CN113304782A - Preparation method and application of catalyst for catalytic oxidation of tetrahydronaphthalene - Google Patents
Preparation method and application of catalyst for catalytic oxidation of tetrahydronaphthalene Download PDFInfo
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- CN113304782A CN113304782A CN202110540606.4A CN202110540606A CN113304782A CN 113304782 A CN113304782 A CN 113304782A CN 202110540606 A CN202110540606 A CN 202110540606A CN 113304782 A CN113304782 A CN 113304782A
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- silica gel
- catalyst
- tetrahydronaphthalene
- ethanol
- catalytic oxidation
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 239000000741 silica gel Substances 0.000 claims abstract description 78
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 9
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 9
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- -1 vanadyl ions Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WWYNJERNGUHSAO-XUDSTZEESA-N (+)-Norgestrel Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 WWYNJERNGUHSAO-XUDSTZEESA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003433 contraceptive agent Substances 0.000 description 1
- 230000002254 contraceptive effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- CXEGAUYXQAKHKJ-NSBHKLITSA-N emamectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](NC)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 CXEGAUYXQAKHKJ-NSBHKLITSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229960004400 levonorgestrel Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000003128 rodenticide Substances 0.000 description 1
- VGKDLMBJGBXTGI-SJCJKPOMSA-N sertraline Chemical compound C1([C@@H]2CC[C@@H](C3=CC=CC=C32)NC)=CC=C(Cl)C(Cl)=C1 VGKDLMBJGBXTGI-SJCJKPOMSA-N 0.000 description 1
- 229960002073 sertraline Drugs 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- 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
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/57—Niobium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method and application of a catalyst for catalytic oxidation of tetrahydronaphthalene, and belongs to the technical field of organic synthesis. According to the method, silica gel is used as a substrate, a silane coupling agent is used for grafting an organic group on the surface of the silica gel, the amino functionalized silica gel is prepared, then the material is dispersed in a metal ion solution, and the material is bonded with metal ions through coordination complexing, so that the effect of loading metal active sites is achieved; the catalyst is used for catalyzing and oxidizing the tetrahydronaphthalene, so that higher conversion rate and selectivity can be achieved, and the catalyst can be repeatedly recycled; the invention has the advantages of stable active sites of the catalyst, high catalytic activity, easy separation and recovery, simple preparation process and cheap and easily obtained material matrix.
Description
Technical Field
The invention relates to a preparation method and application of a catalyst for catalytic oxidation of tetrahydronaphthalene, belonging to the technical field of organic synthesis.
Background
Alpha-tetralone is also called tetralone, is colorless oily liquid in appearance, is yellow in industrial grade products, can be gradually deepened to dark red under illumination, emits odor similar to camphor, is insoluble in water and can be mutually dissolved with various organic solvents. The relative molecular weight is 146.18g/mol, the relative density is 1.096g/ml, the melting point is 8 ℃, the flash point is 130 ℃, and the boiling point is 255-257 ℃ (under 101.3 KPa); it can be used as an intermediate for producing dyes, medicines and pesticides in important chemical industry; the compound can be mainly used as a solvent, a plastic softener and the like in the chemical industry, is mainly used for synthesizing sertraline (antidepressant), 18-methylnorethindrone (contraceptive) and other medicinal derivatives in medicine, and can be used as an intermediate for synthesizing emamectin benzoate (insecticide) and rodenticide in the aspect of pesticides; it can also be used as antioxidant and additive in fuel industry. The global market demand for alpha-tetralone has been greater than three billion dollars as reported in 2004.
Chinese patent CN 101544554B discloses a two-step method for catalyzing tetralin to synthesize alpha-tetralone by taking metalloporphyrin as a catalyst, wherein the selectivity of the alpha-tetralone is 94.26-96.29%, but the conversion rate of the tetralin is low, and the highest conversion rate is 34.22%. Chinese patent CN 102836723A discloses a chromium-based catalyst for catalyzing and oxidizing tetrahydronaphthalene to synthesize alpha-tetralone, and the selectivity of the alpha-tetralone can reach 84.64% at most, and the conversion rate is 48.21%. Chinese patent CN 101633611B discloses that benzene and gamma-butyrolactone are used as raw materials, a solid molecular sieve is used as a catalyst, and alpha-tetralone is synthesized by continuous flow, wherein the average yield of the method is 4.9-42.2%. Chinese patent CN101177386 discloses a bi-component non-metal catalytic system composed of quinone compounds and N-hydroxyphthalimide, which uses air or oxygen as oxygen source to catalyze and oxidize tetrahydronaphthalene, the yield of the method can reach 95% at most, but the catalyst is dissolved in organic solvent and can not be recovered.
