CN102295524B - Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane - Google Patents
Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane Download PDFInfo
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- CN102295524B CN102295524B CN2011101681872A CN201110168187A CN102295524B CN 102295524 B CN102295524 B CN 102295524B CN 2011101681872 A CN2011101681872 A CN 2011101681872A CN 201110168187 A CN201110168187 A CN 201110168187A CN 102295524 B CN102295524 B CN 102295524B
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Abstract
The invention discloses a method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane. The method comprises the step of carrying out catalytic oxidation on cyclohexane under the condition that no solvent is added in the presence of a cerium-supported and surface-functionalized MCM-48 mesoporous molecular sieve used as a catalyst and oxygen used as an antioxidant. The method is characterized in that hydrophobic treatment is carried out on the surface of the mesoporous material through organic group functionalization while an oxidation active component is supported in the mesoporous molecular sieve, thereby reducing the polarity of the surface of the catalyst so as to improve the selectivity of the catalyst to cyclohexanol and cyclohexanone.
Description
Technical field
The present invention relates to the method for a kind of cyclohexane selectively oxidizing hexalin processed and pimelinketone, specifically, employing supports cerium and surface-functionalized MCM-48 mesopore molecular sieve is catalyzer, take oxygen as oxygenant, catalytic oxidation of cyclohexane is generated to hexalin and pimelinketone under the condition of not adding solvent.
Background technology
Hexalin and pimelinketone are the important intermediate of producing nylon, in fields such as industrial coating, medicine and agricultural chemicals, also have a wide range of applications simultaneously, so the cyclohexane selectively oxidizing reaction industrial have very important.At present, domestic and international hexalin and pimelinketone more than 90% is to adopt the cyclohexane oxidation process (DSM/HPO) of Dutch mining company exploitation to produce.This technology is the most ripe present industrial technology, but the per pass conversion of hexanaphthene only has 4% left and right, and selectivity is about 80%, and production efficiency is low, and material consumption is large, and generation is polluted comparatively serious.In order to develop the production technique of hexalin and pimelinketone, Chinese scholars has been done a large amount of research work for cyclohexane selectively oxidizing hexalin processed and pimelinketone reaction.Wherein, employing oxygen is oxygenant, in the situation that do not add any solvent, cyclohexane selectively oxidizing is generated to the operational path of hexalin and pimelinketone, and less energy consumption, refuse are few because it has, advantages of environment protection, has been subject to investigators' extensive concern.
For example, patent CN101822990A discloses a kind of load type nano gold catalyst for cyclohexane oxidation, wherein Au is as the main active component of catalyzer, the quality percentage composition is 1%, Al is the carrier of catalyzer, and Co, Zr and Ce etc. are as the auxiliary agent of carrier, under the 1.5MPa Oxygen Condition, 150 ℃ of stirring reaction 3h, cyclohexane conversion is only 9% left and right; Patent CN101862660A discloses a kind of nano catalyst for cyclohexane oxidation, wherein Si is the carrier of catalyzer, Ti etc. are as the auxiliary agent of carrier, under the 1.5MPa Oxygen Condition, 150 ℃ of stirring reaction 3h, cyclohexane conversion is lower than 10%, and the selectivity of hexalin and pimelinketone is the highest is only also 93%; Zhao etc. have prepared the mesopore silicon oxide catalyzer of Au load, under the 1MPa Oxygen Condition, and 150 ℃ of stirring reaction 2h, cyclohexane conversion can reach 16.6%, and the selectivity of hexalin and pimelinketone reaches 92.4%, and (Catal.Today 2010,158:220); Patent CN1305824C discloses the catalyzer of a kind of titanium silicon micro porous molecular sieve load P d, as Pd and SiO
2Mol ratio be 0.008: 1 o'clock, under the 1MPa Oxygen Condition, 120 ℃ of reaction 2h, cyclohexane conversion can reach 14%, and the overall selectivity of hexalin and pimelinketone reaches 92%.Although noble metal catalyst has cyclohexane oxidation activity preferably, the cost of such catalyzer is higher, and this will limit its industrial applications prospect greatly.
