings of the substituted quinoline is one or more, and the substituents on the benzene rings or the pyridine rings of the substituted quinoline are halogen, C1-C3 alkoxy, hydroxyl or phenyl.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the mass of the heterogeneous catalyst is 0.1-10% of the mass of the quinoline compounds.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the temperature for performing the selective hydrogenation reaction is 20-80 ℃, the pressure is 0.1-2 MPa, and the solvent is water or ethanol.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. in the preparation process of the catalyst carrier, tiO is selected as titanium dioxide 2 (B) And TiO of 2 (B) Has a sheet-like multi-layered structure which is unstable at high temperatures and in which O is desorbed during high-temperature calcination in an inert atmosphere, thereby forming oxygen vacancies. In the catalyst prepared by the invention, the strong interaction between the noble metal particles and the titanium dioxide carrier with oxygen vacancy causes the noble metalThe contact surface between the metal particles and the titanium dioxide carrier is increased, the dissociation of hydrogen is promoted, and the contact surface is not easily attached by quinoline, so that the coordination bond formed by nitrogen atoms in the quinoline and the catalyst is inhibited, the catalytic activity is reduced, and the poisoning phenomenon of the catalyst can be effectively avoided.
2. In the heterogeneous catalyst, due to the strong interaction between the noble metal particles and the titanium dioxide carrier with oxygen vacancies and the effectiveness of hydrogen reduction (namely, the hydrogen effectively reduces the ionic noble metal into a simple substance), the noble metal particles of the heterogeneous catalyst prepared by the invention have uniform size and good dispersity, and the average diameter of the noble metal particles can reach 1-10 nm. The heterogeneous catalyst is stable to air, water and heat, the catalytic quinoline hydrogenation activity is not reduced after the heterogeneous catalyst exists in the air for 5 months, and the metal valence state is kept unchanged.
3. Compared with the common titanium dioxide supported noble metal catalyst, when the heterogeneous catalyst is applied to the selective hydrogenation reaction of the catalytic quinoline compound, the noble metal in the heterogeneous catalyst and the oxygen vacancy of the titanium dioxide act together to cause the shift of electrons, so that the noble metal is rich in charges (the electron-rich noble metal particles are more beneficial to the dispersion of the electron-rich noble metal particles on the catalyst carrier, and are more beneficial to the exposure of metal active sites and the improvement of catalytic activity), and the catalytic activity of the heterogeneous catalyst is improved. Taking the catalytic quinoline hydrogenation reaction to prepare 1,2,3, 4-tetrahydroquinoline as an example, the conversion rate of quinoline can reach 100%, and the selectivity of 1,2,3, 4-tetrahydroquinoline can reach more than 95%.
Drawings
FIG. 1 is a HRTEM image of the catalyst obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 based on TiO 2-x Heterogeneous catalyst loaded with Ru
0.4g of TiO was taken 2 (B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO 2-x A material.
The TiO prepared above was then added to a 100mL beaker 2-x 0.2g of material, 0.15ml of previously prepared RuCl was added 3 Aqueous solution (RuCl) 3 Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated 3 Adsorbing on TiO 2-x On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO 2-x A supported Ru catalyst.
Example 2 based on TiO 2-x Pd-supported heterogeneous catalyst
0.4g of TiO was taken 2 (B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO 2-x A material.
The TiO prepared above was then added to a 100mL beaker 2-x 0.2g of material, 0.15ml of previously prepared PdCl were then added 3 Aqueous solution (PdCl) 3 The concentration of the aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that PdCl 3 Adsorbing on TiO 2-x On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Pd after later-stage calcination are closely and uniformly combined.
The prepared solid mixture is placed in a tube furnace and calcined for 1h at the temperature of 300 ℃ in the hydrogen atmosphere to obtain TiO 2-x A supported Pd catalyst.
Example 3 based on TiO 2-x Heterogeneous catalyst loaded with Au
0.4g of TiO was taken 2 (B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO 2-x A material.
The TiO prepared above was then added to a 100mL beaker 2-x 0.2g of the material was added to 0.15ml of the material and prepared in advanceHAuCl of 4 ·4H 2 O aqueous solution (HAuCl) 4 Concentration of 4H2O aqueous solution 10 mg/mL), and uniformly mixing the mixture with stirring to give HAuCl 4 ·4H 2 O adsorption on TiO 2-x On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and Au after later-stage calcination are closely and uniformly combined.
