CN101972677A - Preparation method of nano zinc oxide supported metalloporphyrin catalyst and application thereof to catalytic oxidation of toluol - Google Patents
Preparation method of nano zinc oxide supported metalloporphyrin catalyst and application thereof to catalytic oxidation of toluol Download PDFInfo
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Abstract
The invention relates to a preparation method of a nano zinc oxide supported metalloporphyrin catalyst. The preparation method comprises the following steps of: stirring and dispersing a supported metalloporphyrin carrier Zn(OH)2 in an organic solvent; adding metalloporphyrin dissolved in the organic solvent, keeping a temperature of 60-70 DEG C, stirring for 5-6 h and decompressing and distilling to remove the organic solvent; and carrying out suction filtration and washing and drying a filter cake for 5-8 h in vacuum at 100-170 DEG C to obtain the nano zinc oixde supported metalloporphyrin catalyst. The nano zinc oxide supported metalloporphyrin catalyst of the invention is prepared by catalyzing air to oxide the toluol under the reaction conditions that the air pressure is 0.4-1.0 MPa, the reaction temperature is 150-190 DEG C, and the time is 2.0-4.5 h, the conversion rate of the toluol is over 7.5 percent, the selectivity of aldehyde alcohol is over 78 percent, the turn-over number of the supported catalyst reaches 8.8*104, and every 2.0 mg of the metalloporphyrin can be repeatedly used more than fifteen times and has basically unchanged catalytic efficiency.
Description
Technical field
The present invention relates to a kind of nano zine oxide supported metalloporphyrin Preparation of catalysts method and the application in catalytic oxidation toluene thereof.
Background technology
Phenmethylol and benzaldehyde are important fine chemical products, and phenmethylol and benzaldehyde are produced in the environmental protection of research catalytic air oxidation toluene, have important practical significance.In recent ten years, many toluene oxidation technology has been invented in Chinese scholars research, comprise 1.. chlorinolysis: obtain dichloro-toluene at the Benzyl Side-Chain chloro earlier, and be catalyst with the benzal chloride/zinc salt that is about 1/2000,70～80 ℃ with sodium carbonate basic hydrolysis 5～6h, can get yield and be 96～97% benzaldehyde.Complicated, the difficult control of reaction but the method course of reaction is long, product is chloride and give off be corrosive gas and debirs, and contaminative is big.In addition, the usefulness of this production route is not high yet.Therefore abroad now seldom use.2.. the gas phase oxidation of toluene method: fixed bed or fluidized-bed reactor are adopted in reaction, with air, O
2, or O
3Make oxidant, employing be vanadium, molybdenum, cerium or antimony, its oxide and salt, so their immobilized thing as catalyst, reaction is controlled under 350～550 ℃ and the 0.5～2.5MPa condition to be carried out.Primary product has benzaldehyde, benzoic acid, phenmethylol, hydrocarbon etc.Reaction condition is relatively harsher, also difficult to improve the selectivity of benzaldehyde.The conversion ratio that generally can control toluene is less than 4% obtaining 70% benzaldehyde selectivity, thereby avoids the generation of benzoic acid, phenol, carbon dioxide, carbon monoxide and tar.The catalyst development of high activity and high selectivity awaits to study.3.. the toluene liquid phase oxidation: the catalyst of producing benzaldehyde can be the soluble metal salt class, and great majority are halide or acylates of cobalt or manganese, is oxidant with the air, adds bromine and does co-catalyst.Can Rhodia, Dow and Snia-Viscosa catalytic process are as representative: its operation system is being catalyst at the homogeneous phase cobalt salt that contains acetic acid, under 165 ℃ and 1.0MPa, carry out, under the optimum reaction condition, the benzoic selectivity of principal product is 90%, and have only 3% selectivity as the benzaldehyde of accessory substance, toluene conversion is 15%.And acetate solvate and halogen ion are absolutely necessary.This can cause the heavy corrosion of equipment.
In the research of bionic catalysis air oxidation alkane and alkene, metalloporphyrin has great importance, this class catalyst action mild condition, and its high efficiency and the feature of environmental protection have enjoyed the concern of Chinese scholars.Under 8 atmospheric pressures and 160 ℃, be 3.2 * 10 only with concentration
-5The tetraphenyl cobalt porphyrin catalytic oxidation toluene of M can obtain 8.9% toluene conversion and 60% benzaldehyde and benzyl alcohol selective.This type of homogeneous catalysis system need not any solvent and additive, and equipment without any corrosiveness, is seldom brought pollution to environment.More regrettably: the catalysis of metalloporphyrin agent, because the synthesis yield of its free alkali is lower, the price comparison costliness.Therefore, homogeneous catalysis system can make metalloporphyrin reclaim and the recycling difficulty.
