CN107803220B - Supported imidazole ionic liquid catalyst and application thereof in preparation of cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane - Google Patents

Supported imidazole ionic liquid catalyst and application thereof in preparation of cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane Download PDF

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CN107803220B
CN107803220B CN201710972915.2A CN201710972915A CN107803220B CN 107803220 B CN107803220 B CN 107803220B CN 201710972915 A CN201710972915 A CN 201710972915A CN 107803220 B CN107803220 B CN 107803220B
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sba
cyclohexane
cyclohexanol
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CN107803220A (en
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胡玉林
陈刚
高川
巩珣
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Chongqing Chemical Research Institute Co., Ltd
Chongqing Chemical Research Institute Material Technology Co., Ltd
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China Three Gorges University CTGU
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    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a supported imidazole ionic liquid catalyst and application thereof in preparing cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane. The method uses cyclohexane as a reactant, oxygen as an oxidant and transition metal doped SBA-16 mesoporous molecular sieve supported ionic liquid as a catalyst, does not need to add any organic solvent and additive in the reaction process, and prepares cyclohexanol and cyclohexanone through high-selectivity oxidation reaction. After the reaction is finished, the catalyst and the product can be separated by simple filtration, and the catalyst can be well recycled. The catalyst of the invention is easy to prepare, has the advantages of less catalyst consumption, high catalytic efficiency, high reaction selectivity and simple operation, and is a high-efficiency and environment-friendly synthesis method.

Description

Supported imidazole ionic liquid catalyst and application thereof in preparation of cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane
Technical Field
The invention relates to a method for preparing cyclohexanol and cyclohexanone by using cyclohexane as a raw material to catalyze selective oxidation of molecular oxygen, a novel transition metal doped mesoporous molecular sieve supported ionic liquid catalyst used by the method and a preparation method of the catalyst.
Technical Field
Cyclohexanol and cyclohexanone are important chemical raw materials and are widely applied to the production of compounds such as pharmaceutical and pesticide intermediates, high polymer materials, industrial coatings and the like. At present, the main methods for producing cyclohexanol and cyclohexanone at home and abroad are cyclohexane oxidation methods, mainly cyclohexane catalytic oxidation methods and cyclohexane non-catalytic oxidation methods, wherein the cyclohexane catalytic oxidation method is the most important method for industrially producing cyclohexanol and cyclohexanone. At present, cobalt salt or boric acid is mainly used as a catalyst in industry, and cyclohexane and air are subjected to catalytic oxidation reaction to generate main products of cyclohexanol and cyclohexanone, but the method has low production efficiency, the conversion rate of cyclohexane is less than 5%, the total selectivity of the products is only about 80%, the resource utilization rate is low, and the residue discharge amount is large. Therefore, the catalytic oxidation reaction technology of cyclohexane is always a challenging research subject, and how to design a catalyst with high conversion rate and high selectivity for preparing cyclohexanol and cyclohexanone by catalytic oxidation of cyclohexane has been widely concerned by chemists at home and abroad.
CN1781889A adopts microporous molecular sieve to load Pd or Pt noble metal catalyst, oxygen is oxidant, cyclohexane is catalyzed and oxidized at 100-130 ℃ under 0.9-1.0MPa, the conversion rate of cyclohexane is less than 15%, the total selectivity of cyclohexanol and cyclohexanone is about 90%, CN1810746A adopts prepared AIPO-5 molecular sieve which loads Ce as catalyst, high-pressure oxygen is introduced, cyclohexane oxidation is catalyzed at 160 ℃ under 130-160 ℃, the maximum conversion rate of cyclohexane is only 13%, the total selectivity of cyclohexanol and cyclohexanone is 90%, other reported catalysts are V-ZSM-5 molecular sieve (CN102211035A), transition metal alloy catalyst (CN101264446A), MOR-D load [ FeCl2{ η 3-HC (pz)3}]Complexes (L. M.D.R.S.Martins, A.Martinsa, E.C.B.A.Alegr, A.P.Carvalho, A.J. L. Pombeiro, appl.Catal.A: Gen.,2013, 464-aCobOxManganese cobalt mixed oxides (m.wu, w.zhan, y.guo, y.wang, &lttttransition = L "&tttl &ttt/t &gtt &.wang, g. L u, appl.catal.a: gen.,2016,523,97), 8-hydroxyquinoline iron (III) complexes (y.wang, z.fu, x.wen, c.rong, w.wu, c.zhang, j.deng, b.dai, s.r.kirk, d.yin, j.mol.catal.a: chem.,2014,383, 384,46), graphene oxide, etc. (y.xiao, j. L iu, k.xie, w.ang, y.fang, wal, cal.7, 2017. cyclohexanone, cyclohexane, cyclohexanone, etc. have a more or less important catalytic activity than or less catalytic activity, and more or less efficient catalytic systems, thus, and more or less environmentally friendly catalytic reaction conditions exist for developing new and more or less efficient catalytic reactions.