Besides the oxidation of tetralin, the traditional process also includes Friedel-crafts method for preparing alpha-tetralone, which usually uses benzene and gamma-butyrolactone as raw materialIs readily available, however AlCl3The catalyst not only has high consumption and can not be recycled, but also can generate a large amount of acid wastewater in the process to cause damage to production equipment and pollution to the environment. The method using benzene and gamma-phenylbutyryl chloride as raw materials has the defects that the chloride salt of the catalyst is easy to dissolve, the acidic wastewater generated in the production process needs to be subjected to post-treatment, in addition, the method also has a synthetic route using gamma-phenylbutyric acid as a raw material, concentrated sulfuric acid or phosphoric acid is used as a catalyst to react at 90 ℃, the raw material is subjected to cyclization dehydration to generate alpha-tetralone, and AlCl is used in combination with the consideration and limitation of economic cost3The reaction of benzene with gamma-butyrolactone as starting material is still one of the major routes for the industrial preparation of alpha-tetralone.
At present, in a reaction system for synthesizing alpha-tetralone by catalyzing tetrahydronaphthalene, the problems mainly comprise that the conversion rate and the selectivity are not ideal enough, a catalyst cannot be recovered, the risk of heavy metal leakage and environmental pollution exists in the catalyst, the catalyst is volatile and can not be recycled, and the reaction conditions are harsh.
Disclosure of Invention
The invention aims to overcome the technical defects of the existing catalyst, provides a preparation method of a catalyst for catalyzing and oxidizing tetrahydronaphthalene, realizes high conversion rate of the catalytic tetrahydronaphthalene and high selectivity of alpha-tetralone under mild conditions, and specifically comprises the following steps:
(1) preparation of amino-functionalized modified silica gel:
performing amino functional modification on Silica Gel by adopting a silane coupling agent, dispersing the Silica Gel (Silica Gel) in 150-500 ml of organic solvent, adding the silane coupling agent, condensing and refluxing for 32-64 h at 60-120 ℃, cooling reaction liquid, filtering to obtain powder, washing by using ethanol and dichloromethane, and performing vacuum drying (vacuum drying for 24h at 100 ℃) to obtain the amino functional modified Silica Gel;
(2) the amino-functionalized silica gel supports vanadium as an active site:
dispersing the amino functional material prepared in the step (1) in ethanol or aqueous solution of vanadyl sulfate with the concentration of 0.4-1 mol/L, ultrasonically vibrating for 30-60 min, and then placing the mixture in magnetic stirringStirring for 16-24 h by using a stirrer; filtering to obtain powder after stirring, washing with a large amount of water or ethanol, and drying (vacuum drying at 100 ℃ for 24 hours) to obtain metal-loaded modified silica gel; in this step, aminated silica gel and VO are added2+Forming coordinate bonds, thereby realizing the supporting of vanadyl ions as active sites.
Preferably, the organic solvent in step (1) of the present invention includes anhydrous toluene, anhydrous ethanol, anhydrous butanol, acetone, dichloromethane, anisole or cyclohexane.
Preferably, in the step (1) of the present invention, the silane coupling agent is 3-Aminopropyltriethoxysilane (APTES), and the mass ratio of the silica gel to the silane coupling agent is 1:2 to 1: 8.
The invention also aims to provide a method for using the catalyst prepared by the method for catalytic oxidation of tetrahydronaphthalene, which comprises the following specific steps: adding an organic solvent and an oxidant into the obtained catalyst, adding tetrahydronaphthalene, condensing and refluxing at the temperature of 60-120 ℃, reacting for 6-12 h, and synthesizing alpha-tetralone; the method has the advantages of simple preparation process, low catalyst consumption and catalyst recycling.
Preferably, the oxidizing agent is hydrogen peroxide, tert-butyl hydroperoxide or oxygen.
Preferably, the organic solvent is ethanol, acetonitrile, acetic acid or butyl acetate.
Preferably, the molar mass ratio of the organic solvent to the oxidant is 1:3 to 1:10, and the mass ratio of the catalyst to the raw materials of the tetrahydronaphthalene is as follows: 1:1 to 1: 10.