At present, supported metalloporphyrin is a kind of method that overcomes the existing deficiency of its homogeneous system.In order to address these problems; improve the stability of metalloporphyrin; improve its catalytic performance; Chinese scholars has also been done many significant work in synthetic and this field of protection metalloporphyrin; wish by synthesising stability higher; the better novel metal porphyrin of catalytic performance; also wish simultaneously to find some not only effective supported metalloporphyrins but also can improve the excellent carriers of its catalytic performance; prepare the supported metalloporphyrin catalyst that can be fit to wideer reaction environment, to satisfy the needs of Industrial Catalysis development.Supported metalloporphyrin also has significant progress in recent ten years.Generally speaking, still do not find a kind of suitable carrier, make immobilized metalloporphyrin can continue efficiently to repeat catalysis, and be used in actual industrial process.
Summary of the invention
The object of the invention provides a kind of nano zine oxide supported metalloporphyrin Preparation of catalysts method and the application in catalytic oxidation toluene thereof.This catalyst can efficiently be reused, and selective catalytic oxidation toluene is produced benzaldehyde and phenmethylol.Overcome the deficiency that the conversion per pass that exists in the present toluene oxidation technology is low, selectivity is not high, the pollution big, unit mass metalloporphyrin repeat usage is low.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of nano zine oxide supported metalloporphyrin Preparation of catalysts method is with the carrier Zn (OH) of supported metalloporphyrin
2Be scattered in the organic solvent through mechanical agitation, the metalloporphyrin that adds organic solvent dissolution again, keep 60 to 70 ℃ and stir 5～6h, utilize decompression distillation to remove organic solvent, promptly get nano zine oxide supported metalloporphyrin catalyst at 100～170 ℃ of vacuum drying 5～8h through suction filtration, washing, filter cake.
Described organic solvent is mainly lower boiling alcohols and ketone, for example: ethanol and acetone or the like organic solvent.
Used metalloporphyrin general structure is
Wherein, R=H, OH, NO
3X=Co, Mn, Fe, used carrier is mainly nano-ZnO etc.
The method that described nano-ZnO supported metalloporphyrin is used for catalytic air oxidation toluene is: get the nano-ZnO solid-carried catalyst that contains 0.5～2.0mg metalloporphyrin and put into the 500ml autoclave, add 200ml toluene.Atmospheric pressure is controlled at 0.4～1.0MPa, and temperature is controlled at 150～190 ℃, and speed of agitator is controlled at 200～600 rev/mins, and air mass flow is 0.04m
3/ h, reach design temperature after bubbling air react, the reaction time is at 2.0～4.5h.
Compare with existing toluene oxidation technology, outstanding advantage of the present invention is:
1, with the immobilized catalysis of metalloporphyrin agent of nano-ZnO, the relative molar concentration of core catalyst-metalloporphyrin is 2～5 * 10
-6Mol/L, selectivity catalytic air oxidation toluene is produced phenmethylol and benzaldehyde is obtained reasonable effect.The conversion ratio of toluene surpasses 8%, and the alcohol ketone selectivity is higher than 75%, and the catalyst turn over number can reach 5.0 * 10
4, catalyst still keeps good catalytic activity after reusing 10 times.
2, the nano-ZnO supported metalloporphyrin is as a kind of different-phase catalyst, and the catalytic performance that likens to the metalloporphyrin of homogeneous catalyst improves a lot, and has more Practical significance.This type of solid-carried catalyst preparation is simple, cost is low, the metalloporphyrin consumption is few, be easy to separate from product also suitable simultaneously various reaction units.The most important thing is by immobilized, effectively protected not oxidized dose of destruction of metalloporphyrin, it can efficiently be reused, is a kind of industrial bionic catalyst of environmental protection.
The specific embodiment
By the following examples technical scheme of the present invention is described further.
Embodiment 1
1, the method for preparing nano-ZnO immobilized four (to hydroxyl) phenyl cobalt porphyrin (THPPCo (II)) catalyst: with Zn (OH)
2Be scattered in the organic solvent through mechanical agitation, the metalloporphyrin that adds organic solvent dissolution again, keep 60 to 70 ℃ and stir 5～6h, utilize decompression distillation to remove organic solvent, promptly get nano-ZnO supported metalloporphyrin catalyst through suction filtration, washing, filter cake at 100～170 ℃ of vacuum drying 5～8h, described organic solvent is ethanol or acetone.
