CN103965014A - Method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane - Google Patents
Method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane Download PDFInfo
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- CN103965014A CN103965014A CN201410203979.2A CN201410203979A CN103965014A CN 103965014 A CN103965014 A CN 103965014A CN 201410203979 A CN201410203979 A CN 201410203979A CN 103965014 A CN103965014 A CN 103965014A
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- molecular sieve
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- cyclohexane
- cerium
- mesopore molecular
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
- C07C29/50—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 with molecular oxygen only
-
- 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
- C07C45/33—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 CHx-moieties
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
Abstract
The invention discloses a method for preparing cyclohexanol and cyclohexanone through selective oxidation of cyclohexane. The method comprises the steps of performing catalytic oxidation on cyclohexane in the absence of a solvent by taking supported cerium and a surface-functionalized MCM-48 mesoporous molecular sieve as a catalyst and oxygen as an oxidant to generate cyclohexanol and cyclohexanone. The surface of a mesoporous material is subjected to hydrophobic treatment through organic gene functionalization while oxidative active components are supported in the mesoporous molecular sieve, so that the surface polarity of the catalyst is reduced and the selectivity on cyclohexanol and cyclohexanone caused by the catalyst is improved. The reaction is performed in the presence of 1.0MPa oxygen at 120-160 DEG C for 4 hours, so that the cyclohexane conversion rate can maximally reach 9.2% and the selectivity of cyclohexanol and cyclohexanone can reach 85.7%.
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, taking 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 to produce the important intermediate of nylon, also have a wide range of applications in fields such as industrial coating, medicine and agricultural chemicals simultaneously, therefore cyclohexane selectively oxidizing reaction industrial have very important.At present, domestic and international more than 90% hexalin and pimelinketone is to adopt the cyclohexane oxidation process (DSM/HPO) of Dutch mining company exploitation to produce.This technology is the most ripe current 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 not adding any solvent, cyclohexane selectively oxidizing is generated to the operational path of hexalin and pimelinketone, because it has, less energy consumption, refuse are few, 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, 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 1.5 MPa Oxygen Conditions, 150 DEG C of stirring reaction 3 h, cyclohexane conversion is only 9% left and right; Patent CN101862660A discloses a kind of nano catalyst for cyclohexane oxidation, the carrier that wherein Si is catalyzer, Ti etc. are as the auxiliary agent of carrier, under 1.5 MPa Oxygen Conditions, 150 DEG C of stirring reaction 3 h, 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 1MPa Oxygen Condition, and 150 DEG C of stirring reaction 2 h, cyclohexane conversion can reach 16.6%, the selectivity of hexalin and pimelinketone reaches 92.4%(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 while being 0.008:1, under 1 MPa Oxygen Condition, 120 DEG C of reaction 2 h, cyclohexane conversion can reach 14%, and the overall selectivity of hexalin and pimelinketone reaches 92%.Although noble metal catalyst has good cyclohexane oxidation activity, 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 0.5MPa Oxygen Condition, and 140 DEG C of reaction 4 h, 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 the AlPO-5 molecular sieve catalyst of discovery Gd doping is the highest, under 0.5 MPa Oxygen Condition, 140 DEG C of reaction 4 h, 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 0.5MPa Oxygen Condition, 140 DEG C of reaction 4 h, 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 and there is 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, this need to, on the basis of understanding 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, mesoporous material surface is modified, the former function is to provide catalytic oxidation activity center, the latter's function is the polarity on modulation mesoporous material surface, make surface, duct there is identical polarity with reactant, improve the absorption of catalyzer to reactant.By the synergistic effect of above two kinds of effects, reach the object 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: be in reactant injecting reactor by 4 grams of cyclohexane gives, add 20 milligrams to support cerium and surface-functionalized MCM-48 mesopore molecular sieve, and add the TBHP of 10 μ L, then pass into the oxygen of 1.0 Mpa pressure, 120 DEG C ~ 160 DEG C are reacted 4 hours, obtain reaction product hexalin and pimelinketone.
Described catalyzer, first adopts hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, then it is carried out surface-functionalizedly, obtains final catalyzer; The concrete steps that wherein hydrothermal synthesis method preparation supports the MCM-48 mesopore molecular sieve of Ce comprise:
(a) Neutral ammonium fluoride, sodium hydroxide and water are mixed, obtain sodium hydroxide solution;
(b) in (a) solution, add cetyl trimethylammonium bromide, at 35 DEG C, stir 1 hour, form clear gel;
(c) cerium salt is mixed with water, obtain the solution containing cerium;
(d), under agitation condition, by adding in the gel of gained in step (b) containing the solution of cerium, at 35 DEG C, stir 0.5 hour;
(e) tetraethoxy is slowly added drop-wise in the mixed solution of steps d gained, at 35 DEG C, stirs 3 hours;
(f) mixed solution of step e gained is transferred in autoclave, crystallization after 3 days at 100 DEG C, filtering separation, deionized water wash, 100 DEG C are dry, and 550 DEG C of roastings 6 hours in air obtain supporting the MCM-48 mesopore molecular sieve of Ce.Then the MCM-48 mesopore molecular sieve that supports Ce preparing in said process is carried out surface-functionalizedly, concrete steps are as follows:
(a) n-octyl triethoxyl silane is mixed with toluene solution, then adds the MCM-48 mesopore molecular sieve that supports Ce, after ultrasonic dispersion at 110 DEG C stirring and refluxing 12 hours;
(b) filtering separation, absolute ethanol washing, 80 DEG C are dried 12 hours, obtain supporting cerium and surface-functionalized MCM-48 mesopore molecular sieve.
