CN101235007A - Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene - Google Patents
Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene Download PDFInfo
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- CN101235007A CN101235007A CNA2007100343302A CN200710034330A CN101235007A CN 101235007 A CN101235007 A CN 101235007A CN A2007100343302 A CNA2007100343302 A CN A2007100343302A CN 200710034330 A CN200710034330 A CN 200710034330A CN 101235007 A CN101235007 A CN 101235007A
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- isopropyl benzene
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- metalloporphyrin
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- air
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Abstract
The invention discloses a method for catalyzing and selectively oxidizing cumene into cumene hydroperoxide, which comprises in a mixture of oxidant air, oxygen-enriched air, or of oxygen gas and inertia gas, at an absolute reaction pressure of 0.1 to 1.0 MPa and a reaction temperature of 70 to130 DEG C, using the single metalloporphyrin of a formula (1), mu-oxgen double metalloporphyrin or relative carrier as catalyst at the density of 1 to 80 ppm without additional materials. The metalloporphyrin of low density can effectively and high selectively catalyze air to oxidize cumene into cumene hydroperoxide. The catalyst of the invention has low consumption, low synthesis cost, low catalysis reaction temperature, quick initiation, less byproduct, high selectivity and simple process, while cumene hydroperoxide yield is higher than industrial non-catalysis reaction yield and the reaction time is shorter than industrial non-catalysis reaction.
Description
Technical field:
The present invention relates to a kind ofly under catalysis of metalloporphyrin, the direct catalyzed oxidation of mixed gas that isopropyl benzene is formed by air or oxygen-rich air or oxygen and rare gas element is the method for isopropyl benzene hydroperoxide.
Background technology:
Cumene oxidation prepares isopropyl benzene hydroperoxide (being called for short CHP), is the crucial intermediate steps that present industrial cumene method is produced phenol and coproduction acetone process.Cumene method is produced the technology of phenol and cogeneration of propanone and is made up of three-step reaction, i.e. benzene and propylene alkylation synthesizing iso-propylbenzene, and isopropyl benzene is oxidised with air to isopropyl benzene hydroperoxide, and isopropyl benzene hydroperoxide is phenol and acetone through acid catalyzed decomposition.Phenol more than 90% all adopts cumene method production in the world at present.Except being used for synthesizing phenol, isopropyl benzene hydroperoxide also is widely used in other field of fine chemistry industry, macromolecular material and organic synthesis.It can be used as chain type autoxidation reaction and initiator of polyreaction, the promotor of the vulcanization of rubber, the oxygenant of organic compound etc.
In present cumene method phenol-acetone technology, non-catalyst oxidation technology is adopted in the preparation of isopropyl benzene hydroperoxide, add a certain amount of isopropyl benzene hydroperoxide (CHP) as initiator, also will add the acidic by-products that a certain amount of alkaline additive produces with neutralization in the reaction process.Because oxygen molecule is difficult to activation under the on-catalytic condition, therefore existing cumene oxidation technology exists the defective that decomposition induction time is long, speed is slow, side reaction is many, selectivity is low.
US3141046 discloses a kind of method that alkaline additives such as sodium salt or magnesium salts carry out the atmospheric oxidation isopropyl benzene that adds in reaction solution; TW229068B discloses a kind of NH of using
3Replace basic metal and alkaline-earth metal as additive with the metal ammonium salt, make the technical process of isopropyl benzene hydroperoxide; US2005272959 discloses and has a kind ofly made additive with ammonium salt (wt%=0.001-0.5%) and ammoniacal liquor (wt%=0.001-0.5%), wherein, ammoniacal liquor: ammonium salt (mass ratio)=1: 100 to 100: 1, under High Temperature High Pressure, the method for aqueous emulsion oxidation isopropyl benzene; US2006014985 discloses a kind of solid alkaline medium such as pyrimidine resin, method of carrying out the cumene oxidation reaction of adding in the isopropyl benzene reaction solution.These methods are all existing shortcomings such as long reaction time, technical process complexity, pre-treatment or postprocessing working procedures are various in varying degrees.
Summary of the invention:
The invention provides little, the synthetic low price of a kind of used catalyst metal porphyrin consumption, the catalyzed reaction temperature is low, initiation is fast, by product is few, technology is simple, isopropyl benzene hydroperoxide productivity ratio industry non-catalytic reaction productive rate is big, reaction times shortens dramatically than industrial non-catalytic reaction, can be efficiently, highly selective catalytic air oxidation isopropyl benzene is the novel process of isopropyl benzene hydroperoxide.
The present invention is achieved in that and is feeding under the condition of air that absolute pressure is 0.1-1.0MPa or oxygen-rich air or oxygen and the mixed gas of rare gas element composition, temperature of reaction is 70-130 ℃, select for use the monometallic porphyrin of general formula (1) or (2) and μ-oxygen bimetallic porphyrin or their immobilized thing as catalyzer, catalyst concn is 1-80ppm.No longer add other materials.Reaction times 0.5-10 hour.Metalloporphyrin is can be under extremely low concentration efficient, highly selective catalytic air oxidation isopropyl benzene is an isopropyl benzene hydroperoxide.
