CN107694610A - A kind of phase transfer catalyst for cyclohexanol synthesizing cyclohexanone and preparation method thereof - Google Patents
A kind of phase transfer catalyst for cyclohexanol synthesizing cyclohexanone and preparation method thereof Download PDFInfo
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- phase transfer
- cyclohexanol
- graphene oxide
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003444 phase transfer catalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical class CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000003408 phase transfer catalysis Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000012071 phase Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010669 acid-base reaction Methods 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 abstract 1
- 238000002444 silanisation Methods 0.000 abstract 1
- 238000006276 transfer reaction Methods 0.000 abstract 1
- 239000011964 heteropoly acid Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- -1 graphite alkene Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 2
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- FDXBUMXUJRZANT-UHFFFAOYSA-N 6-phenylhexan-1-ol Chemical compound OCCCCCCC1=CC=CC=C1 FDXBUMXUJRZANT-UHFFFAOYSA-N 0.000 description 1
- OPVIFYCKRBJEDI-UHFFFAOYSA-N C1(CCCCC1)O.[O] Chemical compound C1(CCCCC1)O.[O] OPVIFYCKRBJEDI-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- AXKGUOXGBWHEGY-UHFFFAOYSA-N silane 3-trimethoxysilylpropan-1-amine Chemical compound [SiH4].CO[Si](CCCN)(OC)OC AXKGUOXGBWHEGY-UHFFFAOYSA-N 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
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of phase transfer catalyst for cyclohexanol synthesizing cyclohexane 1 reactive ketone and preparation method thereof, this method is using graphene oxide as carrier, it is by Silanization reaction that 3 aminopropyl trimethoxysilanes are immobilized in surface of graphene oxide first, it is then by solid phase acid-base reaction that phosphotungstic acid is immobilized in surface of graphene oxide, produce required phase transfer catalyst.The catalyst has good catalytic performance in the phase transfer reaction of cyclohexanol synthesizing cyclohexanone, and for cyclohexanol high conversion rate up to 89.2%, cyclohexanone selectivity is up to 95.4%.The catalyst preparation process is simple, and phase transfer catalysis (PTC) activity is high, and multiplexing performance is good, and product post processing is simple, has very high application value.
Description
Technical field
The present invention relates to the preparation field of phase transfer catalyst, more particularly to a kind of phase of cyclohexanol synthesizing cyclohexanone
Transfer catalyst and preparation method thereof.
Background technology
Cyclohexanone is to obtain the chemical intermediate of caprolactam and adipic acid, and caprolactam is the monomer of nylon 6, adipic acid
It can be used for that filled nylon 66 is made, in addition, it is organic used also as the various fields such as industrial coating, agricultural chemicals, medicine
Solvent.These industrial products occupy indispensable status in daily life, drastically increase the life of contemporary people
Quality living.
The conventional synthesis route of cyclohexanone has cyclohexene hydration method, phenol hydrogenation oxidizing process, producing cyclohexane by benzene hydrogenation liquid phase
Oxidizing process etc..Problems be present in these production technologies, as the conversion ratio of raw material and the selectivity of product are low, process route is long,
Energy consumption and cost is higher, conventional oxidation agent causes serious environmental pollution etc..
In order to solve drawback present in above traditional processing technology, domestic and international researcher make great efforts to explore green non-pollution,
The production technology of the good cyclohexanone of economy.The process route that cyclohexanone is directly prepared by cyclohexanol one-step oxidation process is simple
And it is environment-friendly, preferable production ways can be turned into.