Disclosure of Invention
The invention aims to provide a method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane, which has high conversion rate, high selectivity and environmental friendliness.
The invention takes cyclohexane as raw material, mesoporous molecular sieve supported ionic liquid as catalyst and oxygen as oxidant to realize the selective oxidation of cyclohexane to prepare cyclohexanol and cyclohexanone.
The catalytic reaction principle of the invention is as follows:
Figure BDA0001437947310000021
the catalyst is Fe, Cu, Co, Mn-Co transition metal doped SBA-16 mesoporous molecular sieve supported imidazole ionic liquid.
The chemical reaction principle and the structure for preparing the transition metal doped SBA-16 mesoporous molecular sieve supported imidazole ionic liquid used by the invention are as follows:
Figure BDA0001437947310000022
the anion of the ionic liquid in the general formula can be FeCl4,CuCl3,CrCl4The transition metal M can be single metal Mn, Cu, Co or double metal Mn-Co, general formula M-SBA-16@ I L [ anion]The reaction principle of the catalyst comprises the following steps:
(1) reacting N-methylimidazole, 3-chloropropyltriethoxysilane and a toluene solvent at the temperature of 80-110 ℃ for 10-25 hours, recovering the solvent, and drying to obtain an intermediate 1;
(2) reacting the intermediate 1, the metal-doped mesoporous molecular sieve M-SBA-16 and a toluene solvent at the temperature of 80-110 ℃ for 20-30 hours, filtering and drying to obtain an ionic liquid 2;
(3) and continuously reacting the ionic liquid 2 with ferric chloride, copper chloride or chromium chloride in an acetonitrile solvent at the temperature of between 50 and 90 ℃ for 20 to 30 hours, filtering, washing with acetonitrile, and drying to obtain the mesoporous molecular sieve supported imidazole ionic liquid catalyst.
In the step (1), the molar ratio of N-imidazole to 3-chloropropyltriethoxysilane is 1: 1-1.5;
in the step (2), the mass ratio of the intermediate 1 to the metal modified molecular sieve M-SBA-16 is 0.2-2.0: 1;
in the step (3), the molar ratio of the intermediate 2 to ferric chloride, cupric chloride or chromium chloride is 1: 1-3;
in the above reaction process, the toluene solvent was added in excess.
The invention is characterized in that cyclohexane is used as a reactant, oxygen is used as an oxidant, and the mass ratio of the used catalyst to the cyclohexane is 1-20: 150, the materials and the supported ionic liquid catalyst are fed, mixed, stirred and reacted according to the proportion.
The reaction temperature is 100-140 ℃.
The reaction time is 2-8 hours.
The reaction pressure of the invention is controlled between 0.5 MPa and 2.0 MPa.
The catalyst is one of M-SBA-16 mesoporous molecular sieve supported imidazole ferric chloride salt ionic liquid, M-SBA-16 mesoporous molecular sieve supported imidazole cupric chloride salt ionic liquid and M-SBA-16 mesoporous molecular sieve supported imidazole chromium chloride salt ionic liquid.
The catalyst with higher activity is Mn-Co-SBA-16@ I L [ FeCl4]、Mn-Co-SBA-16@IL[CuCl3]Or Mn-Co-SBA-16@ I L [ CrCl4]。
The invention relates to a method for preparing cyclohexanol and cyclohexanone by catalyzing the oxidation of cyclohexane molecular oxygen through transition metal doped SBA-16 mesoporous molecular sieve supported imidazole ionic liquid, wherein the catalytic reaction is carried out in a stainless steel reaction kettle, after the reaction is finished, the reaction kettle is cooled and kept stand, catalyst particles are deposited at the bottom of the flask, the catalyst can be recovered and reused without being treated after filtration, and the catalyst is fed in proportion for the next batch of catalytic oxidation reaction.
According to the method for preparing cyclohexanol and cyclohexanone, the key technology is that the prepared transition metal doped SBA-16 mesoporous molecular sieve supported imidazole ionic liquid is adopted to catalyze the selective oxidation reaction of cyclohexane molecular oxygen to obtain the cyclohexanol and the cyclohexanone.