2, the using method of nano-ZnO immobilized four (to hydroxyl) phenyl cobalt porphyrin catalyst: the nano-ZnO solid-carried catalyst that will contain 2.0mg four (to hydroxyl) phenyl cobalt porphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 7.18%, aldehyde alcohol selectivity 65.3%, catalyst turn over number 4.15 * 10
4The catalyst that reclaims repeats catalysis 15 times under this reaction condition, the average conversion ratio of toluene is 7.08%, and average selectivity is 64.7%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was: 6.85%, and selectivity is 65.9%, turn over number is 7.72 * 10
4
Embodiment 2
1, prepares the method for nano-ZnO immobilized four (to hydroxyl) phenyl manganoporphyrin (THPPMn (II)) porphyrin catalyst with embodiment 1.
2, the using method of nano-ZnO immobilized four (to hydroxyl) phenyl manganoporphyrin catalyst: the nano-ZnO solid-carried catalyst that will contain 2.0mg four (to hydroxyl) phenyl manganoporphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 5.98%, aldehyde alcohol selectivity 74.5%, catalyst turn over number 3.5 * 10
4The catalyst that reclaims repeats catalysis 15 times under this reaction condition, the average conversion of toluene is: 5.64%; Average selectivity is 72.8%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was: 5.45%, and selectivity is 77.3%, turn over number is 6.4 * 10
4
Embodiment 3
1, prepares the method for nano-ZnO immobilized four (to hydroxyl) phenyl ferriporphyrin (THPPFe (II)) catalyst with embodiment 1.
2, the using method of nano-ZnO immobilized four (to hydroxyl) phenyl ferriporphyrin catalyst: the nano-ZnO solid-carried catalyst that will contain 2.0mg four (to hydroxyl) phenyl ferriporphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 5.14%, aldehyde alcohol selectivity 78.4%, catalyst turn over number 3.1 * 10
4The catalyst that reclaims repeats catalysis 15 times under this reaction condition, the average conversion of toluene is: 4.86%, and average selectivity is 75.3%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was respectively: 4.91%, and selectivity is 81.3%, turn over number is 6.7 * 10
4
Embodiment 4
1, prepares the method for nano-ZnO immobilized four (to nitro) phenyl cobalt porphyrin (TNPPCo (II)) catalyst with embodiment 1.
2, the using method of nano-ZnO immobilized four (to nitro) phenyl cobalt porphyrin catalyst: the nano-ZnO solid-carried catalyst that will contain 2.0mg four (to nitro) phenyl cobalt porphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 7.85%, aldehyde alcohol selectivity 71.5%, catalyst turn over number 4.8 * 10
4The catalyst that reclaims repeats catalysis 10 times under this reaction condition, the average conversion of toluene is: 7.34%, and average selectivity is 70.4%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was respectively: 7.04%, and selectivity is 75.7%, turn over number is 9.5 * 10
4
Embodiment 5
1, prepares the method for nano-ZnO immobilized four (to nitro) phenyl manganoporphyrin (TNPPMn (II)) catalyst with embodiment 1.
2, the using method of the violent porphyrin catalyst of immobilized four (to the nitro) phenyl of nano-ZnO: the nano-ZnO solid-carried catalyst that will contain 2.0mg four (to nitro) phenyl manganoporphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 6.13%, aldehyde alcohol selectivity 75.5%, catalyst turn over number 4.4 * 10
4The catalyst that reclaims repeats catalysis 10 times under this reaction condition, the average conversion of toluene is: 5.87%, and average selectivity is 73.8%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was respectively: 5.94%, and selectivity is 75.3%, turn over number is 7.3 * 10
4
Embodiment 6
1, prepares the method for nano-ZnO immobilized four (to nitro) phenyl ferriporphyrin (TNPPFe (II)) catalyst with embodiment 1.
2, the using method of nano-ZnO immobilized four (to nitro) phenyl ferriporphyrin catalyst: the nano-ZnO solid-carried catalyst that will contain 2.0mg four (to nitro) phenyl ferriporphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 5.61%, aldehyde alcohol selectivity 77.4%, catalyst turn over number 2.7 * 10
4The catalyst that reclaims repeats catalysis 10 times under this reaction condition, the average conversion of toluene is: 5.35%, and average selectivity is 76.5%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was respectively: 5.47%, and selectivity is 79.7%, turn over number is 5.1 * 10
4
Embodiment 7
1, prepares the method for the immobilized tetraphenyl cobalt of nano-ZnO porphyrin (TPPCo (II)) catalyst with embodiment 1.