In the preparation method of above-mentioned catalyzer, main innovate point is: support oxidation activity component in mesopore molecular sieve in, hydrophobic treatment is carried out on surface by organic group functionized mesoporous material, reduce the polarity of catalyst surface, to improve the transformation efficiency of catalyst rings hexane and the selectivity to hexalin and pimelinketone.
That prepares with aforesaid method supports cerium and surface-functionalized MCM-48 mesoporous molecular sieve catalyst, for hexanaphthene selective oxidation hexalin processed and pimelinketone reaction.Under 1.0 MPa Oxygen Conditions, 120 DEG C ~ 160 DEG C are reacted 4 hours, and the transformation efficiency of hexanaphthene reaches as high as 9.2 %, and the selectivity of hexalin and pimelinketone can reach 85.7%.
Compared with prior art, the method for cyclohexane selectively oxidizing of the present invention hexalin processed and pimelinketone can realize the high conversion of hexanaphthene simultaneously, and highly selective to hexalin and pimelinketone.
Specific embodiments
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Preparation supports Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of n-octyl triethoxyl silane.1.2 grams of NaOH, 0.26 gram of Neutral ammonium fluoride and 70 grams of deionized waters are mixed to get to mixing solutions, at 35 DEG C, add 10.6 grams of cetyl trimethylammonium bromides, stir 1 hour, form clear gel A; By 0.52 gram of Ce (NO
3)
36H
2o mixes with 10 grams of deionized waters, and stirring and dissolving, obtains cerium solution, then under agitation dropwise adds in clear gel A, stirs after 0.5 hour, in mixed solution, drips 12.6 grams of tetraethoxys, stirs after 3 hours, proceeds to crystallization in autoclave.Autoclave is placed after 3 days at 100 DEG C, through cooling, filter, obtain solid after washing, and through 100 DEG C dry 12 hours, 550 DEG C of roastings 6 hours, obtain the MCM-48 molecular sieve that cerium supports.
Then carry out surface-functionalized to the MCM-48 mesopore molecular sieve that supports Ce preparing in said process.0.6 gram of n-octyl triethoxyl silane is mixed with toluene solution, then add 0.3 gram of MCM-48 mesopore molecular sieve that supports Ce, stirring and refluxing 12 hours at 110 DEG C of temperature.Finally, be separated by filtration, absolute ethanol washing, 80 DEG C are dried 12 hours, obtain supporting cerium and the surface-functionalized MCM-48 mesopore molecular sieve of n-octyl Trimethoxy silane.
20 milligrams of above-mentioned Ce of supporting and surface-functionalized MCM-48 mesoporous molecular sieve catalyst and the 4 grams of cyclohexane solvents of n-octyl triethoxyl silane are put into reactor, add the TBHP of 10 μ L, then pass into the oxygen of 1.0 Mpa pressure, 140 DEG C are reacted 6 hours, be cooled to after room temperature, reaction product hexalin and pimelinketone analyzed by gas-chromatography.The transformation efficiency of hexanaphthene is 9.2%, and the selectivity of hexalin and pimelinketone is 85.7%.
Embodiment 2
Catalyzer preparation condition is identical with embodiment 1.Temperature of reaction is reduced to 120 DEG C by 140 DEG C, and other reaction conditions is identical with embodiment 1, and the transformation efficiency of hexanaphthene is 8.1%, and the selectivity of hexalin and pimelinketone is 87.9%.
Embodiment 3
Catalyzer preparation condition is identical with embodiment 1.Temperature of reaction is increased to 160 DEG C by 140 DEG C, and other reaction conditions is identical with embodiment 1, and the transformation efficiency of hexanaphthene is 9.6%, and the selectivity of hexalin and pimelinketone is 78.1%.
Embodiment 4
Change the consumption of the surface-functionalized reagent n-octyl triethoxyl silane adopting in embodiment 1 into 0.4 gram, other preparation condition of catalyzer is identical with embodiment 1, obtains supporting Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of n-octyl triethoxyl silane.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene obtaining is 8.7 %, and the selectivity of hexalin and pimelinketone is 79.5%.
