CN102294267B - Preparation method and application of zinc oxide solid borne tetra (pentafiuorophenyl)ferriporphyrin - Google Patents
Preparation method and application of zinc oxide solid borne tetra (pentafiuorophenyl)ferriporphyrin Download PDFInfo
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- CN102294267B CN102294267B CN 201110171139 CN201110171139A CN102294267B CN 102294267 B CN102294267 B CN 102294267B CN 201110171139 CN201110171139 CN 201110171139 CN 201110171139 A CN201110171139 A CN 201110171139A CN 102294267 B CN102294267 B CN 102294267B
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- pentafluorophenyl group
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Abstract
A preparation method of zinc oxide solid borne tetra (pentafiuorophenyl) ferriporphyrin. The method comprises steps of: carrying out mechanical stirring on newly prepared Zn(OH)2 to disperse in a certain amount of organic solvent; adding organic solvent dissolved tetra (pentafiuorophenyl) ferriporphyrin, maintaining at 65-75DEG C, and stirring for 5-7h; depriving the organic solvent by a reduced pressure distillation; carrying out a pumping filtration and washing; drying a filter cake in 120-170 DEG C vacuum for 5-8h to obtain the zinc oxide solid borne tetra (pentafiuorophenyl) ferriporphyrin. 1.0mg tetra (pentafiuorophenyl) ferriporphyrin equivalent weight of zinc oxide solid borne tetra (pentafiuorophenyl) ferriporphyrin catalyses oxygen to oxidize cyclohexane under a pressure of 0.7MPa, a reaction temperature of 150 DEG C for 4h; and an average cyclohexane conversion rate is 34.2%; an average selectivity is 57.5%; and an average yield of a main oxidized product is 19.7%. Besides, the catalyst can be repeatedly use for more than 10 times.
Description
Technical field
The present invention relates to the preparation method of a kind of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin, and be catalyst with immobilized four (pentafluorophenyl group) ferriporphyrin of zinc oxide, the oxygen catalytic oxidation cyclohexane prepares the technology of cyclohexanone and cyclohexanol.
Background technology
Nowadays cyclohexanone and cyclohexanol in the industry, the two is commonly called as K/A oil, is preparation caprolactam and adipic acid and then can synthetic nylon-6 and the main intermediate of nylon-66, also is important Organic Chemicals simultaneously.And cyclohexane oxidation prepares cyclohexanol and cyclohexanone is a kind of important organic synthesis.The method of various catalysis cyclohexane oxidations is a lot, and some is also very effective.But over 50 years, various countries fall over each other the method for du pont company is improved, and have formed the process route of various countries, as having at present the Dutch DSM technology of cyclohexane oxidation process, Polish POLIMEX technology and Ube UBE technology etc. abroad.Mainly use catalysis of cobalt salt at present on the world industry, under 158 ℃ and 1MPa pressure, the catalytic air oxidation cyclohexane is produced cyclohexanone and cyclohexanol, and cyclohexane conversion is usually between 4%～6%, alcohol ketone selectively is that 75%～85%, K/A oil productive rate is 3.0%～5.1%.People do not satisfy this productive rate present situation.Therefore this field remains the focus of Chinese scholars research.Since human more and more higher to future life environment and environmental protection requirement, the industrial high efficient technology that more is tending towards the demand environmental protection, and based on this mankind's needs, people appeal the process route of environmental protection.In the last thirty years, metalloporphyrin is widely used in the Catalytic Oxidation of alkanes as the artificial model of oxygenase cytochrome P-450, has started the research boom of such catalyst molecular oxygen oxidation cyclohexane.In recent years, the scientific research team that domestic professor Guo Cancheng of Hunan University leads cooperated first catalysis of metalloporphyrin molecular oxygen oxidation cyclohexane successfully to be applied to industrial production with Ba Ling branch company of China Petrochemical Industry in 2004, had realized the industrialization of green bionic catalysis cyclohexane.Submitted in Daya Gulf economic development zone, Guangdong to national ministries and commissions again in 2009 and plan to build upright " cyclohexane green catalysis oxidizing process is produced the report of cyclohexanone project feasibility ", 100,000 tons cyclohexanone is produced in this project plan per year.This technology is to adopt tetraphenyl cobalt porphyrin homogeneous catalysis oxidizing ethyle alkyl, can obtain 8.7% cyclohexane conversion, alcohol ketone selects performance up to 91%, the alcohol ketone yield is about 7.9%, and reduced environmental pollution, reasonably utilize resource and the energy, reduced production cost, met current requirement of developing a circular economy.Because supported metalloporphyrin has its specific superiority, also all strive for obtaining new discovery and new application both at home and abroad in this field.Simultaneously, domestic and international research has found that: second class and the 3rd metalloid porphyrin with electron-withdrawing group have stronger catalytic capability than first kind metalloporphyrin.Just because non-supported metalloporphyrin belongs to homogeneous catalysis system, it is difficult to reclaim metalloporphyrin.This catalytic oxidation system can obtain the selective and relative higher cyclohexane conversion of higher K/A oil, but the metalloporphyrin of costliness can not reclaim the repetition recycling, has caused the serious waste of core catalyst.
