CN102295524A - 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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- CN102295524A CN102295524A CN2011101681872A CN201110168187A CN102295524A CN 102295524 A CN102295524 A CN 102295524A CN 2011101681872 A CN2011101681872 A CN 2011101681872A CN 201110168187 A CN201110168187 A CN 201110168187A CN 102295524 A CN102295524 A CN 102295524A
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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 system hexalin and pimelinketone, specifically, employing supports cerium and surface-functionalized MCM-48 mesopore molecular sieve is a catalyzer, with oxygen is oxygenant, under the condition of not adding solvent the hexanaphthene catalyzed oxidation is generated hexalin and pimelinketone.
Background technology
Hexalin and pimelinketone are the important intermediate of producing nylon, also have a wide range of applications in fields such as industrial coating, medicine and agricultural chemicals simultaneously, so cyclohexane selectively oxidizing be reflected at 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 sophisticated industrial technology at present, but the per pass conversion of hexanaphthene has only about 4%, and selectivity is about 80%, and production efficiency is low, and material consumption is big, produce pollute comparatively serious.In order to develop the production technique of hexalin and pimelinketone, Chinese scholars has been done number of research projects at cyclohexane selectively oxidizing system hexalin and pimelinketone reaction.Wherein, employing oxygen is oxygenant, under the situation of not adding any solvent, cyclohexane selectively oxidizing is generated the operational path of hexalin and pimelinketone, because it has less energy consumption, few, the advantages of environment protection of refuse, has been subjected to investigators' extensive concern.
For example, patent CN101822990A discloses a kind of load type nano gold catalyst that is used 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 1.5MPa oxygen condition, 150 ℃ of stirring reaction 3h, cyclohexane conversion only is about 9%; Patent CN101862660A discloses a kind of nano catalyst that is used for cyclohexane oxidation, wherein Si is the carrier of catalyzer, Ti etc. are as the auxiliary agent of carrier, under 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 also only to be 93%; Zhao etc. have prepared the mesopore silicon oxide catalyzer of Au load, under 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 1MPa oxygen condition, 120 ℃ of reaction 2h, cyclohexane conversion can reach 14%, and the overall selectivity of hexalin and pimelinketone reaches 92%.Though 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, at 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 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 adulterated AlPO-5 molecular sieve catalyst of Gd is the highest, under 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 preparation such as Lu
2/ V-HMS catalyzer, under 0.5MPa oxygen condition, 140 ℃ of reaction 4h, cyclohexane conversion can reach 18%, but the selectivity of hexalin and pimelinketone be 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 hexanaphthene catalyzed oxidation.But the activity of these catalyst systems and selectivity more or less also have the space of some raisings, and this need understand on the basis of reaction mechanism, and catalyzer is designed and optimizes.
The present invention to the main design thought of catalyzer is: mesopore molecular sieve is carried out heteroatoms is adulterated to be modified the mesoporous material surface simultaneously, the former function provides the catalytic oxidation activity center, the latter's function is the polarity on modulation mesoporous material surface, make the surface, duct have identical polarity, improve the absorption of catalyzer reactant with 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 system hexalin and pimelinketone, and key has been to prepare a kind of molecular oxygen catalysis oxidizing ethyle alkyl is reacted and has had highly active cerium and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of supporting.
The method of a kind of cyclohexane selectively oxidizing system hexalin and pimelinketone, it is characterized in that, employing supports cerium and surface-functionalized MCM-48 mesopore molecular sieve is a catalyzer, and oxygen is oxygenant, under the condition of not adding solvent the hexanaphthene catalyzed oxidation is generated hexalin and pimelinketone.Concrete steps are as follows: with the 10ml cyclohexane give is in the reactant injecting reactor, add 50mg and support cerium and surface-functionalized MCM-48 mesopore molecular sieve, feed the oxygen of 0.5Mpa pressure then, 140 ℃～180 ℃ were reacted 4～12 hours, and obtained reaction product hexalin and pimelinketone.
Described catalyzer adopts earlier the hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, then it is carried out surface-functionalizedly, obtains final catalyst.
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, stirred 1 hour down, form clear gel in 50 ℃;
(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 the step (b), stirs 0.5 hour down in 50 ℃;
(e) tetraethoxy slowly is added drop-wise in the mixed solution of steps d gained, stirred 3 hours down in 50 ℃;
(f) mixed solution with step e gained is transferred in the autoclave, 100 ℃ of following crystallization after 3 days, and 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 the said process is carried out surface-functionalizedly, concrete steps are as follows:
(a) silylating reagent is mixed with benzole soln, add the MCM-48 mesopore molecular sieve that supports Ce then, stirring and refluxing is 3 hours under 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 the cerous sulfate, and silylating reagent can be a 3-aminopropyl trimethoxysilane, 3,3,3-trifluoro propyl Trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane etc.