With H2O2As green oxygen source, it is ability in recent years to select suitable alcohol oxidation catalyst to be used for the preparation of cyclohexanone
The study hotspot in domain.Many alcohol oxidation catalysts are developed in recent years, are broadly divided into following a few classes：Metallic compound, season
Ammonium salt class, ionic liquid and heteropoly acid etc..During using metallic compound as catalyst, to improve alcohol oxidation products yield consumption
When it is longer, while inevitably result from metallic wastewater, cause environmental pollution, increase treatment cost.Using quaternary ammonium salt as urging
During agent, although catalytic activity is higher, its intrinsic equal phase behaviour, the commercial Application of quaternary ammonium salt catalyst is limited.With
When ionic liquid is as catalyst, the preparation process of ionic liquid is cumbersome, the larger progress for hindering reaction of oneself viscosity, ionic liquid
Body is equally homogeneous catalyst, causes product to be difficult to separate with catalyst.Heteropolyacid catalyst compared with above-mentioned several catalyst,
Have the advantages that reaction condition is gentle, the catalytic reaction time is short, catalyst amount is few, but it falls within homogeneous catalyst, it is readily soluble
It is not easily recycled in polar solvent, the reuse to catalyst causes difficulty.It is, thus, sought for a kind of suitable carrier is used
It is immobilized in heteropoly acid, it is used for heterogeneous catalytic reaction as heterogeneous catalysis.
In summary, find that a kind of method is simple, cost is low, the good supported heteropolyacid catalyst preparation side of immobilized effect
Method is significant for the course of reaction of cyclohexanol synthesizing cyclohexanone.
The content of the invention
The technical problem to be solved in the present invention be for current cyclohexanol synthesizing cyclohexanone process catalyst activity it is low,
The defects of multiplexing performance difference.There is provided a kind of supported heteropolyacid phase transfer catalyst that cyclohexanol prepares cyclohexanone process and
Its preparation method, this method can realize heteropoly acid in the efficient immobilized of surface of graphene oxide, and method is simple, cost
It is low, phase transfer catalysis (PTC) effect is good.
The technical solution adopted for the present invention to solve the technical problems is：One kind prepares cyclohexanone mistake for cyclohexanol
The supported heteropolyacid phase transfer catalyst of journey, its structural formula are as follows：
The specific preparation method of the supported heteropolyacid phase transfer catalyst is as follows：
(1) in tetrahydrofuran, graphene oxide and 3- aminopropyl trimethoxysilanes are mixed, wherein graphene oxide
Mass ratio with silane is 1:5~1:10, magnetic agitation under nitrogen protection, flow back 12-24h under 80-100 DEG C of oil bath.Then
Filtering, is washed with ethanol, gained solid is dried in vacuo into 12h at 60 DEG C.
Shown in formula specific as follows：
(2) solid matter obtained by step (1) is put into agate mortar with phosphotungstic acid, wherein solid and phosphotungstic acid mass ratio
For 2:1~1:1, it is fully ground at room temperature 1 hour, thing to be mixed stops as grey powder thing, as required phase transfer
Catalyst.
Shown in formula specific as follows：
Graphene oxide of the present invention is prepared in accordance with the following methods：
In ice-water bath, 5g crystalline flake graphites and 2.5g sodium nitrate are well mixed with the 115mL concentrated sulfuric acid, in stirring slowly
Add 15gKMnO4, less than 2 DEG C sustained response 1h are kept, 35 DEG C of water-bath 30min is transferred them to, is gradually added 250mL
Deionized water, temperature rise to 98 DEG C and continued after reacting 1h, can substantially observe mixture by brown stain into glassy yellow.Further
Continuously it is diluted with water, and with the H of mass fraction 30%2O2Solution processing.Above-mentioned solution is filtered, with 5%HCl solution wash to
Neutrality, filter cake is put into baking oven 80 DEG C and is fully drying to obtain graphite oxide.0.1g graphite oxides are taken to be put into 50mL deionized waters
In, 1.5h (180W, 60Hz) is ultrasonically treated, is then filtered, filter cake is put into vacuum drying oven 40 DEG C (10Pa) and dries 6h
Produce required graphene oxide.