In addition, for the reaction of molecular oxygen catalysis oxidizing ethyle alkyl, investigators have also prepared multiple non-precious metal catalyst.For example, patent CN1810746A discloses a kind of Ce/AlPO-5 molecular sieve catalyst, under the 0.5MPa Oxygen Condition, and 140 ℃ of reaction 4h, cyclohexane conversion can reach 13%, and the overall selectivity of hexalin and pimelinketone reaches 92%; Lu etc. have prepared various rare earth doped AlPO-5 molecular sieve catalysts, the activity of finding the AlPO-5 molecular sieve catalyst that Gd adulterates is the highest, under the 0.5MPa Oxygen Condition, and 140 ℃ of reaction 4h, cyclohexane conversion can reach 13.1% (Catal.Lett.2010,137:180); Patent CN101747142A discloses a class nano ferrite catalyzer, and transformation efficiency is more than 12%, and the selectivity of hexalin and pimelinketone is more than 92%.The CeO of the preparation such as Lu
2/ V-HMS catalyzer, under the 0.5MPa Oxygen Condition, 140 ℃ of reaction 4h, cyclohexane conversion can reach 18%, but the selectivity of hexalin and pimelinketone is 68% (Ind.Eng.Chem.Res.2010,49:5392).In sum, by well-designed, also can obtain to have the highly active non-precious metal catalyst of catalytic oxidation of cyclohexane.But the activity and selectivity of these catalyst systems more or less also has the space of some raisings, and this need to, understanding on the basis of reaction mechanism, design and optimize catalyzer.
The present invention to the main design thought of catalyzer is: when mesopore molecular sieve is carried out to Heteroatom doping, the mesoporous material surface is modified, the former function is to provide the catalytic oxidation activity center, the latter's function is the polarity on modulation mesoporous material surface, make the surface, duct have identical polarity with reactant, improve the absorption of catalyzer to reactant.By the synergistic effect of above two kinds of effects, reach the purpose that improves catalyst catalytic performance.
Summary of the invention
The object of the invention is to provide the method for a kind of cyclohexane selectively oxidizing hexalin processed and pimelinketone, and key has been to prepare a kind ofly has highly active cerium and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of supporting to molecular oxygen catalysis oxidizing ethyle alkyl reaction.
The method of a kind of cyclohexane selectively oxidizing hexalin processed and pimelinketone, it is characterized in that, employing supports cerium and surface-functionalized MCM-48 mesopore molecular sieve is catalyzer, and oxygen is oxygenant, catalytic oxidation of cyclohexane is generated to hexalin and pimelinketone under the condition of not adding solvent.Concrete steps are as follows: by the 10ml cyclohexane give, be in the reactant injecting reactor, add 50mg to support cerium and surface-functionalized MCM-48 mesopore molecular sieve, then pass into the oxygen of 0.5Mpa pressure, 140 ℃～180 ℃ were reacted 4～12 hours, and obtained reaction product hexalin and pimelinketone.
Described catalyzer, first adopt hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, then it carried out surface-functionalizedly, obtains final catalyzer.
Wherein the hydrothermal synthesis method preparation concrete steps that support the MCM-48 mesopore molecular sieve of Ce comprise:
(a) NaOH and water are mixed, obtain sodium hydroxide solution;
(b) in sodium hydroxide solution, add cetyl trimethylammonium bromide, under 50 ℃, stirred 1 hour, form clear gel;
(c) cerium salt is mixed with water, obtain containing the solution of cerium;
(d) under agitation condition, the solution that will contain cerium adds in the gel of gained in step (b), under 50 ℃, stirs 0.5 hour;
(e) tetraethoxy slowly is added drop-wise in the mixed solution of steps d gained, under 50 ℃, stirred 3 hours;
(f) mixed solution of step e gained is transferred in autoclave, 100 ℃ of lower crystallization after 3 days, filtering separation, deionized water wash, 100 ℃ of dryings, 550 ℃ of roastings are 6 hours in air, obtain supporting the MCM-48 mesopore molecular sieve of Ce.