The prepared solid mixture is placed in a tube furnace and calcined for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO 2-x A supported Au catalyst.
Example 4 based on TiO 2-x Pt-supported heterogeneous catalyst
0.4g of TiO was taken 2 (B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO 2-x A material.
The TiO prepared above was then added to a 100mL beaker 2-x 0.2g of material, 0.15ml of previously prepared H 2 PtCI 6 ·6H 2 O aqueous solution (H) 2 PtCI 6 ·6H 2 The concentration of the O aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that H is added 2 PtCI 6 ·6H 2 O adsorption on TiO 2-x On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Pt are closely and uniformly combined after the later-stage calcination.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO 2-x A supported Pt catalyst.
Example 5 based on TiO 2-x Ag-supported heterogeneous catalyst
0.4g of TiO was taken 2 (B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO 2-x A material.
The TiO prepared above was then added to a 100mL beaker 2-x 0.2g of the material was added to 0.15ml of the material and prepared in advanceAgNO placed 3 Aqueous solution (AgNO) 3 The concentration of the aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that AgNO is mixed 3 Adsorbing on TiO 2-x On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ag after the later calcination are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO 2-x A supported Ag catalyst.
Example 6 example 1 TiO 2-x Characterization of the Supported Ru catalyst
The TiO obtained in example 1 was examined by high-resolution transmission electron microscope (HRTEM) 2-x The supported Ru catalyst was characterized, and the characterization results are shown in FIG. 1, which confirmed that the catalyst was composed of titanium dioxide nano-metal Ru. Ru nano particles are uniformly distributed on TiO 2-x On the material, the Ru and the titanium dioxide are in close contact, which shows that obvious interaction exists between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 1.8 nm by counting 150 nanometer Ru metal particles.
Example 7 preparation of tetrahydroquinoline by hydrogenation of quinoline using the heterogeneous catalyst prepared in example 1
After charging 118. Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 1 and 10 mL of methylene chloride into a 50 mL stainless steel autoclave, and evacuating the inside of the stainless steel autoclave with hydrogen 3 times (i.e., the inside of the stainless steel autoclave was replaced with air by hydrogen and the inside of the stainless steel autoclave was evacuated, which is equivalent to the following example), charging hydrogen to 1MPa and sealing, heating in a 60 ℃ water bath, magnetically stirring, and carrying out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the quinoline to be 98% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 97%.
EXAMPLE 8 preparation of tetrahydroquinoline by hydrogenation of quinoline over the heterogeneous catalyst prepared in example 2
Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 2 and 10 mL of tetrahydrofuran were charged into a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, charging hydrogen to 1MPa and sealing were carried out, and the mixture was heated in a water bath at 80 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully removed, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of quinoline to be 99% and the selectivity of 1,2,3, 4-tetrahydroquinoline to be 90%.
Example 9 preparation of tetrahydroquinoline by catalytic hydrogenation of quinoline using the heterogeneous catalyst prepared in example 3
Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 3 and 10 mL of ethanol were placed in a 50 mL stainless steel autoclave, the inside of the stainless steel autoclave was charged and discharged with hydrogen 3 times, charged with hydrogen to 1MPa and sealed, heated in a water bath at 60 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. Separating the heterogeneous catalyst from the reaction liquid by a centrifugal method, detecting the reaction liquid by gas chromatography, and detecting and calculating that the conversion rate of quinoline is 98% and the selectivity of 1,2,3, 4-tetrahydroquinoline is 95%.
Example 10 preparation of tetrahydroquinoline by catalytic hydrogenation of quinoline using the heterogeneous catalyst prepared in example 4
Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 4 and 10 mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, the autoclave was charged with hydrogen to 1MPa and sealed, heated in a 60 ℃ water bath, magnetically stirred, subjected to selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating that the conversion rate of quinoline is 99% and the selectivity of 1,2,3, 4-tetrahydroquinoline is 96%.
EXAMPLE 11 preparation of tetrahydroquinoline by hydrogenation of quinoline over the heterogeneous catalyst prepared in example 5
Mu.l of quinoline, 10 mg of the catalyst of example 5 and 10 mL of N, N-dimethylformamide were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, charging hydrogen to 1MPa and sealing were carried out, and the mixture was heated in a water bath at 60 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully removed, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating by detection that the conversion rate of quinoline is 90% and the selectivity of 1,2,3, 4-tetrahydroquinoline is 95%.
Examples 8-11 illustrate that titania with vacancies supporting a noble metal all have good activity and selectivity for quinoline hydrogenation.
