CN102698793A - Catalyst for preparing cyclohexanol and cyclohexanone from cyclohexane through catalytic oxidation - Google Patents
Catalyst for preparing cyclohexanol and cyclohexanone from cyclohexane through catalytic oxidation Download PDFInfo
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- CN102698793A CN102698793A CN2012101847285A CN201210184728A CN102698793A CN 102698793 A CN102698793 A CN 102698793A CN 2012101847285 A CN2012101847285 A CN 2012101847285A CN 201210184728 A CN201210184728 A CN 201210184728A CN 102698793 A CN102698793 A CN 102698793A
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Abstract
The invention discloses a Ce-carrying MCM-48 mesoporous molecular sieve catalyst for preparing cyclohexanol and cyclohexanone from cyclohexane through catalytic oxidation, and a preparation method of the Ce-carrying MCM-48 mesoporous molecular sieve catalyst. The catalyst prepared by the preparation method disclosed by the invention is characterized in that firstly, a hydrothermal method is adopted for preparing MCM-48 mesoporous molecular sieves, then, the Ce is carried onto the MCM-48 mesoporous molecular sieves through the complexing effect of organic silylating reagents on the rare earth Ce and the reaction with hydroxyls on the surfaces of the MCM-48 mesoporous molecular sieves, and the catalyst is obtained. Under the conditions that oxygen gas is used as oxidants and no solvent is adopted, the catalyst prepared by the preparation method is adopted, the cyclohexane convertion rate can reach 18.6 percent, and the total selectivity of the cyclohexanol and the cyclohexanone can be as high as 90.8 percent. The catalyst prepared by the preparation method has the characteristics that high activity and high alcohol ketone selectivity can be simultaneously obtained, and in addition, catalyst active ingredients Ce cannot easily lose in the reaction process.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application that is used for cyclohexane catalytic oxidation system cyclohexanol and cyclohexanone; Specifically; Be that a kind of organic-silylation reagent that passes through is to the complexing of Rare-Earth Ce and the hydroxyl reaction surperficial with mesopore molecular sieve; Ce supported on the MCM-48 mesopore molecular sieve process catalyst, solvent-free and be under the condition of oxidant with oxygen, the catalytic oxidation cyclohexane generates cyclohexanol and cyclohexanone.
Background technology
The cyclohexane catalytic oxidation is a very important course of reaction, is important Organic Chemicals and organic solvent by resulting cyclohexanol of cyclohexane oxidation and cyclohexanone, and they are raw materials of making nylon-6 and nylon-66.In addition, cyclohexanol and cyclohexanone also as the solvent of resin, fat, paraffin oils, butyl rubber etc., are widely used in industries such as medicine, coating, rubber, agricultural chemicals.
At present; Cyclohexanol and cyclohexanone mainly adopt cyclohexane oxidation process production, and the cyclohexane oxidation technology (DSM/HPO) of wherein Dutch mining company exploitation is the most ripe at present industrial technology, but the conversion per pass of cyclohexane has only about 4%; Selectivity is about 80%; Production efficiency is low, and material consumption is big, pollutes comparatively serious.In order to develop the production technology of cyclohexanol and cyclohexanone, Chinese scholars has been done number of research projects to cyclohexane selectively oxidizing system cyclohexanol and cyclohexanone reaction.With respect to oxidants such as hydrogen peroxide solution and TBHPs; Employing oxygen is oxidant; Under the situation of not adding any solvent; Cyclohexane selectively oxidizing is generated the process route of cyclohexanol and cyclohexanone,, received researchers' extensive concern because it has less energy consumption, few, the advantages of environment protection of refuse.