Summary of the invention
The object of the invention provides preparation method and the application thereof of a kind of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin, this solid-carried catalyst has the ability of efficient repeated use catalytic molecular oxygen oxidizing ethyle alkyl, high cyclohexane conversion is arranged, overcome in the current catalytic molecular oxygen oxidizing ethyle alkyl technology that conversion ratio is low, the unit mass metalloporphyrin is reused inefficient problem.
In recent years, our research proved, by the phenyl ring of tetraphenyl metalloporphyrin is modified, can significantly improve the catalysis of metalloporphyrin performance.The more many catalytic activitys of strong electron-withdrawing substituent number that the tetraphenyl catalysis of metalloporphyrin activity that has electron-withdrawing substituent on the phenyl ring will be higher than on the tetraphenyl metalloporphyrin, particularly phenyl ring that has electron donating group on the phenyl ring are just more high.Four (pentafluorophenyl group) ferriporphyrin is exactly to have strong electrophilic fluorine atom on the phenyl ring, is the second metalloid porphyrin with high catalytic activity.It is widely used in the catalytic oxidation of epoxide, removes carbonylation and to the hydroxylating of aliphatic hydrocarbon.But because its synthetic cost is higher, and in catalytic process also oxidized destruction, can only use catalysis once namely to consume, cause serious waste.Therefore, limited the application of this type of metalloporphyrin in industrial production to a great extent.In order to protect the not oxidized destruction of metalloporphyrin, improve and reuse number of times and keep its efficient catalytic performance.This has done many researchs to domestic and international research worker on the one hand at the protection metalloporphyrin, has obtained good effect.
We once used immobilized four (4-hydroxy phenyl) the cobalt porphyrin of zinc oxide to come catalytic oxidation toluene, and the result shows that this solid-carried catalyst can repeat catalysis 15 times, and toluene conversion is 6.8%, all is higher than not immobilized cobalt porphyrin.Illustrated that ZnO is a kind of good carrier, can keep the catalytic activity of metalloporphyrin and reuse efficient.On this research basis, we have prepared immobilized four (pentafluorophenyl group) ferriporphyrin catalyst with strong electron-withdrawing group of zinc oxide, and for the oxygen catalytic oxidation cyclohexane, improved conversion of cyclohexane greatly, and improved main oxidation product alcohol ketone productive rate, have and reuse catalytic efficiency preferably, provide a kind of oxidizing ethyle alkyl to produce the new technology of K/A oil.
The present invention realizes above-mentioned purpose by the following technical solutions: the preparation method of a kind of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin is with freshly prepd Zn (OH)
2Through mechanical agitation be scattered in a certain amount of organic solvent in, add four (pentafluorophenyl group) ferriporphyrin with organic solvent dissolution again, keep 65～75 ℃ and stir 5～7h, utilize decompression distillation to remove organic solvent, after suction filtration, washing, the gained filter cake namely gets zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin at 120～170 ℃ of vacuum drying 5～8h, and described organic solvent is methyl alcohol or butanone.