EXAMPLE 12 preparation of tetrahydroquinoline by catalytic hydrogenation of quinoline after 5 months' storage with the catalyst prepared in example 3
The heterogeneous catalyst prepared in example 3 is placed in an environment with cool room temperature and 70% -80% of relative humidity for 5 months, and then the catalytic activity of the heterogeneous catalyst is verified according to the following steps: mu.l of quinoline, 10 mg of the catalyst prepared in example 3 after leaving to stand for 5 months, and 10 mL of ethanol were placed in a 50 mL stainless steel autoclave, and after the inside of the stainless steel autoclave was purged with hydrogen 3 times, the inside was charged with hydrogen to 1MPa and sealed, and the mixture was heated in a water bath at 60 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the quinoline to be 96% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 92%. By comparing example 14 with example 10, it can be seen that the catalyst obtained in example 3 is very stable and inert to both air and moisture.
Examples 13 to 20
Examples 14 to 21 are examples in which a functional hydride was produced by a hydrogenation reaction of a quinoline compound using the heterogeneous catalyst prepared in example 1, the procedure of examples 14 to 21 was the same as in example 7, and the molar charge amount of the reaction substrate, the volume of the solvent added, and the amount of the catalyst added were the same as in example 7. Table 1 shows the reaction conditions and the corresponding reaction results for each example.
TABLE 1
As can be seen from examples 13-20, the catalysts have very good versatility and the different substituents are well preserved during the reaction, i.e., ru/TiO 2-x The catalyst is a high-activity and high-selectivity catalyst in the catalytic hydrogenation of quinoline compounds.
Comparative example 1 is based on TiO 2 (B) Ru-supported heterogeneous catalyst for quinoline hydrogenation
0.2g of TiO was added to a 100mL beaker 2 (B) Then 0.15ml of previously prepared RuCl was added 3 Aqueous solution (RuCl) 3 Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated 3 Adsorbing on TiO 2 (B) On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO 2 (B) A supported Ru catalyst.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of TiO prepared as described above 2 (B) The supported Ru catalyst and 10 mL of ethanol were added to a 50 mL stainless steel autoclave, and after 3 cycles of charging and discharging with hydrogen, charging hydrogen to 1MPa and sealing, heating in a 60 ℃ water bath, magnetic stirring, and reaction for 3h. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. Separating the catalyst from the reaction solution by centrifugation, detecting the reaction solution by gas chromatography, and calculating to obtain the product with a quinoline conversion rate of 20% and a 1,2,3, 4-tetrahydroquinoline selectivity of 85%%。
Comparative example 2 preparation of tetrahydroquinoline by hydrogenation of quinoline based on a catalyst with titanium dioxide P25 supporting Ru
Preparing a catalyst: adding titanium dioxide P25.2 g into a 100ml beaker, adding 0.15ml of previously prepared RuCl 3 Aqueous solution (RuCl) 3 Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated 3 Adsorbed on the titanium dioxide P25. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. The solid mixture prepared above was placed in a tube furnace and calcined at 300 ℃ for 1h under a hydrogen atmosphere to obtain a P25-supported Ru catalyst.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of the P25-supported Ru catalyst prepared above and 10 mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of evacuation with hydrogen, the autoclave was charged with hydrogen to 1MPa and sealed, heated in a 60 ℃ water bath, magnetically stirred, and reacted for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the quinoline is 25% and the selectivity of the 1,2,3, 4-tetrahydroquinoline is 96%.
As can be seen from comparative examples 1 and 2, tiO alone 2 (B) Or when the titanium dioxide P25 is a carrier loaded with the nano metal Ru, the catalytic activity of the catalyst is lower than that of the catalyst prepared in the example 3, and the fact that the oxygen vacancy of the titanium dioxide plays an important role is confirmed.
Comparative example 3 is based on TiO 2-x NaBH for loading Ru 4 Reduced heterogeneous catalyst
0.4g of TiO was taken 2 (B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO 2-x A material.