2, the using method of the immobilized tetraphenyl cobalt of nano-ZnO porphyrin catalyst: the nano-ZnO solid-carried catalyst that will contain 2.0mg tetraphenyl cobalt porphyrin is put in the 500ml reactor, add 200ml toluene, 180 ℃ of reaction temperatures, reaction pressure 0.5MPa, mixing speed is 300 rev/mins, reaction time 4.0h.The conversion ratio of toluene is 6.17%, aldehyde alcohol selectivity 72.4%, catalyst turn over number 3.8 * 10
4The catalyst that reclaims repeats catalysis 7 times under this reaction condition, the average conversion of toluene is: 5.98%, and average selectivity is 71.5%.When the catalyst input amount was 1.0mg, the conversion ratio of toluene was respectively: 5.87%, and selectivity is 74.6%, turn over number is 5.7 * 10
4
Claims (2)
1. a nano zine oxide supported metalloporphyrin Preparation of catalysts method is characterized in that: with the carrier Zn (OH) of supported metalloporphyrin
2Be scattered in the organic solvent through mechanical agitation, the metalloporphyrin that adds organic solvent dissolution again, keep 60 to 70 ℃ and stir 5～6h, utilize decompression distillation to remove these organic solvents, promptly get nano zine oxide supported metalloporphyrin catalyst through suction filtration, washing, filter cake at 100～170 ℃ of vacuum drying 5～8h, described organic solvent is ethanol or acetone.
2. the application of the described nano zine oxide supported metalloporphyrin of claim 1 catalyst in catalytic oxidation toluene is characterized in that, its application process step is:
Get contain 0.5～2.0mg metalloporphyrin the nano-ZnO solid-carried catalyst in the 500ml autoclave, add 200ml toluene.Atmospheric pressure is controlled at 0.4～1.0MPa, and temperature is controlled at 150～190 ℃, and speed of agitator is controlled at 200～600 rev/mins, and oxygen flow is 0.04m
3/ h, reach design temperature after bubbling air react, the reaction time is at 2.0～4.5h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294267A (en) * | 2011-06-23 | 2011-12-28 | 广西大学 | Preparation method and application of zinc oxide solid borne tetra (pentafiuorophenyl)ferriporphyrin |
| CN102671702A (en) * | 2012-03-06 | 2012-09-19 | 广西大学 | Method for preparing zinc oxide ionic bond grafting and coordination supported tetra(4-carboxyl phenyl) metalloporphyrin catalyst |
| CN106000468A (en) * | 2016-06-01 | 2016-10-12 | 中山大学惠州研究院 | Metalloporphyrin-inorganic crystal composite microspheres and preparation method thereof |
| CN106076420A (en) * | 2016-06-08 | 2016-11-09 | 广西大学 | The preparation method and application of cadmium sulfide immobilized four (4 carboxyl phenyl) iron porphyrin catalysis material |
| CN106179502A (en) * | 2016-07-05 | 2016-12-07 | 广西大学 | The preparation method and application of graphene oxide immobilized four (4 carboxyl phenyl) manganoporphyrin catalysis material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367709A (en) * | 2008-09-22 | 2009-02-18 | 广西大学 | Method for catalysis of atmospheric oxidation cyclohexane with ultra-fine A100H-supported metalloporphyrin |
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2010
- 2010-09-30 CN CN 201010298194 patent/CN101972677A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367709A (en) * | 2008-09-22 | 2009-02-18 | 广西大学 | Method for catalysis of atmospheric oxidation cyclohexane with ultra-fine A100H-supported metalloporphyrin |
Non-Patent Citations (1)
| Title |
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| 《Chin.J.Chem.Eng.》 20071231 LI Yongfei et al. Toluene Oxyfunctionalization with Air over Metalloporphyrins and Reaction Condition Optimization 第453页第2.2节及表2 2 第15卷, 第3期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294267A (en) * | 2011-06-23 | 2011-12-28 | 广西大学 | Preparation method and application of zinc oxide solid borne tetra (pentafiuorophenyl)ferriporphyrin |
| CN102671702A (en) * | 2012-03-06 | 2012-09-19 | 广西大学 | Method for preparing zinc oxide ionic bond grafting and coordination supported tetra(4-carboxyl phenyl) metalloporphyrin catalyst |
| CN106000468A (en) * | 2016-06-01 | 2016-10-12 | 中山大学惠州研究院 | Metalloporphyrin-inorganic crystal composite microspheres and preparation method thereof |
| CN106076420A (en) * | 2016-06-08 | 2016-11-09 | 广西大学 | The preparation method and application of cadmium sulfide immobilized four (4 carboxyl phenyl) iron porphyrin catalysis material |
| CN106076420B (en) * | 2016-06-08 | 2018-10-23 | 广西大学 | The preparation method and application of cadmium sulfide immobilized four (4- carboxyl phenyls) ferriporphyrin catalysis material |
| CN106179502A (en) * | 2016-07-05 | 2016-12-07 | 广西大学 | The preparation method and application of graphene oxide immobilized four (4 carboxyl phenyl) manganoporphyrin catalysis material |
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Application publication date: 20110216 |