In the above-mentioned Preparation of catalysts method, main innovate point is: support in mesopore molecular sieve in the oxidation activity component, carry out hydrophobic treatment by organic group functionized surface to mesoporous material, reduce the polarity of catalyst surface, to improve the selectivity of catalyzer to hexalin and pimelinketone.
With method for preparing support cerium and surface-functionalized MCM-48 mesoporous molecular sieve catalyst, be used for the reaction of hexanaphthene selective oxidation system hexalin and pimelinketone.Under 0.5MPa oxygen condition, 140 ℃～180 ℃ were reacted 4～12 hours, and conversion of cyclohexane reaches as high as 23.9%.In addition, catalyzer also demonstrates reaction stability preferably.
Compared with prior art, the method for cyclohexane selectively oxidizing system hexalin of the present invention 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 mixing are obtained sodium hydroxide solution, add 10.5 gram cetyl trimethylammonium bromides down, stirred 1 hour, form clear gel A at 50 ℃; With 0.52 gram Ce (NO
3)
3NH
2O mixes with 10 gram deionized waters, and stirring and dissolving obtains cerium solution, under agitation dropwise adds then among the clear gel A, stirs after 0.5 hour, drips 12.5 gram tetraethoxys in mixed solution, stirs after 3 hours, changes crystallization in the autoclave over to.With autoclave 100 ℃ place 3 days after, through cooling, filter, obtain solid after the washing, and through 100 ℃ of dryings 2 hours, 550 ℃ of roastings 6 hours promptly obtain the MCM-48 molecular sieve that cerium supports.
Carry out surface-functionalized to the MCM-48 mesopore molecular sieve that supports Ce for preparing in the said process then.0.54 gram 3-aminopropyl trimethoxysilane is mixed with benzole soln, add the MCM-48 mesopore molecular sieve that 0.3 gram supports Ce then, stirring and refluxing is 3 hours under 125 ℃ of temperature.At last, separate after 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 reactor, feed the oxygen of 0.5Mpa pressure then, 140 ℃ were reacted 4 hours, after being cooled to room temperature, reaction product hexalin and pimelinketone are analyzed with gas-chromatography.Conversion of cyclohexane is 8.3%, and the selectivity of hexalin and pimelinketone is 93.2%.
Embodiment 2
With the Ce (NO that adds among the 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 conversion of cyclohexane that obtains is 14.6%, and the selectivity of hexalin and pimelinketone is 86%.
Embodiment 3
With the cerium source of adopting among the 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 conversion of cyclohexane that obtains is 7.1%, and the selectivity of hexalin and pimelinketone is 99.5%.
Embodiment 4
The Preparation of Catalyst 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 conversion of cyclohexane is 14.6%, and the selectivity of hexalin and pimelinketone is 89.4%.
Embodiment 5
The Preparation of Catalyst 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 conversion of cyclohexane is 14.9%, and the selectivity of hexalin and pimelinketone is 87.8%.
Embodiment 6
Change the surface-functionalized reagent that adopts among the embodiment 1 into 3 by the 3-aminopropyl trimethoxysilane, 3,3-trifluoro propyl Trimethoxy silane, other preparation condition of catalyzer is identical with embodiment 1, obtain supporting Ce and 3,3, the MCM-48 mesoporous molecular sieve catalyst that 3-trifluoro propyl Trimethoxy silane is surface-functionalized.Reaction conditions is identical with embodiment 1, and the conversion of cyclohexane that obtains is 18.9%, and the selectivity of hexalin and pimelinketone is 88.2%.
Embodiment 7
Change the surface-functionalized reagent that adopts among the embodiment 1 into 3,3 by the 3-aminopropyl trimethoxysilane, 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 3,3, the MCM-48 mesoporous molecular sieve catalyst that 3-trifluoro propyl Trimethoxy silane is surface-functionalized.Reaction conditions is identical with embodiment 1, and the conversion of cyclohexane that obtains is 21.2%, and the selectivity of hexalin and pimelinketone is 85.6%.
Embodiment 8
Change the surface-functionalized reagent that adopts among the embodiment 1 into 3 by the 3-aminopropyl trimethoxysilane, 3,3-trifluoro propyl Trimethoxy silane, other preparation condition of catalyzer is identical with embodiment 1, obtain supporting Ce and 3,3, the MCM-48 mesoporous molecular sieve catalyst that 3-trifluoro propyl Trimethoxy silane is surface-functionalized.Temperature of reaction is 160 ℃, and other reaction conditions is identical with embodiment 1, and the conversion of cyclohexane that obtains is 23.4%, and the selectivity of hexalin and pimelinketone is 84.7%.