At present, more existing patents disclose the some kinds of molecular sieve catalysts that are used for the reaction of dioxygen oxidation cyclohexane.Chinese patent CN102211035A discloses a kind of vanadium doping ZSM-5 molecular sieve catalyst that is used for cyclohexane oxidation.The mol ratio of vanadium and silicon is 0.02～0.03 in catalyst, and oxygen pressure is 0.5～2.5MPa, and when reaction temperature was 80～150 ℃, reaction 1～10h cyclohexane conversion reached as high as 14.7%, and the overall selectivity of cyclohexanol and cyclohexanone is 97.3%.Chinese patent CN101773849A discloses a kind of copper doped with Al PO-5 molecular sieve catalyst that is used for cyclohexane oxidation; When oxygen pressure is 0.5MPa; When reaction temperature was 140 ℃, reaction 5h cyclohexane conversion was 8.2%, and the overall selectivity of cyclohexanol and cyclohexanone reaches 98%.Chinese patent CN1781889A discloses a kind of micro porous molecular sieve load P d or Pt noble metal catalyst that is used for cyclohexane oxidation.When oxygen pressure is 0.9-1.0MPa, reaction temperature is 100-130 ℃, and when noble metal was Pt, cyclohexane conversion was 13.5%, and the overall selectivity of cyclohexanol and cyclohexanone is higher than 92%.Chinese 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 cyclohexanol and cyclohexanone is 92%.
In addition, some documents also have the reporter molecule sieve catalyst to be applied to the research of cyclohexane catalytic oxidation.People such as Li prepared the different metal element (Ce, Ti, Co, Al, Cr, V, Zr) the HMS molecular sieve catalyst of modification is discovered CeO
2The activity of/V-HMS molecular sieve catalyst is the highest, under 0.5MPa oxygen condition, and 140 ℃ of reaction 4h, cyclohexane conversion can reach 18%, but the selectivity of cyclohexanol and cyclohexanone is lower, be merely 68% (Ind.Eng.Chem.Res.2010,5392:5399).People such as Zhan have adopted Hydrothermal Preparation Ce doped mesoporous MCM-48; At oxygen pressure is 0.5MPa, reacts 5h under 140 ℃ of conditions, and cyclohexane conversion reaches as high as 8.1%; The selectivity of cyclohexanol and cyclohexanone is that 98.7% (J.RareEarths 2008,515:522).People such as Zhao have prepared mesopore silicon oxide load Au catalyst, stirring reaction 2h under 1MPa oxygen pressure and 150 ℃ of conditions, and cyclohexane conversion can reach 16.6%, and the selectivity of cyclohexanol and cyclohexanone reaches 92.4%, and (Catal.Today 2010,158:220).People such as Yang have prepared the mesoporous molecular sieve carried Ag catalyst of MCM-41, with O
2Being oxidant, is that 150 ℃ and pressure are under the condition of 1.4MPa in temperature, stir 3h after, conversion of cyclohexane can reach 10.7%, the overall selectivity of alcohol ketone be 83.4% (J Porous Mater.2011,18:735).
In sum, through different metal is supported on the molecular sieve, can obtain cyclohexane oxidation is had the molecular sieve catalyst of certain activity, it is active directly related with the character of carrying metal.But also there is following deficiency in existing catalyst: (1) is difficult to obtain simultaneously higher cyclohexane conversion and alcohol ketone selectivity; (2) the highly active catalyst of part is active component with the noble metal, and the catalyst cost is higher.Therefore; This patent is active component with Ce; Utilize the complexing of organic-silylation reagent to Rare-Earth Ce, the hydroxyl reaction with the mesopore molecular sieve surface supports Ce on the MCM-48 mesopore molecular sieve with point-to-point mode then, prepares the MCM-48 mesoporous molecular sieve catalyst that supports Ce.This preparation method's advantage is and can more active component Ce be supported on the molecular sieve with the state of high degree of dispersion; Thereby it is active to give the higher cyclohexane oxidation of catalyst; The catalyst stability of simultaneously this method preparation is better, and active component Ce is difficult for running off in course of reaction.
Summary of the invention
The objective of the invention is to, to the complexing of Rare-Earth Ce and the hydroxyl reaction surperficial, prepare a kind of MCM-48 mesoporous molecular sieve catalyst that supports Ce with mesopore molecular sieve through organic-silylation reagent.At oxygen is that this catalyst has higher activity and alcohol ketone selectivity to cyclohexane oxidation under oxidant and the condition such as solvent-free.
Organic-silylation reagent is respectively aminopropyl trimethoxysilane (APTMS) or 3,3,3-trifluoro propyl trimethoxy silane (FPTES), and wherein the Ce mass fraction is 0.9%～9.5%, carrying capacity is 0.56～1.54mmol/g on the organic matter.