The present invention is successfully realized the efficient immobilized of heteropoly acid, with biography in a mild condition using graphene oxide as carrier
The solid-carrying heteropolyacid material molecule sieve of system has compared significant excellent properties with high molecular polymer.Compared with molecular sieve, oxygen
Not only specific surface area is high for graphite alkene, and material hardness is strong, and course of reaction resistance to mass tranfer is small, and preparation cost is low, is easy to industrialize
Using.Compared with high molecular polymer, method of the invention is it is possible to prevente effectively from the swelling operation of macromolecule polymer material, letter
The problem of having changed catalyst preparation process, and having avoided the high-temperature behavior difference of high molecular polymer.With traditional Supported on Zeolite
Heteropolyacid catalyst is compared with high molecular polymer solid-carrying heteropolyacid catalyst, and catalyst used in the present invention is in cyclohexanol oxygen
Change prepare cyclohexanone phase transfer catalysis (PTC) process performance it is excellent the main reason for be due to used carrier amphiphilic performance.Aoxidize stone
The oxygen-containing functional group on black alkene surface causes it to have significant hydrophily, and the hexatomic ring carbon structure of itself makes it show to show
The lipophile of work.The reaction system that cyclohexanol prepares cyclohexanone with hydrogen peroxide reaction is water-oil phase, using graphene oxide as load
Supported heteropolyacid catalyst prepared by body can freely be worn using the amphipathic property of surface of graphene oxide in water-oil phase
Shuttle, so as to realize the quick transmission of active group, therefore phase transfer catalysis (PTC) better performances.Amphiphilic of the invention by graphene oxide
The phase transfer catalytic oxidation process that performance is used for benzene hexanol at home and abroad still belongs to the first time.In addition, the present invention is also first by solid phase
Acid-base reaction is used for the preparation process of carried heteropoly acid catalyst, and this method is compared with traditional organic phase solid support method, no
It is only green, and flow is simple, greatlys save the production cost of catalyst.
Brief description of the drawings
Fig. 1 is to recycle the FT-IR spectrograms of rear catalyst and fresh catalyst three times.
Embodiment
The present invention will be described further with regard to following examples, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1：
In tetrahydrofuran, by graphene oxide and 3- aminopropyl trimethoxysilane silane mixtures, wherein graphite oxide
Alkene and the mass ratio of 3- aminopropyl trimethoxysilanes are 1:5, magnetic agitation under nitrogen protection, flow back 12h under 80 DEG C of oil baths.
Then filtering, is washed with ethanol, gained solid is dried in vacuo into 12h at 60 DEG C.Gained solid matter is put into phosphotungstic acid
In agate mortar, wherein solid and phosphotungstic acid mass ratio are 2:1, it is fully ground at room temperature 1 hour, thing to be mixed turns into gray powder
Last shape thing stops, and as required phase transfer catalyst, is designated as CAT1.
Embodiment 2：
In tetrahydrofuran, graphene oxide and 3- aminopropyl trimethoxysilanes are mixed, wherein graphene oxide with
The mass ratio of 3- aminopropyl trimethoxysilanes is 1:10, magnetic agitation under nitrogen protection, flow back 12h under 100 DEG C of oil baths.With
After filter, washed with ethanol, gained solid be dried in vacuo 12h at 60 DEG C.Gained solid matter and phosphotungstic acid are put into agate
In Nao mortars, wherein solid and phosphotungstic acid mass ratio are 1:1, it is fully ground at room temperature 1 hour, thing to be mixed turns into grey powder
Shape thing stops, and as required phase transfer catalyst, is designated as CAT2.
Embodiment 3：
In tetrahydrofuran, graphene oxide and 3- aminopropyl trimethoxysilanes are mixed, wherein graphene oxide with
The mass ratio of 3- aminopropyl trimethoxysilanes is 1:8, magnetic agitation under nitrogen protection, flow back 24h under 90 DEG C of oil baths.Then
Filtering, is washed with ethanol, gained solid is dried in vacuo into 12h at 60 DEG C.Gained solid matter and phosphotungstic acid are put into agate
In mortar, wherein solid and phosphotungstic acid mass ratio are 2:1, it is fully ground at room temperature 1 hour, thing to be mixed turns into grey powder
Thing stops, and as required phase transfer catalyst, is designated as CAT3.