The principle of the invention is as follows: the transition metal can catalyze and oxidize organic matters, the transition metal ions are loaded on the organic functionalized silicon material, high dispersion degree of active sites in the material can be realized, good contact with the organic matters is realized to realize catalytic reaction, meanwhile, the metal ions can be stably anchored in the material through coordination with organic bonds, and the metal active sites cannot be lost in the catalytic process.
The invention has the beneficial effects that:
(1) the catalyst has the advantages of simple preparation process, low economic cost of raw materials and no obvious difference in performance of catalysts prepared in different batches.
(2) The metal active site loaded by the method disclosed by the invention is high in content, and the metal active site is anchored in the catalyst through coordination with the organic group, so that the metal active site is not easy to lose and lose in the catalytic process, and the pollution hazard to the environment caused by metal leakage is avoided.
(3) The catalytic oxidation reaction of the tetrahydronaphthalene with the catalyst can directly oxidize the tetrahydronaphthalene into alpha-tetralone by only one step, the conversion rate of the catalytically oxidized tetrahydronaphthalene is high, the alpha-tetralone selectivity in the product is high, the reaction conditions are mild, the toxicity of the selected organic solvent is low, and the reaction does not pollute the environment.
(4) Compared with a homogeneous catalyst, the catalyst is solid powder, cannot be dissolved in an organic solvent, can be recycled, and has good recycling performance, and the catalytic activity of the catalyst is not obviously reduced after at least more than 4 times of recycling.
Drawings
FIG. 1 is a scheme showing the synthesis of VO-NH2-Silica Gel;
FIG. 2 is an XPS characterization of catalytic materials;
FIG. 3 is an infrared characterization of the catalytic material.
Detailed Description
The present invention will be further described with reference to the following detailed description, but the scope of the present invention is not limited to the description.
Example 1
(1) Preparation of aminated silica gel: weighing 5g of Silica Gel (Silica Gel) and 40g of APTES (3-aminopropyltriethoxysilane), adding into 150ml of absolute ethanol, condensing and refluxing for 64h at 60 ℃, washing with ethanol and dichloromethane, and vacuum drying at 100 ℃ for 24h to obtain the aminated modified Silica Gel material named as NH2-Silica Gel。
（2）NH2-silicon Gel loaded vanadyl ion: dispersing the aminated modified silica gel material obtained by drying in 0.4mol/L vanadyl sulfate solution, ultrasonically oscillating for 30min, stirring for 16h, washing with a large amount of ethanol and water, vacuum drying at 100 ℃ for 24h, and dryingThe catalyst carrying metal active sites is named as VO-NH2-Silica Gel。
Adopts ICP-OES to carry out the VO-NH reaction2Quantitative detection and analysis are carried out on the content of vanadium in Silica Gel, and the result shows that the content of vanadium is 4.10wt%, and the content of vanadium in the catalyst after being recycled for three times is 4.01 wt%.
VO-NH prepared in this example2XPS characterization of-Silica Gel is shown in FIG. 2, wherein FIG. 2(a) represents the Silica Gel matrix, NH2-Silica Gel, VO-NH2Variation of the elemental composition of Silica Gel, (b) represents VO-NH loaded with vanadyl ions as active sites2-binding sites of vanadium Silica Gel, (c) represents NH modified by amine functionalization2N element fitting of Silica Gel, (d) VO-NH carrying vanadyl ion as active site2N element fitting of Silica Gel. As can be seen from the figure, the silica gel matrix material only presents two elements of Si and O, and NH modified by APTES organic functionalization2The N element appears in the Silica Gel material, which indicates that APTES has been successfully grafted on the Silica Gel matrix material, VO-NH2The appearance of a new element V at 516.95eV in the silicon Gel material indicates NH2The Silica Gel material is successfully coordinated with vanadyl ions in vanadyl sulfate solution, and successfully loads active sites. Simultaneously in NH2-Silica Gel and VO-NH2In both materials, the nitrogen element can be fitted with two peaks, NH2N1s in Silica Gel presents two peaks, VO-NH, at 399.02eV and 400.92eV2Two peaks of Silica Gel at 399.32eV and 401.35eV, and N1s at 399.21eV and 399.02eV can be assigned as the aliphatic amino group (NH)2) N1s at 401.13eV and 400.92eV can be assigned as protonated aliphatic amino (NH)3）。
VO-NH prepared in this example2The IR spectrum of the Silica Gel matrix of Silica Gel is shown in FIG. 3 at 3450cm-1At 1635cm-1At 1235cm-1At 1090cm-1At 960cm-1At a distance of 800cm-1At a distance of 460cm-1An absorption peak appears. After the representative is modified by APTESAmine-functionalized NH of (A)2-Infrared Spectrum of Silica Gel at 2944cm, outside the original absorption peak of the matrix-1At 1530cm-1At 700cm-1A new absorption peak appears. Represents VO-NH taking vanadyl ions as active sites2Infrared spectrum of Silica Gel, 1530cm-1The position of the absorption peak of (A) is moved to 1497cm-1To (3).