Then the MCM-48 mesopore molecular sieve that supports Ce for preparing in said process is carried out surface-functionalizedly, concrete steps are as follows:
(a) silylating reagent is mixed with benzole soln, then add the MCM-48 mesopore molecular sieve that supports Ce, stirring and refluxing is 3 hours at 125 ℃ of temperature;
(b) filtering separation, absolute ethanol washing, 100 ℃ of dryings 2 hours, obtain supporting cerium and surface-functionalized MCM-48 mesopore molecular sieve.
Described cerium salt can be any in cerous nitrate and cerous sulfate, and silylating reagent can be 3-aminopropyl trimethoxysilane, 3,3,3-trifluoro propyl Trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane etc.
In the preparation method of above-mentioned catalyzer, main innovate point is: when in mesopore molecular sieve, supporting the oxidation activity component, by organic group functionized surface to mesoporous material, carry out hydrophobic treatment, reduce the polarity of catalyst surface, to improve the selectivity of catalyzer to hexalin and pimelinketone.
With prepared by aforesaid method, support cerium and surface-functionalized MCM-48 mesoporous molecular sieve catalyst, for hexanaphthene selective oxidation hexalin processed and pimelinketone reaction.Under the 0.5MPa Oxygen Condition, 140 ℃～180 ℃ were reacted 4～12 hours, and the transformation efficiency of hexanaphthene reaches as high as 23.9%.In addition, catalyzer also demonstrates reaction stability preferably.
Compared with prior art, the method for cyclohexane selectively oxidizing of the present invention hexalin processed and pimelinketone, can realize simultaneously the high conversion of hexanaphthene, and to the highly selective of hexalin and pimelinketone.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
Preparation supports Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of 3-aminopropyl trimethoxysilane.
1.2 gram NaOH and 70 gram deionized waters are mixed to get to sodium hydroxide solution, under 50 ℃, add 10.5 gram cetyl trimethylammonium bromides, stirred 1 hour, form clear gel A; By 0.52 gram Ce (NO
3)
3NH
2O mixes with 10 gram deionized waters, and stirring and dissolving, obtain cerium solution, then under agitation dropwise adds in clear gel A, stirs after 0.5 hour, in mixed solution, drips 12.5 gram tetraethoxys, stirs after 3 hours, changes crystallization in autoclave over to.By autoclave 100 ℃ place 3 days after, through cooling, filter, obtain solid after washing, and through 100 ℃ of dryings 2 hours, 550 ℃ of roastings 6 hours, namely obtain the MCM-48 molecular sieve that cerium supports.
Then to the MCM-48 mesopore molecular sieve that supports Ce for preparing in said process, carry out surface-functionalized.0.54 gram 3-aminopropyl trimethoxysilane is mixed with benzole soln, then add 0.3 gram to support the MCM-48 mesopore molecular sieve of Ce, stirring and refluxing is 3 hours at 125 ℃ of temperature.Finally, be separated by filtration, absolute ethanol washing, 100 ℃ of dryings 2 hours, obtain supporting cerium and the surface-functionalized MCM-48 mesopore molecular sieve of 3-aminopropyl trimethoxysilane.
50 milligrams of above-mentioned Ce of supporting and surface-functionalized MCM-48 mesoporous molecular sieve catalyst and the 10 milliliters of cyclohexane solvents of 3-aminopropyl trimethoxysilane are put into to reactor, then pass into the oxygen of 0.5Mpa pressure, 140 ℃ were reacted 4 hours, after being cooled to room temperature, with gas-chromatography, reaction product hexalin and pimelinketone are analyzed.The transformation efficiency of hexanaphthene is 8.3%, and the selectivity of hexalin and pimelinketone is 93.2%.
Embodiment 2
By the Ce (NO that adds in embodiment 1
3)
3NH
2O is increased to 0.78 gram, and other preparation condition of catalyzer is identical with embodiment 1, obtains supporting Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of 3-aminopropyl trimethoxysilane.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 14.6%, and the selectivity of hexalin and pimelinketone is 86%.
Embodiment 3
By the cerium source of adopting in embodiment 1 by Ce (NO
3)
3NH
2O changes Ce (SO into
4)
24H
2O, Ce (SO
4)
24H
2Addition 0.78 gram of O, other preparation condition of catalyzer is identical with embodiment 1, obtains supporting Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of 3-aminopropyl trimethoxysilane.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 7.1%, and the selectivity of hexalin and pimelinketone is 99.5%.