Embodiment 4：
In tetrahydrofuran, graphene oxide and 3- aminopropyl trimethoxysilanes are mixed, wherein graphene oxide with
The mass ratio of 3- aminopropyl trimethoxysilanes is 1:5, magnetic agitation under nitrogen protection, flow back 24h under 100 DEG C of oil baths.With
After filter, washed with ethanol, gained solid be dried in vacuo 12h at 60 DEG C.Gained solid matter and phosphotungstic acid are put into agate
In Nao mortars, wherein solid and phosphotungstic acid mass ratio are 2:1, it is fully ground at room temperature 1 hour, thing to be mixed turns into grey powder
Shape thing stops, and as required phase transfer catalyst, is designated as CAT4.
The immobilized ionic-liquid catalyst CAT1-CAT4 that embodiment 1~4 is obtained is used for cyclohexanol and reacted with hydrogen peroxide
In synthesizing cyclohexane 1 reactive ketone, reaction condition is：
Under air pressure, by 0.6g catalyst, 40mmol cyclohexanol, the aqueous hydrogen peroxide solutions of 100mmol 30%, add
Enter into 50mL two mouthfuls of round-bottomed flasks, stirred under 90 DEG C of oil baths.Question response is cooled to room temperature, Filtration of catalyst after terminating
Afterwards, filtrate is extracted with ether.Supernatant is centrifuged, examined on SP-6890 types gas chromatograph (GC) using FID
Survey device and FFAP capillary columns (are analyzed.The data of GC conversions and selectivity are calculated using internal standard dodecane.By filtering from
Catalyst is reclaimed in reactant mixture, and is handled by washing with water to reuse.
Concrete outcome is as shown in table 1.
The catalytic activity of the catalyst of table 1
| Catalyst | Hexamethylene alcohol conversion (%) | Cyclohexanone selectivity (%) |
| CAT1 | 85.1 | 94.8 |
| CAT2 | 89.2 | 95.4 |
| CAT3 | 89.0 | 95.2 |
| CAT4 | 87.4 | 95.3 |
As it can be seen from table 1 the catalyst of the present invention is applied in cyclohexanol reaction, catalyst has higher
Activity.
The catalyst in reaction solution is reclaimed using the method for filtering, reused after drying, catalyst CAT2 is in ring
The reuse result that hexanol oxidation is prepared in the reaction of cyclohexanone is as shown in table 2.
The repetition experimental result of the catalyst of table 2
| Cycle-index | Hexamethylene alcohol conversion (%) | Cyclohexanone selectivity (%) |
| 1 | 89.2 | 95.4 |
| 2 | 89.0 | 96.1 |
| 3 | 88.7 | 95.7 |
From table 2 it can be seen that the catalyst, after 3 multiplexings, the conversion ratio of cyclohexanol is basicly stable, illustrates that this is urged
Agent can be reused without reducing its catalytic activity, have good effect.
The FT-IR spectrograms that rear catalyst three times and fresh catalyst are recycled from accompanying drawing 1 can be seen that：After three times
Sample in C-N stretching vibrations functional group, and main functional group on heteropoly acid is still present, and illustrates the activity on catalyst
Component is not lost in, therefore is a kind of highly stable supported heteropolyacid catalyst.
It is complete by above-mentioned description, relevant staff using the above-mentioned desirable embodiment according to the present invention as enlightenment
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to determines its technical scope according to right.