It can be observed at 3450cm-1The strong absorption peak near the absorption peak is attributed to the asymmetrical stretching vibration absorption of absorbed moisture and surface hydroxyl (-OH); at 1650cm-1Near absorption peaks attributable to H-O-H bending vibration of physically adsorbed water; 960cm-1The absorption peak near the surface is attributed to out-of-plane bending vibration of Si-OH on the surface of the silica gel material; at 1235cm-1At and 1090cm-1The absorption peak near the position corresponds to the asymmetric stretching vibration of Si-O-Si bonds in the silica gel material and is 800cm-1Near and 460cm-1The absorption peak near the position corresponds to the symmetric stretching vibration peak of an S-O-Si bond in the silica gel material; 1635cm-1The absorption peak in the vicinity of (a) corresponds to the H-O-H bending vibration of physically adsorbed water.
NH modified by APTES amido functionalization2Silica Gel at 2944cm-1At 700cm-1New appearance of vibration absorption peak, which is corresponding to CH2Asymmetric stretching vibration of (A) — (CH)2）nAbsorption of rocking vibrations at 1530cm-1The absorption peak is N-H bending vibration, and the surface silica gel is successfully modified by amino functionalization
VO-NH after coordination adsorption with vanadyl ions in vanadyl sulfate solution2Silica Gel, original 1530cm-1The position of the absorption peak is shifted to 1497cm-1The binding material changes from pure white to green, and the surface amine groups are coordinated and bound by vanadyl ions. At the same time, 3450cm-1Asymmetric stretching vibration absorption of surface hydroxyl group and 960cm-1The absorption peak of the out-of-plane bending vibration of the surface hydroxyl is gradually weakened and disappeared, which shows that the hydroxyl is mostly modified and absorbed in the APTES functionalizationThe process of attaching metal is replaced.
In conclusion, infrared characterization shows that the amination modification of silica gel is successfully carried out, and vanadium metal loading is successfully carried out on the amination modified material.
VO-NH prepared in this example2-Silica Gel catalytic oxidation of tetrahydronaphthalene: 0.05g of VO-NH was weighed2Adding 20ml of acetonitrile serving as a solvent, 3mmol of TBHP (tert-butyl hydroperoxide) serving as an oxidant and 1mmol of tetrahydronaphthalene into the Silica Gel catalyst, condensing and refluxing the mixture at the temperature of 80 ℃, and reacting the mixture for 12 hours to achieve the effect of catalyzing and oxidizing the tetrahydronaphthalene.
The selectivity of alpha-tetralone synthesized in this example was 77.23% and the conversion of tetralin was 86.73%.
Example 2
(1) Preparation of aminated silica gel: weighing 15g of Silica Gel (Silica Gel) and 50g of APTES (3-aminopropyltriethoxysilane), adding into 500ml of absolute ethanol, condensing and refluxing for 48h at 80 ℃, washing with ethanol and dichloromethane, and vacuum drying at 100 ℃ for 24h to obtain the aminated modified Silica Gel material named as NH2-Silica Gel。
（2）NH2-silicon Gel loaded vanadyl ion: dispersing the obtained aminated modified silica gel material obtained by drying in 0.8mol/L vanadyl sulfate solution, ultrasonically oscillating for 60min, stirring for 16h, washing with a large amount of ethanol and water, vacuum drying at 100 ℃ for 24h, and naming the catalyst loaded with metal active sites as VO-NH2-Silica Gel。
VO-NH prepared in this example2Infrared characterization and XPS characterization of-Silica Gel, similar to example 1, using ICP-OES for VO-NH2Quantitative detection and analysis are carried out on the content of vanadium in Silica Gel, and the result shows that the content of vanadium is 3.98wt%, and the content of vanadium in the catalyst after being recycled for three times is 3.92 wt%.