Compared with the prior catalysis technology, the invention has the advantages that: (1) the molecular sieve supported imidazole ionic liquid catalyst has high catalytic activity, good stability, simple separation of products and the catalyst and recycling. (2) The reaction selectivity is good, the highest cyclohexane conversion rate can reach 15.8%, and the selectivity of cyclohexanol and cyclohexanone can reach 96.7%. (3) The whole reaction system is simple, green and efficient, and does not need to add organic solvents and additives, so the method is an environment-friendly catalytic oxidation method.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.
One embodiment of the preparation method of the transition metal doped SBA-16 mesoporous molecular sieve supported imidazole ionic liquid catalyst comprises the following steps:
(1) reacting N-methylimidazole (0.5mol), 3-chloropropyltriethoxysilane (0.5mol) and toluene (800m L) at 110 ℃ for 24 hours, recovering the solvent, and vacuum-drying at 70 ℃ for 6 hours to obtain an intermediate 1;
(2) reacting the intermediate 1(8g), the metal-doped mesoporous molecular sieve M-SBA-16(10g) and toluene (200M L) at 100 ℃ for 24 hours, filtering, and vacuum-drying at 70 ℃ for 8 hours to obtain ionic liquid 2;
(3) and continuously reacting the ionic liquid 2(0.01mol) with ferric chloride (0.01mol), copper chloride (0.01mol) or chromium chloride (0.01mol) in acetonitrile (80M L) at 70 ℃ for 24 hours, filtering, washing with acetonitrile, and drying to respectively obtain M-SBA-16 mesoporous molecular sieve supported imidazole ferric chloride salt ionic liquid, M-SBA-16 mesoporous molecular sieve supported imidazole cupric chloride salt ionic liquid and M-SBA-16 mesoporous molecular sieve supported imidazole chromium chloride salt ionic liquid.
The specific synthetic mechanism and route are as follows:
Figure BDA0001437947310000041
example 1
In a stainless steel reactor, cyclohexane 10m L, 0.2g Mn-SBA-16@ I L [ FeCl ] was charged4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis result shows that the cyclohexane conversion rate is 10.7 percent, the total selectivity of the cyclohexanol and the cyclohexanone is 89.2 percent, wherein the selectivity of the cyclohexanol is 39.8 percent, and the selectivity of the cyclohexanone is 49.4 percent.
Example 2
In a stainless steel reactor, cyclohexane 10m L, 0.2g Mn-SBA-16@ I L [ CuCl ] was charged3]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperatureAnd filtering to recover the catalyst. The GC-MS analysis showed that the cyclohexane conversion was 10.3%, the overall selectivity for cyclohexanol and cyclohexanone was 90.3%, with the selectivity for cyclohexanol being 42.5%.
Example 3
In a stainless steel reactor, cyclohexane 10m L, 0.2g Mn-SBA-16@ I L [ CrCl ] was charged4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 11.0% cyclohexane conversion, 89.8% overall cyclohexanol and cyclohexanone selectivity, with 41.2% cyclohexanol selectivity.
Example 4
In a stainless steel reactor, cyclohexane 10m L, 0.2g Cu-SBA-16@ I L [ FeCl ] was charged4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 10.2% cyclohexane conversion, 89.6% overall cyclohexanol and cyclohexanone selectivity, with 43.6% cyclohexanol selectivity.
Example 5
In a stainless steel reactor, cyclohexane 10m L, 0.2g Cu-SBA-16@ I L [ CrCl ] was charged4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 10.5% cyclohexane conversion, 91.5% overall cyclohexanol and cyclohexanone selectivity, with 44.8% cyclohexanol selectivity.
Example 6
In a stainless steel reactor, cyclohexane 10m L, 0.2g Co-SBA-16@ I L [ FeCl ] was charged4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 11.9% cyclohexane conversion, 90.8% overall cyclohexanol and cyclohexanone selectivity, with 39.7% cyclohexanol selectivity.
Example 7
In a stainless steel reactor, cyclohexane 10m L, 0.2g Co-SBA-16@ I L [ CuCl ] was charged3]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature,The catalyst was recovered by filtration. The GC-MS analysis showed 11.7% cyclohexane conversion, 91.7% overall cyclohexanol and cyclohexanone selectivity, with 46.0% cyclohexanol selectivity.
Example 8
In a stainless steel reactor, cyclohexane 10m L, 0.2g Co-SBA-16@ I L [ CrCl ] was charged4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 12.2% cyclohexane conversion, 92.0% overall selectivity for cyclohexanol and cyclohexanone, with 44.5% cyclohexanol selectivity.