Embodiment 9
Change the surface-functionalized reagent that adopts among the embodiment 1 into 3 by the 3-aminopropyl trimethoxysilane, 3,3-trifluoro propyl Trimethoxy silane, other preparation condition of catalyzer is identical with embodiment 1, obtain supporting Ce and 3,3, the MCM-48 mesoporous molecular sieve catalyst that 3-trifluoro propyl Trimethoxy silane is surface-functionalized.Reaction times is 12 hours, and other reaction conditions is identical with embodiment 1, and the conversion of cyclohexane that obtains is 23.9%, and the selectivity of hexalin and pimelinketone is 85.1%.
Embodiment 10
Change the surface-functionalized reagent that adopts among the embodiment 1 into 3,3 by the 3-aminopropyl trimethoxysilane, 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 3,3, the MCM-48 mesoporous molecular sieve catalyst that 3-trifluoro propyl Trimethoxy silane is surface-functionalized.Reaction conditions is identical with embodiment 1, and the conversion of cyclohexane that obtains is 7.9%, and the selectivity of hexalin and pimelinketone is 89.1%.
Claims (6)
1. the method for cyclohexane selectively oxidizing system hexalin and pimelinketone, it is characterized in that, employing supports cerium and surface-functionalized MCM-48 mesopore molecular sieve is a catalyzer, and oxygen is oxygenant, under the condition of not adding solvent the hexanaphthene catalyzed oxidation is generated hexalin and pimelinketone.May further comprise the steps: with cyclohexane give is in the reactant injecting reactor, add and support cerium and surface-functionalized MCM-48 mesopore molecular sieve, feed the oxygen of 0.5Mpa pressure then, 140 ℃～180 ℃ were reacted 4～12 hours, and obtained reaction product hexalin and pimelinketone.
2. catalyzer according to claim 1 is characterized in that, adopts earlier the hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, then it is carried out surface-functionalizedly, obtains final catalyst.
3. catalyzer according to claim 2 is characterized in that, at first adopts the hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, comprises the following steps:
(a) NaOH and water are mixed, obtain sodium hydroxide solution;
(b) in sodium hydroxide solution, add cetyl trimethylammonium bromide, stirred 1 hour down, form clear gel in 50 ℃;
(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 the step (b), stirs 0.5 hour down in 50 ℃;
(e) tetraethoxy slowly is added drop-wise in the mixed solution of steps d gained, stirred 3 hours down in 50 ℃;
(f) mixed solution with step e gained is transferred in the autoclave, 100 ℃ of following crystallization after 3 days, and 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 the said process is carried out surface-functionalizedly, comprise the following steps:
(a) silylating reagent is mixed with benzole soln, add the MCM-48 mesopore molecular sieve that supports Ce then, stirring and refluxing is 3 hours under 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.
4. preparation method according to claim 3 is characterized in that, described cerium salt can be any in cerous nitrate and the cerous sulfate.
5. preparation method according to claim 3 is characterized in that, the mass content of cerium salt is 1%～10% in the described catalyzer.
6. preparation method according to claim 3 is characterized in that, described silylating reagent can be a 3-aminopropyl trimethoxysilane, 3,3,3-trifluoro propyl Trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane etc.
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Cited By (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 |
| CN103551192A (en) * | 2013-11-22 | 2014-02-05 | 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 |
| CN106831387A (en) * | 2017-01-19 | 2017-06-13 | 上海科技大学 | A kind of saturation C-H bond direct oxidation method of visible light catalytic |
| 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 |
| CN114632538A (en) * | 2022-04-01 | 2022-06-17 | 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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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103551192A (en) * | 2013-11-22 | 2014-02-05 | 东北石油大学 | Preparation method of rare-earth modified MCM-48 loaded double-function catalyst |
| 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 |
| CN106831387A (en) * | 2017-01-19 | 2017-06-13 | 上海科技大学 | A kind of saturation C-H bond direct oxidation method of visible light catalytic |
| WO2018133473A1 (en) * | 2017-01-19 | 2018-07-26 | 上海科技大学 | Visible light catalysed saturated carbon hydrogen bond direct oxidation method |
| 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 |
| US11008272B1 (en) * | 2017-01-19 | 2021-05-18 | Shanghaitech University | Visible-light-induced direct oxidation method for saturated hydrocarbon bonds |
| 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 |
| CN114632538A (en) * | 2022-04-01 | 2022-06-17 | 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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