VO-NH prepared in this example2-Silica Gel catalytic oxidation of tetrahydronaphthalene: 0.10g of VO-NH was weighed2-Silica Gel catalyst, adding 15ml of acetic acid as solvent, 5mmol of TBHP (tert-butyl hydroperoxide) is used as an oxidizing agent, 1mmol of tetrahydronaphthalene is added to be condensed and refluxed at the temperature of 110 ℃, and the reaction lasts for 6 hours, so that the effect of catalytic oxidation of the tetrahydronaphthalene can be achieved.
The selectivity of the alpha-tetralone synthesized in this example was 75.87% and the conversion of tetralin was 90.38%.
Example 3
(1) Preparation of aminated silica gel: weighing 7g of Silica Gel (Silica Gel) and 25g of APTES (3-aminopropyltriethoxysilane), adding into 300ml of anhydrous toluene, condensing and refluxing for 32h at 120 ℃, washing with ethanol and dichloromethane, and vacuum drying at 100 ℃ for 24h to obtain the aminated modified Silica Gel material named as NH2-Silica Gel。
（2）NH2-silicon Gel loaded vanadyl ion: dispersing the obtained aminated modified silica gel material obtained by drying in 1.0mol/L vanadyl sulfate solution, ultrasonically oscillating for 40min, stirring for 16h, washing with a large amount of ethanol and water, vacuum drying at 100 ℃ for 24h, and naming the catalyst loaded with metal active sites as VO-NH2-Silica Gel。
VO-NH prepared in this example2The infrared appearance and XPS characterization of Silica Gel was similar to that of example 1. Adopts ICP-OES to carry out the VO-NH reaction2Quantitative detection and analysis are carried out on the content of vanadium in Silica Gel, and the result shows that the content of vanadium is 3.85wt%, and the content of vanadium in the catalyst after being recycled for three times is 3.83 wt%.
VO-NH prepared in this example2-Silica Gel catalytic oxidation of tetrahydronaphthalene: 0.04g of VO-NH was weighed2Adding 25ml of butyl acetate as a solvent, adding 20mmol of TBHP (tert-butyl hydroperoxide) as an oxidant and adding 2mmol of tetrahydronaphthalene, condensing and refluxing at 100 ℃, and reacting for 8 hours to achieve the effect of catalytically oxidizing the tetrahydronaphthalene.
The selectivity of the alpha-tetralone synthesized in this example was 88.60%, and the conversion of tetralin was 90.41%.
Example 4
A method for preparing silica gel amination to catalyze and oxidize tetrahydronaphthalene specifically comprises the following steps:
(1) preparation of aminated silica gel: weighing 9g of Silica Gel (Silica Gel), 18g of APTES (3-aminopropyltriethoxysilane) and 280ml of acetone, condensing and refluxing the mixture at 80 ℃ for 48h, washing the mixture with ethanol and dichloromethane, and drying the mixture in vacuum at 100 ℃ for 24h, wherein the name of NH is2-Silica Gel。
（2）NH2-silicon Gel loaded vanadyl ion: dispersing the obtained aminated modified silica gel material in 0.75mol/L vanadyl sulfate solution, ultrasonically oscillating for 50min, stirring for 24h, washing with a large amount of ethanol and water, vacuum drying at 100 ℃ for 24h, and naming as VO-NH2-Silica Gel。
VO-NH prepared in this example2The infrared appearance and XPS characterization of Silica Gel was similar to that of example 1. Adopts ICP-OES to carry out the VO-NH reaction2Quantitative detection and analysis are carried out on the content of vanadium in Silica Gel, and the result shows that the content of vanadium is 4.01wt%, and the content of vanadium in the catalyst after being recycled for three times is 3.90 wt%.
VO-NH prepared in this example2-Silica Gel catalytic oxidation of tetrahydronaphthalene: 0.05g of VO-NH was weighed2Adding 15ml of acetonitrile serving as a solvent, 12mmol of TBHP (tert-butyl hydroperoxide) serving as an oxidant and 4mmol of tetrahydronaphthalene into the Silica Gel catalyst, condensing and refluxing the mixture at 95 ℃, and reacting the mixture for 10 hours to achieve the effect of catalytically oxidizing the tetrahydronaphthalene.
