CN102294268A - Preparation method and application of aluminic acid supported tetra(pentafluorophenyl) iron porphyrin - Google Patents
Preparation method and application of aluminic acid supported tetra(pentafluorophenyl) iron porphyrin Download PDFInfo
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- CN102294268A CN102294268A CN201110171140A CN201110171140A CN102294268A CN 102294268 A CN102294268 A CN 102294268A CN 201110171140 A CN201110171140 A CN 201110171140A CN 201110171140 A CN201110171140 A CN 201110171140A CN 102294268 A CN102294268 A CN 102294268A
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- aluminic acid
- pentafluorophenyl
- ferriporphyrin
- pentafluorophenyl group
- cyclohexane
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Abstract
The invention relates to a preparation method of aluminic acid supported tetra(pentafluorophenyl) iron porphyrin. The preparation method comprises the following steps: transferring newly generated Al(OH)3 to a three-necked flask with a certain amount of organic solvent, and heating to 55-75 DEG C under the condition of power-driven stirring; slowly adding tetra(pentafluorophenyl) metal porphyrin dissolved by the organic solvent, continuing stirring for 5-7 hours; carrying out suction filtering at reduced pressure after cooling; eluting a filter cake with distilled water, and then carrying out vacuum drying for 4-7 hours at the temperature of 150-170 DEG C so as to obtain aluminic acid supported tetra(pentafluorophenyl) metal porphyrin. According to the invention, tetra(pentafluorophenyl) metal porphyrin equivalent to1.5mg of tetra(pentafluorophenyl) iron porphyrin is used to catalyze air so as to oxidize cyclohexane under the conditions of air pressure of 0.9MPa, reaction temperature of 145 DEG C and reaction time of 4 hours; the aluminic acid supported catalyst can be repeatedly used to catalyze the air so as to oxidize cyclohexane for 10 times, the conversion rate of cyclohexane is averagely 18.5% each time, the selectivity of alcohol and ketone is 64.4% and the yield of the main product is 13.2%.
Description
Technical field
The present invention relates to the preparation method of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin, and be catalyst with four (pentafluorophenyl group) ferriporphyrin of meta-aluminic acid load, the molecular oxygen selective oxidation cyclohexane in the catalytic air prepares cyclohexanone and cyclohexanol.
Background technology
Cyclohexanone and cyclohexanol in the current 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 or the like 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%, the alcohol ketone selectivity is 75%～85%, and K/A oil productive rate is 3.0%～5.1%.Scientific circles do not satisfy this productive rate present situation.This field remains the focus of Chinese scholars research.Human demand for following high-quality life environment forces industry more to be tending towards the process route of high-efficiency environment friendly.In the last thirty years, metalloporphyrin has been applied to the Catalytic Oxidation of alkanes as the artificial model of oxygenase cytochrome P-450, has started the research boom of such bionic catalysis 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 the resource and the energy, reduced production cost, met current requirement of developing a circular economy.Yet the carried metal porphyrin has its specific superiority, makes domestic and international researcher fall over each other in this field and will obtain new discovery and new application.Simultaneously, domestic and international research had proved already that second class and the 3rd metalloid porphyrin with electron-withdrawing group had stronger catalytic capability than first kind metalloporphyrin.Just because the metalloporphyrin in the homogeneous catalysis system reclaims quite difficulty.And this type of metalloporphyrin can the catalytic oxidation cyclohexane and obtain very high K/A oil selectivity and cyclohexane conversion, promptly quite high alcohol ketone productive rate.Expensive metalloporphyrin can not reclaim and repeat to utilize again, has caused the serious waste of core catalyst.
Summary of the invention
The object of the invention provides the preparation method and the application thereof of a kind of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin, it has the ability of efficient repeated use catalytic air oxidation cyclohexane, higher cyclohexane conversion is arranged, overcome low, the not high defective of unit mass metalloporphyrin repeated use efficient of conversion ratio in the present catalytic molecular oxygen oxidizing ethyle alkyl technical process.
We also prove in research in recent years, by the phenyl ring of tetraphenyl metalloporphyrin is modified, can significantly improve the catalysis of metalloporphyrin performance.The many more 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 high more.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 promptly 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 came load tetraphenyl cobalt or manganoporphyrin with AlOOH, the research that the different-phase catalyst of making is used for catalytic molecular oxygen oxidizing ethyle alkyl has obtained result preferably: the former repeats catalysis 10 times continuously, the average conversion of cyclohexane is about 9.2%, the alcohol ketone average selectivity is about 92.1%, alcohol ketone yield 8.5%; The latter repeats catalysis 9 times continuously, and the average conversion of cyclohexane is about 12.1%, and the alcohol ketone average selectivity is about 85.6%, alcohol ketone yield 10.4%.Both all are better than the metalloporphyrin of not load.Illustrated that AlOOH is a kind of excellent carriers, can keep the catalytic activity of metalloporphyrin and reuse efficient.On this research basis, prepared four (pentafluorophenyl group) ferriporphyrin catalyst that the meta-aluminic acid load has strong electron-withdrawing group, and be used for the catalytic air 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 is achieved through the following technical solutions above-mentioned purpose:
The preparation method of a kind of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin comprises the steps: with newly-generated Al (OH)
3Transfer in the three-neck flask that a certain amount of organic solvent is housed, under the electronic stirring, and be heated to 55～75 ℃, four (pentafluorophenyl group) metalloporphyrin that slowly adds organic solvent dissolution continues to stir 5～7h, decompress filter after cooling, after with distilled water drip washing filter cake, at 150～170 ℃ of following vacuum drying 4～7h, promptly get meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin, described organic solvent is methyl alcohol or butanone.