Atoms metal M in the above-mentioned metal porphyrins structure, M
1, M
2Can be transition metal atoms or lanthanide series metal atom; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin.Dentate X can be an acetate, acetate acetone, halogen.
Catalyzer can be one or more of above-mentioned metalloporphyrin in the cumene oxidation technology of the present invention.Also can be above-mentioned metalloporphyrin and supported metalloporphyrin inorganic and that organic polymer constitutes by physics or chemical process.
The carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, titanium dioxide, porous ceramics, polyvinyl chloride, poly-peroxide ethene, polystyrene, Mierocrystalline cellulose, chitosan, chitin or their modifier.
Test shows that described catalysis of metalloporphyrin agent becomes the reaction of isopropyl benzene hydroperoxide to have good catalytic performance to the atmospheric oxidation isopropyl benzene.With the catalysis of metalloporphyrin agent composition and the variation in temperature of reaction and reaction times, the isopropyl benzene hydroperoxide transformation efficiency is between 16-45%, and selectivity is between 90%-99%.Because temperature of reaction is low, the reaction times is short, has effectively controlled the further decomposition of the deep oxidation and the isopropyl benzene hydroperoxide of isopropyl benzene.
Embodiment:
Embodiment 1:
With the metalloporphyrin that 1mg has general formula (1) structure, R
1=Cl, R
2=R
3=H, M=Mn, X=Cl adds in the isopropyl benzene of 150ml, and feeding absolute pressure with the flow of 600ml/min is the air of 0.1MPa.110 ℃ of following stirring reactions 4 hours, the productive rate of isopropyl benzene hydroperoxide was 24.9%, and selectivity is 94.5%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, the isopropyl benzene hydroperoxide productive rate has only 2.4%, and selectivity is 96.1%.
Embodiment 2:
With the metalloporphyrin that 2mg has general formula (1) structure, R
1=Cl, R
2=R
3=H, M=Fe, X=Cl adds in the isopropyl benzene of 300ml, and feeding absolute pressure with the flow of 500ml/min is the air of 0.1MPa.110 ℃ of following stirring reactions 4 hours, the productive rate of isopropyl benzene hydroperoxide was 20.6%, and selectivity is 96.0%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, the isopropyl benzene hydroperoxide productive rate has only 2.2%, and selectivity is 96.5%.
Embodiment 3:
The metalloporphyrin that 5mg is had general formula (1) structure dissolves in the 150ml isopropyl benzene R
1=Cl, R
2=R
3=H, M=Mn, feeding absolute pressure with 600ml/min gas speed is the air of 0.1MPa, and 120 ℃ of following reactants 3 hours, the isopropyl benzene hydroperoxide productive rate was 38.85%, and selectivity is 90.5%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, the isopropyl benzene hydroperoxide productive rate has only 2.9%, and selectivity is 95.2%.
Embodiment 4:
With the metalloporphyrin that 3mg has general formula (2) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn adds in the isopropyl benzene of 375ml, and to feed absolute pressure with the flow of 600ml/min be 0.1MPa, contain oxygen is 30% oxygen-rich air.120 ℃ of following stirring reactions 3 hours, the isopropyl benzene hydroperoxide productive rate was 39.7%, and selectivity is 91.6%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, the isopropyl benzene hydroperoxide productive rate has only 2.9%, and selectivity is 95.2%.
Embodiment 5:
With the metalloporphyrin that supported on silica-gel 1.5mg has general formula (1) structure, R
1=Cl, R
2=R
3=H, M=Mn, X=Cl adds in the isopropyl benzene of 250ml, and feeding absolute pressure with the flow of 600ml/min is the air of 0.1MPa.110 ℃ of following stirring reactions 4 hours, the isopropyl benzene hydroperoxide productive rate was 27.5%, and selectivity is 95.0%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, the isopropyl benzene hydroperoxide productive rate has only 2.4%, and selectivity is 96.1%.
Embodiment 6:
With the metalloporphyrin that 3mg has general formula (2) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn adds in the isopropyl benzene of 375ml, and feeding absolute pressure with the flow of 600ml/min is the air of 0.3MPa.100 ℃ of following stirring reactions 3 hours, the isopropyl benzene hydroperoxide productive rate was 25.3%, and selectivity is 92.3%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, the isopropyl benzene hydroperoxide productive rate has only 2.1%, and selectivity is 96.6%.
Claims (4)
1. a catalytic air oxidation isopropyl benzene prepares the method for isopropyl benzene hydroperoxide, it is characterized in that: feeding absolute pressure is the air of 0.1-1.0MPa or the mixed gas of oxygen-rich air or oxygen and rare gas element composition, temperature of reaction is 70-130 ℃, select for use the monometallic porphyrin of general formula (1) or (2) and μ-oxygen bimetallic porphyrin or their immobilized thing as catalyzer, catalyst concn is 1-80ppm, reaction times 0.5-10 hour.