The selectivity of the alpha-tetralone synthesized in this example was 88.45% and the conversion of tetralin was 79.78%.
Example 5
A method for preparing silica gel amination to catalyze and oxidize tetrahydronaphthalene specifically comprises the following steps:
(1) preparation of aminated silica gel: weighing 12g of Silica Gel (Silica Gel), 20g of APTES (3-aminopropyltriethoxysilane), adding 300ml of anisole, condensing and refluxing for 60h at 110 ℃, washing with ethanol and dichloromethane, and vacuum drying at 100 ℃ for 24h, wherein the name of NH is2-Silica Gel。
（2）NH2-silicon Gel loaded vanadyl ion: dispersing the obtained aminated modified silica gel material in 0.75mol/L vanadyl sulfate solution, ultrasonically oscillating for 60min, stirring for 20h, washing with a large amount of ethanol and water, vacuum drying at 100 ℃ for 24h, and naming as VO-NH2-Silica Gel。
VO-NH prepared in this example2The infrared appearance and XPS characterization of Silica Gel was similar to that of example 1. Adopts ICP-OES to carry out the VO-NH reaction2Quantitative detection and analysis are carried out on the content of vanadium in Silica Gel, and the result shows that the content of vanadium is 3.88wt%, and the content of vanadium in the catalyst after being recycled for three times is 3.80 wt%.
VO-NH prepared in this example2-Silica Gel catalytic oxidation of tetrahydronaphthalene: 0.2g of VO-NH is weighed2Adding 15ml of ethanol as a solvent, 6mmol of hydrogen peroxide as an oxidant and 1.5mmol of tetrahydronaphthalene into the Silica Gel catalyst, condensing and refluxing the mixture at 70 ℃, and reacting for 10 hours to achieve the effect of catalyzing and oxidizing the tetrahydronaphthalene.
The selectivity of the alpha-tetralone synthesized in this example was 75.66% and the conversion of tetralin was 80.83%.
Claims (7)
1. A preparation method of a catalyst for catalytic oxidation of tetrahydronaphthalene is characterized by comprising the following steps:
(1) preparation of amino-functionalized modified silica gel:
performing amino functional modification on silica gel by adopting a silane coupling agent, dispersing the silica gel in 150-500 ml of an organic solvent, adding the silane coupling agent, condensing and refluxing for 32-64 h at the temperature of 60-120 ℃, cooling reaction liquid, filtering to obtain powder, washing by using ethanol and dichloromethane, and drying in vacuum to obtain amino functional modified silica gel;
(2) the amino-functionalized silica gel supports vanadium as an active site:
dispersing the amino functional material prepared in the step (1) in ethanol or aqueous solution of vanadyl sulfate with the concentration of 0.4-1 mol/L, ultrasonically vibrating for 30-60 min, placing in a magnetic stirrer, and stirring for 16-24 h; filtering to obtain powder after stirring, washing with a large amount of water or ethanol, and drying to obtain the metal-loaded modified silica gel.
2. The method for preparing a catalyst for catalytic oxidation of tetrahydronaphthalene according to claim 1, characterized in that: the silane coupling agent in the step (1) is 3-aminopropyltriethoxysilane, and the mass ratio of the silica gel to the silane coupling agent is 1: 2-1: 8.
3. The method for preparing a catalyst for catalytic oxidation of tetrahydronaphthalene according to claim 1, characterized in that: the organic solvent in the step (1) comprises anhydrous toluene, anhydrous ethanol, anhydrous butanol, acetone, dichloromethane, anisole or cyclohexane.
4. The method for catalytic oxidation of tetrahydronaphthalene by using the catalyst prepared by the method of claim 1, which is characterized in that: and adding an organic solvent and an oxidant into the obtained catalyst, adding tetrahydronaphthalene, condensing and refluxing at the temperature of 60-120 ℃, reacting for 6-12 h, and synthesizing the alpha-tetralone.
5. The method of claim 4, further comprising: the oxidant is hydrogen peroxide, tert-butyl hydroperoxide or oxygen.
6. The method of claim 4, further comprising: the organic solvent is ethanol, acetonitrile, acetic acid or butyl acetate.
7. The method of claim 6, further comprising: the molar mass ratio of the organic solvent to the oxidant is 1: 1-1: 10, and the mass ratio of the catalyst to the raw materials of the tetrahydronaphthalene is as follows: 10: 1-1: 25.
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