Example 9
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ FeCl ] into a stainless steel reaction kettle4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst.
The GC-MS analysis showed that the cyclohexane conversion was 14.6%, the overall selectivity for cyclohexanol and cyclohexanone was 93.2%, with the selectivity for cyclohexanol being 32.7%.
Example 10
In a stainless steel reactor, cyclohexane 10m L, 0.2g Mn-Co-SBA-16@ I L [ CuCl ] was charged3]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 13.6% cyclohexane conversion, 94.0% overall selectivity for cyclohexanol and cyclohexanone, with a cyclohexanol selectivity of 38.3%.
Example 11
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed that the cyclohexane conversion was 14.9%, the overall selectivity for cyclohexanol and cyclohexanone was 94.5%, with the selectivity for cyclohexanol being 38.6%.
Example 12
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]Oxygen gas of 1.2MPa is filled in the reactor at 1The reaction was stirred at 20 ℃ for 4 hours. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed that the cyclohexane conversion was 15.8%, the overall selectivity for cyclohexanol and cyclohexanone was 96.7%, with the selectivity for cyclohexanol being 36.5%.
Example 13
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]1.2MPa of oxygen is charged, and the reaction is carried out for 4 hours at 130 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed that the cyclohexane conversion was 15.6%, the overall selectivity for cyclohexanol and cyclohexanone was 95.8%, with the selectivity for cyclohexanol being 34.2%.
Example 14
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]Then, 0.8MPa of oxygen was introduced, and the reaction was stirred at 110 ℃ for 4 hours. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed that the cyclohexane conversion was 9.4%, the overall selectivity for cyclohexanol and cyclohexanone was 97.3%, with the selectivity for cyclohexanol being 49.8%.
Example 15
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]1.8MPa of oxygen gas is charged, and the reaction is carried out for 4 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 22.6% cyclohexane conversion, 80.4% overall selectivity for cyclohexanol and cyclohexanone, with 31.7% cyclohexanol selectivity.
Example 16
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]1.2MPa of oxygen is charged, and the reaction is carried out for 2 hours at 110 ℃ with stirring. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed that the cyclohexane conversion was 10.3%, the overall selectivity for cyclohexanol and cyclohexanone was 96.9%, with the selectivity for cyclohexanol being 43.5%.
Example 17
Adding cyclohexane 10m L, 0.2gMn-Co-SBA-16@ I L [ CrCl ] into a stainless steel reaction kettle4]Oxygen of 1.2MPa is chargedThe reaction was stirred at 110 ℃ for 6 hours. Cooling to room temperature, filtering and recovering the catalyst. The GC-MS analysis showed 19.6% cyclohexane conversion, 94.3% overall selectivity for cyclohexanol and cyclohexanone, with 35.8% cyclohexanol selectivity.
Example 18
The catalyst in the embodiment 12 is recovered, the catalytic reaction is carried out according to the conditions in the embodiment 12, the recovered catalyst is repeatedly used for 5 times, and the experimental result shows that the activity of the catalyst is not reduced, the cyclohexane conversion rate is 14.5-15.8%, the total selectivity of cyclohexanol and cyclohexanone is 95.4-96.7%, and the selectivity of cyclohexanol is 34.2-36.5%.

Claims (9)

1. A supported imidazole ionic liquid catalyst is characterized in that transition metal doped SBA-16 mesoporous molecular sieve supported imidazole ionic liquid is adopted, and the specific structure is as follows:
Figure FDA0002471790160000011
the anion ion is a chloride salt compound comprising FeCl4、CuCl3、CrCl4Any one of the above; the transition metal M comprises any one of single metal Mn, Cu, Co and bimetal Mn-Co, and comprises the following steps: (1) reacting N-methylimidazole, 3-chloropropyltriethoxysilane and a toluene solvent at the temperature of 80-110 ℃ for 10-25 hours, recovering the solvent, and drying to obtain an intermediate 1; (2) reacting the intermediate 1, the metal-doped mesoporous molecular sieve M-SBA-16 and a toluene solvent at the temperature of 80-110 ℃ for 20-30 hours, filtering and drying to obtain an ionic liquid 2; (3) the ionic liquid 2 is continuously mixed with FeCl in acetonitrile solvent3Or CuCl2Or CrCl3Reacting at 50-90 ℃ for 20-30 hours, filtering, washing with acetonitrile, and drying to obtain the mesoporous molecular sieve supported imidazole ionic liquid catalyst.