At first through the synthetic MCM-48 mesopore molecular sieve of hydro-thermal method; Then with six nitric hydrate ceriums and aminopropyl trimethoxysilane or 3; 3,3-trifluoro propyl trimethoxy silane mixes, and adds absolute ethyl alcohol again; Add the MCM-48 mesopore molecular sieve after waiting to stir, then at 50～80 ℃ of following stirring and refluxing 3～8h.Carry out suction filtration after question response finishes and use absolute ethanol washing, with the solid that obtains dry 2～24h under 80～120 ℃, make the MCM-48 mesoporous molecular sieve catalyst that supports Ce at last.
Reaction condition of the present invention is: oxygen pressure is 0.5MPa, and reaction temperature is 140 ℃～180 ℃, and the reaction time is 4h～10h, and the catalyst use amount is 5mg.
The specific embodiment
Embodiment 1
Adopt softex kw as template, ethyl orthosilicate prepares pure silicon MCM-48 as the silicon source, and its detailed process is: 0.6g NaOH is dissolved in the 30mL deionized water; Add the 5.2g softex kw then; Dropwise adding the 6.0g ethyl orthosilicate at 50 ℃ after down stirring 1h, stirring and mixture is moved into 100mL behind the 3h and have the teflon-lined crystallizing kettle, 100 ℃ of crystallization after 3 days; Carry out the washing of suction filtration and deionized water; Then that the solid that obtains is dry under 100 ℃, and, promptly obtain the MCM-48 mesopore molecular sieve at 550 ℃ of following roasting 6h.
Get 0.02g six nitric hydrate ceriums and mix, and add the 30mL absolute ethyl alcohol, add 0.3g MCM-48 mesopore molecular sieve after waiting to stir again, then at 80 ℃ of following stirring and refluxing 3h with the 0.54g aminopropyl trimethoxysilane.Carry out suction filtration after the end, and use absolute ethanol washing, the solid that obtains is dry 2h under 100 ℃, promptly obtains supporting the MCM-48 mesoporous molecular sieve catalyst 1 of Ce.
The catalyst activity appreciation condition is: 5mg catalyst and 10mL cyclohexane solution are placed agitated reactor, charge into 0.5MPa oxygen, react 4h down at 140 ℃ then, reaction centrifugalizes after finishing, and product is analyzed with gas chromatograph.The activity rating result is shown in table one.
Embodiment 2
0.02g among the embodiment 1 six nitric hydrate ceriums are increased to 0.15g, and other process is identical with embodiment 1, obtains supporting the MCM-48 mesoporous molecular sieve catalyst 2 of Ce.The catalyst activity appreciation condition is identical with embodiment 1, and the activity rating result is shown in table one.
Embodiment 3
The six nitric hydrate ceriums of 0.02g among the embodiment 1 are increased to 0.20g, and other process is identical with embodiment 1, obtains supporting the MCM-48 mesoporous molecular sieve catalyst 3 of Ce.The catalyst activity appreciation condition is identical with embodiment 1, and the activity rating result is shown in table one.
Embodiment 4
Change the aminopropyl trimethoxysilane among the embodiment 1 into 3,3,3-trifluoro propyl trimethoxy silane, other process is identical with embodiment 1, obtains supporting the MCM-48 mesoporous molecular sieve catalyst 4 of Ce.The catalyst activity appreciation condition is identical with embodiment 1, and the activity rating result is shown in table one.
Embodiment 5
Change the aminopropyl trimethoxysilane among the embodiment 1 into 3,3,3-trifluoro propyl trimethoxy silane, the 0.02g six nitric hydrate ceriums of interpolation are increased to 0.11g, and other process is identical with embodiment 1, obtains supporting the MCM-48 mesoporous molecular sieve catalyst 5 of Ce.The catalyst activity appreciation condition is identical with embodiment 1, and the activity rating result is shown in table one.