Embodiment 4
The catalyzer preparation condition is identical with embodiment 1.Temperature of reaction is increased to 160 ℃ by 140 ℃, and other reaction conditions is identical with embodiment 1, and the transformation efficiency of hexanaphthene is 14.6%, and the selectivity of hexalin and pimelinketone is 89.4%.
Embodiment 5
The catalyzer preparation condition is identical with embodiment 1.Reaction times extended to 10 hours by 4 hours, and other reaction conditions is identical with embodiment 1, and the transformation efficiency of hexanaphthene is 14.9%, and the selectivity of hexalin and pimelinketone is 87.8%.
Embodiment 6
By the 3-aminopropyl trimethoxysilane, change the surface-functionalized reagent that adopts in embodiment 1 into 3,3,3-trifluoro propyl Trimethoxy silane, other preparation condition of catalyzer is identical with embodiment 1, obtain supporting Ce and 3, the MCM-48 mesoporous molecular sieve catalyst that 3,3-trifluoro propyl Trimethoxy silane is surface-functionalized.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 18.9%, and the selectivity of hexalin and pimelinketone is 88.2%.
Embodiment 7
By the 3-aminopropyl trimethoxysilane, change the surface-functionalized reagent that adopts in embodiment 1 into 3,3,3-trifluoro propyl Trimethoxy silane, Ce (NO
3)
3NH
2The addition of O is increased to 0.78 gram, and other preparation condition of catalyzer is identical with embodiment 1, obtains supporting Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of 3,3,3-trifluoro propyl Trimethoxy silane.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 21.2%, and the selectivity of hexalin and pimelinketone is 85.6%.
Embodiment 8
By the 3-aminopropyl trimethoxysilane, change the surface-functionalized reagent that adopts in embodiment 1 into 3,3,3-trifluoro propyl Trimethoxy silane, other preparation condition of catalyzer is identical with embodiment 1, obtain supporting Ce and 3, the MCM-48 mesoporous molecular sieve catalyst that 3,3-trifluoro propyl Trimethoxy silane is surface-functionalized.Temperature of reaction is 160 ℃, and other reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 23.4%, and the selectivity of hexalin and pimelinketone is 84.7%.
Embodiment 9
By the 3-aminopropyl trimethoxysilane, change the surface-functionalized reagent that adopts in embodiment 1 into 3,3,3-trifluoro propyl Trimethoxy silane, other preparation condition of catalyzer is identical with embodiment 1, obtain supporting Ce and 3, the MCM-48 mesoporous molecular sieve catalyst that 3,3-trifluoro propyl Trimethoxy silane is surface-functionalized.Reaction times is 12 hours, and other reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 23.9%, and the selectivity of hexalin and pimelinketone is 85.1%.
Embodiment 10
By the 3-aminopropyl trimethoxysilane, change the surface-functionalized reagent that adopts in embodiment 1 into 3,3,3-trifluoro propyl Trimethoxy silane, the cerium source is by Ce (NO
3)
3NH
2O changes Ce (SO into
4)
24H
2O, Ce (SO
4)
24H
2The addition of O is 0.78 gram, and other preparation condition of catalyzer is identical with embodiment 1, obtains supporting Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of 3,3,3-trifluoro propyl Trimethoxy silane.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene that obtains is 7.9%, and the selectivity of hexalin and pimelinketone is 89.1%.