2. The supported imidazole ionic liquid catalyst of claim 1, wherein the catalyst comprises Mn-Co-SBA-16@ I L [ FeCl4]、Mn-Co-SBA-16@IL[CuCl3]Or Mn-Co-SBA-16@ I L [ CrCl4]。
3. The supported imidazole ionic liquid catalyst of claim 1, wherein in step (1), the molar ratio of N-methylimidazole to 3-chloropropyltriethoxysilane is 1: 1-1.5; in the step (2), the mass ratio of the intermediate 1 to the metal modified molecular sieve M-SBA-16 is 0.2-2.0: 1; in the step (3), the ionic liquid 2 and FeCl3Or CuCl2Or CrCl3In a molar ratio of 1: 1-3; in the above reaction process, the toluene solvent was added in excess.
4. The supported imidazole ionic liquid catalyst of claim 3, wherein in step (1), the molar ratio of N-methylimidazole to 3-chloropropyltriethoxysilane is 1: 1-1.2; in the step (2), the mass ratio of the intermediate 1 to the metal modified molecular sieve M-SBA-16 is 0.8-1.0: 1; in the step (3), the ionic liquid 2 and FeCl3Or CuCl2Or CrCl3The molar ratio of (A) to (B) is 1: 1-1.5; in the above reaction process, the toluene solvent was added in excess.
5. The method for preparing cyclohexanol and cyclohexanone by using the supported imidazole ionic liquid catalyst of any one of claims 1-4, wherein cyclohexane is used as a raw material, oxygen is used as an oxidant, a transition metal is doped with an SBA-16 mesoporous molecular sieve supported imidazole ionic liquid catalyst, and the cyclohexanol and cyclohexanone are obtained by stirring and reacting for 2-8 hours at a temperature of 100-140 ℃ and under a pressure of 0.5-2.0 MPa.
6. The method according to claim 5, wherein the mass ratio of the supported imidazole ionic liquid catalyst to cyclohexane is 1-20: 150.
7. the process of claim 5 wherein the catalyst is Mn-Co-SBA-16@ I L [ CrCl4]And controlling the temperature to be 120-130 ℃.
8. The process of claim 5 wherein the catalyst is Mn-Co-SBA-16@ I L [ CrCl4]The reaction time is controlled to be 4-6 hours.
9. The process of claim 5 wherein the catalyst is Mn-Co-SBA-16@ I L [ CrCl4]The reaction pressure was controlled at 1.2 MPa.
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CN111269142B (en) * 2020-03-08 2023-03-31 三峡大学 Method for catalyzing benzylidene malononitrile compound by SBA-15 supported ionic liquid
CN112299968B (en) * 2020-11-26 2022-05-06 广州彼西络科技有限公司 Preparation method of chemical raw material
CN112299969A (en) * 2020-11-30 2021-02-02 山东卓俊实业有限公司 Application of imidazole carbonate in preparation of important chemical raw materials
CN112615048B (en) * 2020-12-17 2021-12-17 华南理工大学 Ionic liquid grafted molecular sieve imidazole framework composite solid polymer electrolyte and preparation method thereof
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CN114920624A (en) * 2022-05-27 2022-08-19 辽宁石油化工大学 Separation and purification method and system for cyclohexanol and butyl cyclohexyl ether

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101073783A (en) * 2007-06-25 2007-11-21 陕西师范大学 Solid-loaded ionic-liquid catalyst for olefin-dihydroxy reaction, its production and use
CN101709021A (en) * 2008-09-17 2010-05-19 住友化学株式会社 Method for producing cycloalkanol and/or cycloalkanone
CN104056665A (en) * 2013-03-20 2014-09-24 中国科学院大连化学物理研究所 Application of ionic liquid-modified mesoporous material in decomposition of cyclohexyl hydroperoxide
CN104826664A (en) * 2015-01-05 2015-08-12 广东工业大学 Catalyst for cyclohexane selective oxidation reactions, preparation method, and reaction method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101073783A (en) * 2007-06-25 2007-11-21 陕西师范大学 Solid-loaded ionic-liquid catalyst for olefin-dihydroxy reaction, its production and use
CN101709021A (en) * 2008-09-17 2010-05-19 住友化学株式会社 Method for producing cycloalkanol and/or cycloalkanone
CN104056665A (en) * 2013-03-20 2014-09-24 中国科学院大连化学物理研究所 Application of ionic liquid-modified mesoporous material in decomposition of cyclohexyl hydroperoxide
CN104826664A (en) * 2015-01-05 2015-08-12 广东工业大学 Catalyst for cyclohexane selective oxidation reactions, preparation method, and reaction method thereof

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