Embodiment 5
Change the consumption of the surface-functionalized reagent n-octyl triethoxyl silane adopting in embodiment 1 into 0.2 gram, other preparation condition of catalyzer is identical with embodiment 1, obtains supporting Ce and the surface-functionalized MCM-48 mesoporous molecular sieve catalyst of n-octyl triethoxyl silane.Reaction conditions is identical with embodiment 1, and the transformation efficiency of the hexanaphthene obtaining is 8.4 %, and the selectivity of hexalin and pimelinketone is 90.0%.
Claims (6)
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: be in reactant injecting reactor by cyclohexane give, add and support cerium and surface-functionalized MCM-48 mesopore molecular sieve, and add the TBHP of 10 μ L, then pass into the oxygen of 1.0Mpa pressure, 120 DEG C ~ 160 DEG C reactions 4 hours, obtain reaction product hexalin and pimelinketone.
2. catalyzer according to claim 1, is characterized in that, first adopts hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, then it is carried out surface-functionalizedly, obtains final catalyzer.
3. catalyzer according to claim 2, is characterized in that, first adopts hydrothermal synthesis method preparation to support the MCM-48 mesopore molecular sieve of Ce, comprises the following steps:
(a) sodium hydroxide, Neutral ammonium fluoride and water are mixed, obtain mixing solutions;
(b) in (a) mixing solutions, add cetyl trimethylammonium bromide, at 35 DEG C, stir 1 hour, form clear gel;
(c) cerium salt is mixed with water, obtain the solution containing cerium;
(d), under agitation condition, by adding in the gel of gained in step (b) containing the solution of cerium, at 35 DEG C, stir 0.5 hour;
(e) tetraethoxy is slowly added drop-wise in the mixed solution of steps d gained, at 35 DEG C, stirs 3 hours;
(f) mixed solution of step e gained is transferred in autoclave, crystallization after 3 days at 100 DEG C, filtering separation, deionized water wash, 100 DEG C are dry, and 550 DEG C of roastings 6 hours in air obtain supporting the MCM-48 mesopore molecular sieve of Ce;
Then the MCM-48 mesopore molecular sieve that supports Ce preparing in said process is carried out surface-functionalizedly, comprise the following steps:
(a) silylating reagent is mixed with toluene solution, then add the MCM-48 mesopore molecular sieve that supports Ce, stirring and refluxing 12 hours at 110 DEG C of temperature;
(b) filtering separation, absolute ethanol washing, 80 DEG C are dried 12 hours, obtain supporting cerium and surface-functionalized MCM-48 mesopore molecular sieve.
4. preparation method according to claim 3, is characterized in that, the mass content of described Cerium in Catalysts salt is 4%.
5. preparation method according to claim 3, is characterized in that, described silylating reagent is n-octyl triethoxyl silane.
6. preparation method according to claim 3, is characterized in that, the add-on of described n-octyl triethoxyl silane is 0.2 ~ 0.6 gram.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614100A (en) * | 2018-06-20 | 2019-12-27 | 天津工业大学 | Preparation of caprolactone by mesoporous silicon catalyst green oxygen-sharing doped with iron-molybdenum transition metal |
| CN111450875A (en) * | 2020-04-29 | 2020-07-28 | 烟台大学 | Preparation method of cyclohexene hydration liquid-liquid amphiphilic catalyst |
| CN111606789A (en) * | 2019-02-26 | 2020-09-01 | 中国石油化工股份有限公司 | Catalytic oxidation process for cycloalkanes |
| 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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| CN1775673A (en) * | 2005-12-08 | 2006-05-24 | 华东理工大学 | Method for preparing MCM 48 molecular sieve |
| 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 |
| 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 |
| CN103641679A (en) * | 2012-12-27 | 2014-03-19 | 湘潭大学 | Method for catalyzing cyclohexane selective oxidation through microwave catalysts |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1775673A (en) * | 2005-12-08 | 2006-05-24 | 华东理工大学 | Method for preparing MCM 48 molecular sieve |
| 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 |
| 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 |
| CN103641679A (en) * | 2012-12-27 | 2014-03-19 | 湘潭大学 | Method for catalyzing cyclohexane selective oxidation through microwave catalysts |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614100A (en) * | 2018-06-20 | 2019-12-27 | 天津工业大学 | Preparation of caprolactone by mesoporous silicon catalyst green oxygen-sharing doped with iron-molybdenum transition metal |
| CN111606789A (en) * | 2019-02-26 | 2020-09-01 | 中国石油化工股份有限公司 | Catalytic oxidation process for cycloalkanes |
| CN111606789B (en) * | 2019-02-26 | 2022-10-21 | 中国石油化工股份有限公司 | Catalytic oxidation process for cycloalkanes |
| CN111450875A (en) * | 2020-04-29 | 2020-07-28 | 烟台大学 | Preparation method of cyclohexene hydration liquid-liquid amphiphilic catalyst |
| 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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Application publication date: 20140806 |