Described new preparation Zn (OH)
2, its method step is as follows: take by weighing 70g ZnSO
47H
2O is dissolved in the 200mL deionized water, is adjusted to pH=8 with the sodium hydroxide solution of 0.2M, and suction filtration obtains a kind of sediment, and this sediment is freshly prepd Zn (OH)
2
The application of described zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin, be to get zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin of 0.5～1.5mg four (pentafluorophenyl group) ferriporphyrin equivalent in the 500ml autoclave, add the 200ml cyclohexane, reaction pressure control is at 0.6～1.0MPa, temperature control is at 140～155 ℃, mixing speed control is at 300～600 rev/mins, and gas flow is 0.04m
3/ h, reach set reaction temperature after aerating oxygen carry out oxidation reaction 2～4h.
Described zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin (Fe TPFPP) structural formula is abbreviated as: Fe TPFPP/ZnO or TPFPP Fe/ZnO.
Compare with existing cyclohexane oxidation technology, outstanding advantage of the present invention is:
As catalyst, the molar concentration of four (pentafluorophenyl group) ferriporphyrin is 2.4～9.4 * 10 with zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin
-6Mol/L, catalytic oxygen selective oxidation cyclohexane is produced cyclohexanone and cyclohexanol has been obtained good effect: conversion of cyclohexane is up to 44.9%, and alcohol ketone selectively is 52.3%, and the catalyst turn over number can reach 5.8 * 10
5, the keto-alcohol productive rate is 23.5%, post catalyst reaction reclaims reuses catalytic reaction 10 times, still keeps good catalytic activity.
The specific embodiment
Further set forth the preparation method of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin involved in the present invention and the method for its oxygen catalytic oxidation cyclohexane of use by the following examples.
Embodiment 1
The preparation method of a kind of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin: take by weighing 35g ZnSO
47H
2O is dissolved in the 100mL deionized water, is adjusted to pH=8 with the sodium hydroxide solution of 0.2M, and suction filtration obtains freshly prepd Zn (OH)
2Precipitation.Sediment is transferred in the three-necked bottle that the 200mL organic solvent is housed then, under 600 rev/mins of electronic stirrings, 10mg four (pentafluorophenyl group) ferriporphyrin that adds the 25mL organic solvent dissolution, keep 65～75 ℃ and the lasting 5～7h of stirring, utilize decompression distillation to remove organic solvent, after spending deionised water and suction filtration, filter cake namely gets zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin catalyst at 120～170 ℃ of vacuum drying 5～8h.
Embodiment 2
The using method of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin: the zinc oxide solid-carried catalyst of 1.0mg four (pentafluorophenyl group) ferriporphyrin equivalent is put in the 500ml reactor, add the 200ml cyclohexane, mixing speed is 200 rev/mins, reaction time 4.0h, reaction pressure is 0.8MPa, when reaction temperature is 150 ℃, get a sample every half an hour, carry out qualitative and GC gas-chromatography internal standard method through GC-Mass gas chromatography mass spectrometry technology, carry out each product molar content of quantitative assay in conjunction with chemical titration, drawing conversion of cyclohexane is 44.3%, and keto-alcohol selectively is 46.2%, and the catalyst turn over number is 8.8 * 10
5, the alcohol ketone productive rate is 20.5%.
When reaction temperature was 145 ℃, conversion of cyclohexane was 37.5%, and keto-alcohol selectively is 47.3%, and the catalyst turn over number is for being 7.6 * 10
5, the alcohol ketone productive rate is 17.7%.
When reaction temperature was 140 ℃, conversion of cyclohexane was 18.3%, and keto-alcohol selectively is 69.4%, and the catalyst turn over number is 4.0 * 10
5, the alcohol ketone productive rate is 12.7%.
When reaction temperature was 155 ℃, conversion of cyclohexane was 44.2%, and keto-alcohol selectively is 48.5%, and the catalyst turn over number is 8.8 * 10
5, the alcohol ketone productive rate is 21.5%.
Embodiment 3
The using method of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin: the zinc oxide solid-carried catalyst of 1.0mg four (pentafluorophenyl group) ferriporphyrin equivalent is put in the 500ml reactor, add the 200ml cyclohexane, mixing speed is 200 rev/mins, reaction time 4.0h, reaction temperature is 150 ℃, and when reaction pressure was 0.9MPa, conversion of cyclohexane was respectively 31.1%, keto-alcohol selectively is 50.8%, and turn over number is 6.3 * 10
5, the alcohol ketone productive rate is 15.8%.