Embodiment 6
Change the aminopropyl trimethoxysilane among the embodiment 1 into 3,3,3-trifluoro propyl trimethoxy silane, the 0.02g six nitric hydrate ceriums of interpolation are increased to 0.20g, and other process is identical with embodiment 1, obtains supporting the MCM-48 mesoporous molecular sieve catalyst 6 of Ce.The catalyst activity appreciation condition is identical with embodiment 1, and the activity rating result is shown in table one.
Embodiment 7
The Preparation of Catalyst condition is identical with embodiment 5.Reaction temperature is increased to 180 ℃, and other reaction condition is identical with embodiment 1, and conversion of cyclohexane is 18.3%, and the selectivity of cyclohexanol and cyclohexanone is 92.7%.
Embodiment 8
The Preparation of Catalyst condition is identical with embodiment 5.Reaction time extends to 10 hours, and other reaction condition is identical with embodiment 1, and conversion of cyclohexane is 18.6%, and the selectivity of cyclohexanol and cyclohexanone is 90.8%.
Table one catalyst performance evaluation result
Claims (3)
1. catalyst that is used for cyclohexane oxidation system cyclohexanol and cyclohexanone; Through organic-silylation reagent to the complexing of Rare-Earth Ce and with the hydroxyl reaction on mesopore molecular sieve surface, Ce is supported on the MCM-48 mesopore molecular sieve and makes, wherein organic-silylation reagent is respectively aminopropyl trimethoxysilane and 3; 3; 3-trifluoro propyl trimethoxy silane, the Ce mass percent is 0.9%～9.5%, carrying capacity is 0.56～1.54mmol/g on the organic matter.This catalyst can be solvent-free and be under the condition of oxidant with oxygen, and the catalytic oxidation cyclohexane generates cyclohexanol and cyclohexanone.
2. the preparation method who is used for the MCM-48 mesoporous molecular sieve catalyst that supports Ce of cyclohexane oxidation according to claim 1 is characterized in that:
At first through the synthetic MCM-48 mesopore molecular sieve of hydro-thermal method; Then with six nitric hydrate ceriums and aminopropyl trimethoxysilane or 3; 3,3-trifluoro propyl trimethoxy silane mixes, and adds absolute ethyl alcohol again; Add the MCM-48 mesopore molecular sieve after waiting to stir, then at 50～80 ℃ of following stirring and refluxing 3～8h.Carry out suction filtration after question response finishes and use absolute ethanol washing, with the solid that obtains dry 2～24h under 80～120 ℃, make the MCM-48 mesoporous molecular sieve catalyst that supports Ce at last.
3. the described application of MCM-48 mesoporous molecular sieve catalyst in cyclohexane oxidation system cyclohexanol and cyclohexanone that supports Ce of claim 1; It is characterized in that; Employing oxygen is oxidant, does not add any solvent, and reaction temperature is 140～180 ℃; Reaction time is 4～10h, and oxygen pressure is 0.5MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107188775A (en) * | 2017-07-07 | 2017-09-22 | 青岛科技大学 | A kind of method that amphipathic molecule sieve load Ru nano particle catalysis α pinene hydrogenations prepare cis-pinane |
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| US6084055A (en) * | 1999-03-30 | 2000-07-04 | General Electric Company | Method for preparing poly(1,4-cyclohexanedicarboxylates) |
| CN102295524A (en) * | 2011-06-21 | 2011-12-28 | 华东理工大学 | Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane |
-
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- 2012-06-06 CN CN2012101847285A patent/CN102698793A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6084055A (en) * | 1999-03-30 | 2000-07-04 | General Electric Company | Method for preparing poly(1,4-cyclohexanedicarboxylates) |
| CN102295524A (en) * | 2011-06-21 | 2011-12-28 | 华东理工大学 | Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane |
Non-Patent Citations (2)
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| 《中国优秀硕士学位论文全文数据库》 20120428 张欣烨 "Ce掺杂的介孔材料的合成、表征与催化氧化性能" 第12，29-30，46，48，53页 1-3 , * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107188775A (en) * | 2017-07-07 | 2017-09-22 | 青岛科技大学 | A kind of method that amphipathic molecule sieve load Ru nano particle catalysis α pinene hydrogenations prepare cis-pinane |
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Application publication date: 20121003 |