General formula (1)
General formula (2)
Atoms metal M in the above-mentioned metal porphyrins structure, M
1, M
2Can be transition metal atoms or lanthanide series metal atom; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, nitro, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin.Dentate X be can with atoms metal coordinate atom or atomic group.
2. according to the described method of claim 1, it is characterized in that: the atoms metal M in the described general formula (1) is Fe, Mn, Co, Cr, Cu, Zn, Pt, Pd or Tb, and dentate X is acetate, methyl ethyl diketone or halogen; Atoms metal M in the described general formula (2)
1, M
2Be Fe, Mn or Cr.
3. according to claim 1 or 2 described methods, it is characterized in that: the absolute pressure of reaction is 0.1-0.6MPa, oxygenant is the mixed gas of air or oxygen-rich air or oxygen and rare gas element composition, and temperature of reaction is 80-120 ℃, and reaction is the purpose product with the isopropyl benzene hydroperoxide.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that: metalloporphyrin can constitute supported metalloporphyrin with following carrier: silica gel, molecular sieve, aluminum oxide, titanium dioxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, poly-peroxide ethene, polystyrene, Mierocrystalline cellulose, chitosan, chitin or their modifier.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100343302A CN101235007A (en) | 2007-01-29 | 2007-01-29 | Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene |
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|---|---|---|---|
| CNA2007100343302A CN101235007A (en) | 2007-01-29 | 2007-01-29 | Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940948A (en) * | 2010-07-13 | 2011-01-12 | 中北大学 | Method for immobilizing metalloporphyrin by crosslinked polystyrene microspheres |
| CN102911096A (en) * | 2012-10-31 | 2013-02-06 | 华南理工大学 | Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene |
| CN104844493A (en) * | 2015-04-01 | 2015-08-19 | 中石化上海工程有限公司 | Dicumyl peroxide (DCP) and propylene oxied (CHPPO) coproduction method |
| CN104650358B (en) * | 2015-02-04 | 2017-02-22 | 太原理工大学 | Porphyrin-based heteronuclear double-metal polymer, and preparation method and applications thereof |
| CN107098840A (en) * | 2017-06-20 | 2017-08-29 | 惠州宇新化工有限责任公司 | A kind of method that oxidation of isobutane prepares TBHP |
| CN110841698A (en) * | 2018-08-21 | 2020-02-28 | 中国石油化工股份有限公司 | Alkyl benzene hydroperoxide catalyst, preparation method and application thereof |
| CN110845382A (en) * | 2018-08-21 | 2020-02-28 | 中国石油化工股份有限公司 | Process for preparing alkylbenzene hydroperoxide |
| CN111995557A (en) * | 2020-08-27 | 2020-11-27 | 浙江工业大学 | Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with iron (II) porphyrin |
| CN112094214A (en) * | 2020-08-27 | 2020-12-18 | 浙江工业大学 | Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with nickel (II) porphyrin |
-
2007
- 2007-01-29 CN CNA2007100343302A patent/CN101235007A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940948A (en) * | 2010-07-13 | 2011-01-12 | 中北大学 | Method for immobilizing metalloporphyrin by crosslinked polystyrene microspheres |
| CN102911096A (en) * | 2012-10-31 | 2013-02-06 | 华南理工大学 | Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene |
| CN104650358B (en) * | 2015-02-04 | 2017-02-22 | 太原理工大学 | Porphyrin-based heteronuclear double-metal polymer, and preparation method and applications thereof |
| CN104844493A (en) * | 2015-04-01 | 2015-08-19 | 中石化上海工程有限公司 | Dicumyl peroxide (DCP) and propylene oxied (CHPPO) coproduction method |
| CN107098840A (en) * | 2017-06-20 | 2017-08-29 | 惠州宇新化工有限责任公司 | A kind of method that oxidation of isobutane prepares TBHP |
| CN107098840B (en) * | 2017-06-20 | 2019-04-16 | 惠州宇新化工有限责任公司 | A kind of method of oxidation of isobutane preparation tert-butyl hydroperoxide |
| CN110841698A (en) * | 2018-08-21 | 2020-02-28 | 中国石油化工股份有限公司 | Alkyl benzene hydroperoxide catalyst, preparation method and application thereof |
| CN110845382A (en) * | 2018-08-21 | 2020-02-28 | 中国石油化工股份有限公司 | Process for preparing alkylbenzene hydroperoxide |
| CN110845382B (en) * | 2018-08-21 | 2021-11-30 | 中国石油化工股份有限公司 | Process for preparing alkylbenzene hydroperoxide |
| CN110841698B (en) * | 2018-08-21 | 2022-07-08 | 中国石油化工股份有限公司 | Alkyl benzene hydroperoxide catalyst, preparation method and application thereof |
| CN111995557A (en) * | 2020-08-27 | 2020-11-27 | 浙江工业大学 | Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with iron (II) porphyrin |
| CN112094214A (en) * | 2020-08-27 | 2020-12-18 | 浙江工业大学 | Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with nickel (II) porphyrin |
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Open date: 20080806 |