Claims (2)
- A kind of 1. phase transfer catalyst of cyclohexanol synthesizing cyclohexanone, it is characterised in that the following institute of structural formula of the catalyst Show：
- 2. a kind of preparation method of phase transfer catalyst for cyclohexanol synthesizing cyclohexanone as claimed in claim 1, It is characterized in that the preparation method is specifically what is followed the steps below：(1) in tetrahydrofuran, graphene oxide and 3- aminopropyl trimethoxysilanes are mixed, wherein graphene oxide and 3- The mass ratio of aminopropyl trimethoxysilane is 1:5~1:10, magnetic agitation, flows back under 80-100 DEG C of oil bath under nitrogen protection 12-24h, then filtering, is washed with ethanol, gained solid is dried in vacuo into 12h at 60 DEG C,Shown in formula specific as follows：(2) solid matter obtained by step (1) is put into agate mortar with phosphotungstic acid, wherein solid and phosphotungstic acid mass ratio are 2: 1~1:1, it is fully ground at room temperature, thing to be mixed stops as grey powder thing, as required phase transfer catalyst, tool Body is shown below：
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435251A (en) * | 2018-03-19 | 2018-08-24 | 山西大学 | A kind of preparation method and applications of separable emulsion catalyst |
| CN112657553A (en) * | 2020-12-16 | 2021-04-16 | 常州大学 | Preparation method of self-separable Pickering emulsion catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870430A (en) * | 2016-06-20 | 2016-08-17 | 扬州大学 | Method for preparing three-dimensional graphene-phosphotungstate |
| CN106622373A (en) * | 2016-12-23 | 2017-05-10 | 山东大学 | Silicon dioxide-loaded solid heteropolyacid oxidation desulfurization catalyst and preparation method thereof |
| CN106702422A (en) * | 2015-11-17 | 2017-05-24 | 中国科学院过程工程研究所 | Polyacid-graphene composite material and preparation method and application thereof |
| CN106732778A (en) * | 2016-12-30 | 2017-05-31 | 常州大学 | A kind of immobilized heteropoly acid ionic-liquid catalyst and preparation method thereof |
| CN106890636A (en) * | 2017-03-24 | 2017-06-27 | 齐齐哈尔大学 | A kind of heteropoly acid/graphene oxide compound and its preparation method and application |
-
2017
- 2017-09-26 CN CN201710880179.8A patent/CN107694610B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702422A (en) * | 2015-11-17 | 2017-05-24 | 中国科学院过程工程研究所 | Polyacid-graphene composite material and preparation method and application thereof |
| CN105870430A (en) * | 2016-06-20 | 2016-08-17 | 扬州大学 | Method for preparing three-dimensional graphene-phosphotungstate |
| CN106622373A (en) * | 2016-12-23 | 2017-05-10 | 山东大学 | Silicon dioxide-loaded solid heteropolyacid oxidation desulfurization catalyst and preparation method thereof |
| CN106732778A (en) * | 2016-12-30 | 2017-05-31 | 常州大学 | A kind of immobilized heteropoly acid ionic-liquid catalyst and preparation method thereof |
| CN106890636A (en) * | 2017-03-24 | 2017-06-27 | 齐齐哈尔大学 | A kind of heteropoly acid/graphene oxide compound and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| WEIMING XIAO ET AL.: "Anchoring H3PW12O40 on 3-aminopropyltriethoxysilane modified graphene oxide:enhanced adsorption capacity and photocatalytic activity toward methyl orange", 《NEW J. CHEM.》 * |
| 付金贝: "负载型固体杂多酸的制备及其脱硫性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 张龙等主编: "《绿色化学（第二版）》", 31 August 2014 * |
| 顾婷婷等: ""二氧化硅负载磷钨酸催化氧化环己醇为环己酮的研究", 《化学试剂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435251A (en) * | 2018-03-19 | 2018-08-24 | 山西大学 | A kind of preparation method and applications of separable emulsion catalyst |
| CN108435251B (en) * | 2018-03-19 | 2020-12-25 | 山西大学 | Preparation method and application of separable emulsion catalyst |
| CN112657553A (en) * | 2020-12-16 | 2021-04-16 | 常州大学 | Preparation method of self-separable Pickering emulsion catalyst |
| CN112657553B (en) * | 2020-12-16 | 2023-08-29 | 常州大学 | Preparation method of self-separable Pickering emulsion catalyst |
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