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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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052684 Cerium Inorganic materials 0.000 claims description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000013335 mesoporous material Substances 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 14
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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| 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 |
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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 * |
| ZHAN Wangcheng et al..Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane.《JOURNAL OF RARE EARTHS》.2008,第26卷(第4期),515-522. |
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