Claims (2)
1. the method for a cyclohexane selectively oxidizing hexalin processed and pimelinketone, it is characterized in that, employing supports cerium and surface-functionalized MCM-48 mesopore molecular sieve is catalyzer, and oxygen is oxygenant, catalytic oxidation of cyclohexane is generated to hexalin and pimelinketone under the condition of not adding solvent; Comprise the following steps: by cyclohexane give, be in the reactant injecting reactor, add and support cerium and surface-functionalized MCM-48 mesopore molecular sieve, then pass into the oxygen of 0.5MPa pressure, 140 ℃～180 ℃ were reacted 4～12 hours, and obtained reaction product hexalin and pimelinketone;
Described catalyzer specifically makes by following steps:
(a) NaOH and water are mixed, obtain sodium hydroxide solution;
(b) in sodium hydroxide solution, add cetyl trimethylammonium bromide, under 50 ℃, stirred 1 hour, form clear gel:
(c) cerous nitrate is mixed with water, obtain containing the solution of cerium;
(d) under agitation condition, the solution that will contain cerium adds in the gel of gained in step (b), under 50 ℃, stirs 0.5 hour;
(e) tetraethoxy slowly is added drop-wise in the mixed solution of steps d gained, under 50 ℃, stirred 3 hours;
(f) mixed solution of step e gained is transferred in autoclave, 100 ℃ of lower crystallization after 3 days, filtering separation, deionized water wash, 100 ℃ of dryings, 550 ℃ of roastings are 6 hours in air, obtain supporting the MCM-48 mesopore molecular sieve of Ce;
Then the MCM-48 mesopore molecular sieve that supports Ce for preparing in said process is carried out surface-functionalizedly, comprise the following steps:
(a) 3,3,3-trifluoro propyl Trimethoxy silane is mixed with benzole soln, then add the MCM-48 mesopore molecular sieve that supports Ce, stirring and refluxing is 3 hours at 125 ℃ of temperature;
(b) filtering separation, absolute ethanol washing, 100 ℃ of dryings 2 hours, obtain supporting cerium and surface-functionalized MCM-48 mesopore molecular sieve.
2. the method for cyclohexane selectively oxidizing according to claim 1 hexalin processed and pimelinketone, is characterized in that, the mass content of described Cerium in Catalysts salt is 1%～10%.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698793A (en) * | 2012-06-06 | 2012-10-03 | 华东理工大学 | Catalyst for preparing cyclohexanol and cyclohexanone from cyclohexane through catalytic oxidation |
| CN103551192B (en) * | 2013-11-22 | 2015-03-11 | 东北石油大学 | Preparation method of rare-earth modified MCM-48 loaded double-function catalyst |
| CN103965014A (en) * | 2014-05-15 | 2014-08-06 | 华东理工大学 | Method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane |
| CN106831387B (en) * | 2017-01-19 | 2020-12-29 | 上海科技大学 | Direct oxidation method of saturated carbon-hydrogen bond by visible light catalysis |
| CN107983397A (en) * | 2017-12-06 | 2018-05-04 | 上海应用技术大学 | A kind of cobalt manganese bimetallic catalyst aoxidized for cyclohexane selectivity, preparation method and application |
| CN108727180A (en) * | 2018-05-07 | 2018-11-02 | 同济大学 | A kind of method of surface amination Sn-Beta molecular sieve catalytics carbohydrate lactic acid producing |
| CN114632538B (en) * | 2022-04-01 | 2023-06-30 | 黑龙江八一农垦大学 | Pd/Ce-F/MCM-48 catalyst and preparation method and application thereof |
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| CN1810746A (en) * | 2006-02-28 | 2006-08-02 | 华东理工大学 | Cyclohexane selectively oxidizing process to prepare cyclohexanone and cyclohexanol |
| CN101733164A (en) * | 2009-12-21 | 2010-06-16 | 中国科学院长春应用化学研究所 | Catalyst system for liquid-phase catalytic oxidization of cyclohexane for preparing cyclohexanol and cyclohexanone and using method thereof |
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| JP5176426B2 (en) * | 2007-03-16 | 2013-04-03 | 住友化学株式会社 | Process for producing cycloalkanol and / or cycloalkanone |
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| CN1810746A (en) * | 2006-02-28 | 2006-08-02 | 华东理工大学 | Cyclohexane selectively oxidizing process to prepare cyclohexanone and cyclohexanol |
| CN101733164A (en) * | 2009-12-21 | 2010-06-16 | 中国科学院长春应用化学研究所 | Catalyst system for liquid-phase catalytic oxidization of cyclohexane for preparing cyclohexanol and cyclohexanone and using method thereof |
Non-Patent Citations (2)
| Title |
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| Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane;ZHAN Wangcheng et al.;《JOURNAL OF RARE EARTHS》;20080430;第26卷(第4期);515-522 * |
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