Described newly-generated Al (OH)
3Preparation method's step be: take by weighing 0.5molAl (NO
3)
39H
2O is dissolved in the distilled water of 1000ml, under the electronic stirring, drips concentrated ammonia liquor to pH=7～9, and suction filtration promptly obtains newly-generated Al (OH)
3Sediment.
The method that described meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin is used for the catalytic air oxidation cyclohexane is: get 0.52～2.07g meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin catalyst and put into the 500ml autoclave, add the 200ml cyclohexane.Reaction pressure is controlled at 0.8～1.0MPa, and temperature is controlled at 140～150 ℃, and speed of agitator is controlled at 300～600 rev/mins, and gas flow is 0.04m
3/ h, reach design temperature after bubbling air carry out oxidation reaction 2～4h.
Described meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin expression formula is: Fe TPFPP/BM or TPFPP Fe/BM
Used carrier is meta-aluminic acid, i.e. BM.
Compare with existing cyclohexane oxidation technology, outstanding advantage of the present invention is:
With meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin is catalyst, and the molar concentration of four (pentafluorophenyl group) ferriporphyrin is 2.4～9.4 * 10
-6Mol/L, selectivity catalytic air oxidation cyclohexane prepares cyclohexanone and cyclohexanol, and conversion of cyclohexane reaches 24.1%, and the alcohol ketone selectivity is 71.3%, and the catalyst turn over number reaches 3.3 * 10
5, the keto-alcohol productive rate is 17.2%, post catalyst reaction reclaims and reuses 10 times and still can keep advantages of high catalytic activity.
The specific embodiment
By the following examples the preparation method of meta-aluminic acid load four of the present invention (pentafluorophenyl group) ferriporphyrin and the method for use catalytic air oxidation cyclohexane thereof are further specified.
Embodiment 1
The preparation method of a kind of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin takes by weighing 0.25molAl (NO
3)
39H
2O is dissolved in the deionized water of 500ml, under the electronic stirring, drips concentrated ammonia liquor to pH=7～9, and suction filtration obtains newly-generated Al (OH)
3Precipitation, and transfer in the large beaker that the 250ml methanol solvate is housed, with spoon meta-aluminic acid is smashed to pieces, transfer to again in the three-neck flask, be warmed up to after 55～75 ℃ with 700 rev/mins of electronic stirrings and with system.7mg four (pentafluorophenyl group) metalloporphyrin that slowly adds the dissolving of 20ml methyl alcohol continues to stir 5～7h, is decompressed to the 0.09MPa suction filtration after cooling, drains and obtains filter cake.Clarify with distilled water drip washing filter cake to filtrate.Under 150～170 ℃,, promptly get meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin catalyst with filter cake vacuum drying 4～7h.
Embodiment 2
The using method of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin: with meta-aluminic acid supported catalyst (author's notes: write with reference to the patent of passing through second trial of Liu Shangyue of 1.0mg four (pentafluorophenyl group) ferriporphyrin equivalent herein, put in the 500ml reactor down together), add the 200ml cyclohexane, mixing speed is 200 rev/mins, reaction time 4.0h, reaction pressure is 0.9MPa, when reaction temperature is 145 ℃.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 21.2%, the keto-alcohol selectivity is 76.5%, and the catalyst turn over number is 4.5 * 10
5, keto-alcohol productive rate: 16.2%.
When reaction temperature was 150 ℃, conversion of cyclohexane was 16.7%, and the keto-alcohol selectivity is 79.9%, and the catalyst turn over number is 3.5 * 10
5, the alcohol ketone productive rate is 13.4%.
When reaction temperature was 140 ℃, conversion of cyclohexane was 15.3%, and the keto-alcohol selectivity is 75.3%, and the catalyst turn over number is 3.2 * 10
5, the alcohol ketone productive rate is 11.5%.
Embodiment 3
The using method of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin: the meta-aluminic acid supported 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 145 ℃, and reaction pressure is when 0.8MPa, and conversion of cyclohexane is 20.5%, the keto-alcohol selectivity is 72.1%, and the catalyst turn over number is 4.2 * 10
5, the alcohol ketone productive rate is 14.8%.
When reaction pressure was 1.0MPa, conversion of cyclohexane was 22.5%, and the keto-alcohol selectivity is 71.0%, and the catalyst turn over number is 4.6 * 10
5, the alcohol ketone productive rate is 16.0%.