When reaction pressure was 0.7MPa, conversion of cyclohexane was 37.9%, and keto-alcohol selectively is 57.8%, and the catalyst turn over number is 7.8 * 10
5, the alcohol ketone productive rate is 21.9%.
When reaction pressure was 0.6MPa, conversion of cyclohexane was 33.2%, and keto-alcohol selectively is 60.3%, and the catalyst turn over number is 6.9 * 10
5, the alcohol ketone productive rate is 20.0%.
Embodiment 4
The using method of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin: the zinc oxide solid-carried catalyst of 1.5mg four (pentafluorophenyl group) ferriporphyrin equivalent is put in the 500ml reactor, add the 200ml cyclohexane, mixing speed is 200 rev/mins, reaction time 4.0h, reaction temperature is 150 ℃, and when reaction pressure was 0.7MPa, conversion of cyclohexane was 44.9%, keto-alcohol selectively is 52.3%, and turn over number is 5.8 * 10
5, the alcohol ketone productive rate is 23.5%.
Changing this metalloporphyrin equivalent is that (during four (pentafluorophenyl group) ferriporphyrin, conversion of cyclohexane is 35.7% to 0.5mg, and keto-alcohol selectively is 57.1%, and the catalyst turn over number is 1.5 * 10
5, the alcohol ketone productive rate is 20.4%.
Embodiment 5
The use of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin and repeated use catalysis thereof: the zinc oxide solid-carried catalyst of 1.0mg four (pentafluorophenyl group) ferriporphyrin equivalent is put in the 500ml reactor, add the 200ml cyclohexane, mixing speed is 200 rev/mins, reaction time 4.0h, reaction temperature is 150 ℃, and when reaction pressure was 0.7MPa, conversion of cyclohexane was 37.9%, keto-alcohol selectively is 57.8%, and the catalyst turn over number is 7.8 * 10
5, alcohol ketone productive rate: 21.9%.The zinc oxide solid-carried catalyst that reclaims can be reused catalysis 10 times under this reaction condition, its conversion of cyclohexane is respectively: 30.5%, 38.8%, 38.0%, 28.1%, 39.8%, 35.6%, 35.6%, 35.2%, 32.8%, 27.4%, and keto-alcohol selectively is respectively 56.9%, 51.3%, 52.9%, 62.4%, 50.6%, 59.9%, 56.8%, 59.2%, 58.3%, 66.3%.The alcohol ketone productive rate is respectively: 17.3%, 19.9%, 20.1%, 17.5%, 20.1%, 20.3%, 20.2%, 20.8%, 19.1%, 18.1%.
Claims (2)
1. the preparation method of a zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin is characterized in that, comprises the steps:
Take by weighing 35g ZnSO
47H
2O is dissolved in the 100mL deionized water, is adjusted to pH=8 with the sodium hydroxide solution of 0.2M, and suction filtration obtains freshly prepd Zn (OH)
2Precipitation, sediment is transferred in the three-necked bottle that the 200mL organic solvent is housed then, under 600 rev/mins of electronic stirrings, 10mg four (pentafluorophenyl group) ferriporphyrin that adds the 25mL organic solvent dissolution, keep 65～75 ℃ and the lasting 5～7h of stirring, utilize decompression distillation to remove organic solvent, after spending deionised water and suction filtration, filter cake namely gets zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin catalyst at 120～170 ℃ of vacuum drying 5～8h
Described organic solvent is methyl alcohol or butanone.
2. the preparation method of the described zinc oxide of claim 1 immobilized four (pentafluorophenyl group) ferriporphyrin is characterized in that: the application of zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin that is prepared into by this method,
Get zinc oxide immobilized four (pentafluorophenyl group) ferriporphyrin of 0.5～1.5mg four (pentafluorophenyl group) ferriporphyrin equivalent in the 500ml autoclave, add the 200ml cyclohexane, reaction pressure control is at 0.6～1.0MPa, temperature control is at 140～155 ℃, mixing speed control is at 300～600 rev/mins, gas flow is 0.04m3/h, reach set reaction temperature after aerating oxygen carry out oxidation reaction 2～4h.
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| CN106000471B (en) * | 2016-06-03 | 2018-05-01 | 河南大学 | A kind of zinc oxide-porphyrin core-shell nano rod composite material and preparation method thereof |
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