Taking the TiO prepared above 2-x Adding 0.2g of the material into 50 mL of deionized water, performing ultrasonic treatment for 10 min, and adding 0.15mL of pre-prepared RuCl 3 Aqueous solution (RuCl) 3 Aqueous solutionThe concentration of (3) is 10 mg/mL), after ultrasonic treatment is carried out for 10 min, 5mL of freshly prepared sodium borohydride aqueous solution is added to continue ultrasonic treatment (the concentration of the sodium borohydride aqueous solution is 1 mg/mL), and Ru is carried out 3+ Reducing the solution into elementary substance Ru, then performing suction filtration, washing filter residue for multiple times, and drying to obtain TiO 2-x A supported Ru catalyst.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of TiO prepared as described above 2-x The supported Ru catalyst and 10 mL of ethanol were added to a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen, charging hydrogen to 1MPa and sealing were performed, and the mixture was heated in a 60 ℃ water bath, magnetically stirred, and reacted for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of quinoline to be 55% and the selectivity of 1,2,3, 4-tetrahydroquinoline to be 95%.
As can be seen from the comparison of the reaction results of comparative example 3 and example 7, the reduction mode has a close relationship with the catalyst activity. High temperature calcination of Ru in a hydrogen atmosphere 3+ The catalyst prepared by reducing the Ru into the simple substance has higher catalytic activity.
Comparative example 4 preparation of tetrahydroquinoline by hydrogenation of quinoline based on commercial activated carbon-supported Ru catalyst
Preparing a catalyst: adding 0.2g commercial activated carbon (coconut shell activated carbon, 200-300 mesh, available from Jiuding chemical technology Co., ltd.) into 50 mL deionized water, adding 0.15mL of pre-prepared RuCl 3 Aqueous solution (RuCl) 3 Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated 3 Adsorbing on activated carbon. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. And (3) putting the prepared solid mixture into a tubular furnace, and calcining the solid mixture for 1h at the temperature of 300 ℃ in a hydrogen atmosphere to obtain the Ru catalyst supported by the active carbon.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of the commercial activated carbon Ru-supported catalyst prepared above and 10 mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen, charging and sealing were carried out, heating in a water bath at 80 ℃ with magnetic stirring, and reaction was carried out for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the quinoline to be 18% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 43%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (4)
1. The application of a heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the quinoline compounds are mixed with a solvent, and the mixed reaction liquid and hydrogen carry out selective hydrogenation reaction under the action of the heterogeneous catalyst to generate hydrogenated quinoline compounds; wherein the reaction temperature is 0-150 ℃, and the reaction pressure is 0.1-10 MPa; the solvent is water, ethanol, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, N-dimethylformamide, N-hexane or toluene;
the heterogeneous catalyst consists of 10% of noble metal particles and 90% of titanium dioxide having oxygen vacancies, the noble metal particles being supported on the titanium dioxide having oxygen vacancies;
the preparation method of the titanium dioxide with the oxygen vacancy comprises the following steps: calcining titanium dioxide serving as a raw material for 0.5 to 6 hours at the temperature of between 600 and 1200 ℃ in an inert gas atmosphere to obtain the titanium dioxide with oxygen vacancies; the titanium dioxide is TiO 2 (B) The inert gas is nitrogen;
the preparation method of the heterogeneous catalyst comprises the following steps:
1) Adding the titanium dioxide with the oxygen vacancy into an aqueous solution of a noble metal precursor, stirring and mixing uniformly to enable the noble metal precursor to be adsorbed on the titanium dioxide, and then heating and stirring at 60-80 ℃ until the moisture is completely volatilized to obtain a solid mixture;
2) Placing the solid mixture obtained in the step 1) in a tubular furnace, and roasting in an atmosphere of introducing hydrogen to reduce the precious metal precursor loaded on the titanium dioxide into precious metal particles, thus obtaining the heterogeneous catalyst;
the noble metal particles are Au, ag, rh, os, ir, ru, pt or Pd particles; the particle size of the noble metal particles is 1 to 15nm; in the step 2), the roasting temperature is 250-500 ℃.
2. The application of the heterogeneous catalyst in selective hydrogenation of quinoline compounds according to claim 1, wherein the quinoline compounds are quinoline or substituted quinoline, the number of substituents on the benzene ring or pyridine ring of the substituted quinoline is one or more, and the substituents on the benzene ring or pyridine ring of the substituted quinoline are halogen, C1-C3 alkoxy, hydroxyl or phenyl.
3. The use of the heterogeneous catalyst according to claim 1 in selective hydrogenation of quinolines, characterized in that the mass of the heterogeneous catalyst is between 0.1 and 10% of the mass of quinolines.
4. The use of the heterogeneous catalyst according to claim 1 in selective hydrogenation of quinolines, characterized in that the selective hydrogenation is carried out at a temperature of 20-80 ℃ and a pressure of 0.1-2 MPa, the solvent being water or ethanol.
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