Embodiment 4
The using method of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin: the meta-aluminic acid supported catalyst of 0.5mg four (pentafluorophenyl group) ferriporphyrin equivalent is put in the 500ml reactor, add the 200ml cyclohexane, 145 ℃ of reaction temperatures, reaction pressure 0.9MPa, mixing speed is 200 rev/mins, reaction time 4.0h.Conversion of cyclohexane is 19.8%, and the keto-alcohol selectivity is 71.1%, and the catalyst turn over number is 8.2 * 10
5, the alcohol ketone productive rate is 14.1%.
When the input amount of metalloporphyrin became 1.5mg four (pentafluorophenyl group) ferriporphyrin, conversion of cyclohexane was 24.1%, and the keto-alcohol selectivity is 72.3%, and the catalyst turn over number is 3.3 * 10
5, the alcohol ketone productive rate is 17.2%.
(during four (pentafluorophenyl group) ferriporphyrin, conversion of cyclohexane is 15.3%, and the keto-alcohol selectivity is 77.3%, and the catalyst turn over number is 1.6 * 10 when the input amount of metalloporphyrin becomes 2.0mg
5, the alcohol ketone productive rate is 11.8%.
Embodiment 5
The using method of meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin and recycling catalysis cyclohexane oxidation: the meta-aluminic acid supported catalyst of 1.5mg four (pentafluorophenyl group) ferriporphyrin equivalent is put in the 500ml reactor, add the 200ml cyclohexane, 145 ℃ of reaction temperatures, reaction pressure is 0.9MPa, mixing speed is 200 rev/mins, reaction time 4.0h.Conversion of cyclohexane is 24.1%, keto-alcohol selectivity 72.3%, catalyst turn over number 3.3 * 10
5The catalyst that reclaims can repeat catalysis 10 times under this reaction condition, its conversion of cyclohexane is respectively: 22.4%, 20.1%, 20.2%, 19.5%, 16.4%, 18.3%, 18.9%, 16.8%, 14.2%, 17.8%; The keto-alcohol selectivity is respectively 69.9%, 70.3%, 69.6%, 69.1%, 71.9%, 71.9%, 71.7%, 72.2%, 78.2%, 71.2%.The alcohol ketone productive rate is respectively: 15.6%, 14.2%, 14.1%, 13.5%, 11.8%, 13.1%, 13.6%, 12.2%, 11.1%, 12.7%.
Claims (3)
1. the preparation method of a meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin is characterized in that, comprises the steps:
With newly-generated Al (OH)
3Transfer in the three-neck flask that a certain amount of organic solvent is housed, under the electronic stirring, and be heated to 55～75 ℃, four (pentafluorophenyl group) metalloporphyrin that slowly adds organic solvent dissolution continues to stir 5～7h, decompress filter after cooling, after with distilled water drip washing filter cake, at 150～170 ℃ of following vacuum drying 4～7h, promptly get meta-aluminic acid load four (pentafluorophenyl group) ferriporphyrin
Described organic solvent is methyl alcohol or butanone.
2. the preparation method of meta-aluminic acid load four according to claim 1 (pentafluorophenyl group) ferriporphyrin is characterized in that, described newly-generated Al (OH)
3Preparation method's step be: take by weighing 0.5mol Al (NO
3)
39H
2O is dissolved in the distilled water of 1000ml, under the electronic stirring, drips concentrated ammonia liquor to pH=7～9, and suction filtration promptly obtains newly-generated Al (OH)
3Sediment.
3. the application of the described meta-aluminic acid load four of claim 1 (pentafluorophenyl group) ferriporphyrin is characterized in that:
The meta-aluminic acid supported catalyst of getting 0.5～2.0mg four (pentafluorophenyl group) ferriporphyrin equivalent is in the 500ml autoclave, add the 200ml cyclohexane, reaction pressure is controlled at 0.8～1.0MPa, and temperature is controlled at 140～150 ℃, speed of agitator is controlled at 300～600 rev/mins, and gas flow is 0.04m
3/ h, reach set reaction temperature after bubbling air carry out oxidation reaction 2～3.5h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671708A (en) * | 2012-03-06 | 2012-09-19 | 广西大学 | Method for grafting solid-borne tetrakis(4-carboxylphenyl) metal porphyrin by utilizing amphoteric boehmite ionic bonds |
-
2011
- 2011-06-23 CN CN201110171140A patent/CN102294268A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 李小港: "模拟酶催化分子氧对乙苯及其衍生物侧链氧化的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 黄冠等: "勃姆石四（4－硝基苯基）铁卟啉的催化性能", 《广西大学学报：自然科学版》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671708A (en) * | 2012-03-06 | 2012-09-19 | 广西大学 | Method for grafting solid-borne tetrakis(4-carboxylphenyl) metal porphyrin by utilizing amphoteric boehmite ionic bonds |
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Application publication date: 20111228 |