CN102688773A - Catalyst for preparing hydrogen peroxide from alkyl arene through catalytic oxidation, and preparation method and application thereof - Google Patents
Catalyst for preparing hydrogen peroxide from alkyl arene through catalytic oxidation, and preparation method and application thereof Download PDFInfo
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- CN102688773A CN102688773A CN2012101241307A CN201210124130A CN102688773A CN 102688773 A CN102688773 A CN 102688773A CN 2012101241307 A CN2012101241307 A CN 2012101241307A CN 201210124130 A CN201210124130 A CN 201210124130A CN 102688773 A CN102688773 A CN 102688773A
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Abstract
The invention provides a catalyst for preparing hydrogen peroxide from alkyl arene through catalytic oxidation, and a preparation method and application thereof, pertaining to a field of alkyl arene catalytic oxidation technology. An imidazole alkaline ionic liquid catalyst is immobilized in a catalyst on a hybrid mesoporous silicon-based material. Silicone-containing groups are introduced into a cation side chain of the ionic liquid. Anhydrous toluene is added into the silicon-based material and sodium hydroxide is added. After stirring, the ionic liquid is added, and stirring and reflux are carried out for more than 10 hours. The catalyst of the invention is obtained after filtering, washing and vacuum drying. A catalytic application process is that: air is used as a oxygen source, the mass of the added catalyst is 1% to 2.5% of that of the alkyl arene, catalytic oxidation reaction temperature is 80 DEG C to 150 DEG C, an air flow rate is 25 to 120L/ (h*mol alkyl arene) and the reaction time is 15 to 36 hours. With the catalyst of the invention, oxidation rate of the alkylbenzene is improved, yield and selectivity of the hydrogen peroxide are improved and reactants are likely to be separated.
Description
Technical field
The present invention relates to alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing catalyst, the preparation and uses thereof, belong to alkylaromatic hydrocarbon catalytic oxidation technical field.
Background technology
Since the cumene oxidation legal system was equipped with phenol process and is invented, the oxidation of alkylbenzene was by extensive studies, and the phenol 90% or more all adopts the production of cumene oxidation method in the world at present.Along with the cumene oxidation method is produced the development and the maturation of phenol-acetone technology, again the cumene oxidation legal system is equipped with in the production that phenol is generalized to resorcinol and hydroquinones from the 1950's.It is catalyst that the diisopropylbenzene (DIPB) oxidizing process normally adopts NaOH or sodium carbonate, in the oxidation of air, diisopropylbenzene (DIPB) is oxidized to di-isopropylbenzene hydroperoxide, and then under the effect of sulfuric acid, resolves into phenol and acetone.As: people such as Hirohiko Nambu have reported in US4237319 in the diisopropylbenzene (DIPB) oxidation, with the NaOH aqueous solution and NaCO
3The aqueous solution is catalyst, has added 5% the 5%NaOH aqueous solution or 5%NaCO
3Solution (wt) under different pressure and temperature, compares the yield and the selectivity of peroxide.Wu, et al. be at US, and 4935551 and US, reported in 4282384 patents in the diisopropylbenzene (DIPB) peroxidating, be catalyst with alkaline-earth metal BaO, added 0.002%～0.025% (wt), catalytic effect is best, and the peroxide yield can reach 35～45mol%.6350921 of U.S. Pat have been reported the technology of continuous preparation m-Diisopropylbenzene diperoxy hydrogen.Wherein use the 4%NaOH aqueous solution as catalyst; When m-Diisopropylbenzene diperoxy hydrogen content is 15～18%; With the 8%NaOH aqueous solution and m-Diisopropylbenzene extracting and demixing, oil phase then loops back receives that oxidation reactor carries out oxidation, water enrichment m-Diisopropylbenzene diperoxy hydrogen.People (Adv.Synth.Catal.2001.343) such as Osamu Fukuda have reported the application of NHPI at the catalytic oxidation isopropylbenzene.Making solvent with acetonitrile, the NHPI addition is the 10mol% of isopropylbenzene, after 20 hours, handles oxidation liquid with excessive triphenyl phosphorus 75 ℃ of reactions, and it is 77% that GC analyzes the yield that obtains dimethyl benzyl alcohol.Make initator if add AIBN, react after 8 hours, α, the yield of α '-dimethyl benzyl alcohol reaches 75%.Under the same condition, the conversion ratio of m-Diisopropylbenzene reaches 99%, handles 4 hours at 75 ℃ with 0.15mol sulfuric acid, and the yield of resorcinol is 36%.In Chinese patent 200810102379.1, mention and use alkali ionic liquid to be catalyst oxidation isopropylbenzene and diisopropylbenzene (DIPB), can significantly improve the conversion ratio of isopropylbenzene and the selectivity of hydrogen peroxide product.
No matter what adopt in above-mentioned these patents is NaOH, sodium carbonate, NHPI or alkali ionic liquid; First; They all are liquid type or little minute subclass catalyst of alkalescence, and these catalyst are difficult to separate with reactant liquor, all will be along with reactant liquor gets into follow-up sour decomposable process together; The activated centre of neutralizing acid decomposition catalyst; Increase the consumption of liquid acid such as sulfuric acid and the discharging of acid sludge, or the acidic resins decomposition technique of cleaning can't be run well, also made the refining work technology of follow-up phenolic product become complicated; Second, they are all carrying Mg
2+, Fe
3+Deng cation, these cations can make alkalescence anion-exchange resin lose ion-exchange capacity, decompose the antacid ability of intermediate ion exchanger resin thereby reduce follow-up acid.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that is used for alkylated aromatic hydrocarbons catalytic oxidation preparing hydrogen peroxide thing; This catalyst is through the immobilized method of cation, connects a surface to carrier material to ionic liquid, forms through ion-exchange again; Belong to solid base; Oxidation rate at the raising alkylbenzene reaches optionally simultaneously with the yield that improves hydroperoxide, easy and reactants separate, and do not carry Mg secretly
2+, Fe
3+Deng cation, prolong the life-span of decomposition reaction with acidic ion exchange resin catalyst.
A kind of catalyst that is used for alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing of the present invention; It is characterized in that alkaline ionic liquid catalyst
is planted in the catalyst that forms on the hybrid mesoporous silica-base material admittedly.
The above-mentioned catalyst of the present invention, its concrete structure is following:
In the following formula, hybrid mesoporous silica-base material can be selected from multiple micropore, mesoporous or multilevel hole material.Preferred SBA-15, MCM-41.
The method of the catalyst oxidation of alkyl aromatic hydrocarbons preparing hydrogen peroxide thing of a kind of alkylbenzene arenes catalytic oxidation preparing hydrogen peroxide thing of the present invention; It is characterized in that; With air as oxygen source; The alkylaromatic hydrocarbon catalytic oxidation is processed corresponding hydroperoxide, and the adding quality of catalyst is 1%～2.5% of an alkylaromatic hydrocarbon.The reaction temperature of catalytic oxidation is 80～150 ℃, and air mass flow is 25～120L/ (a hmol alkylaromatic hydrocarbon), and the reaction time is 15～36 hours.
Preparation of catalysts conventional method of the present invention: at first the cationic side chain of imidazole ion liquid is introduced the group that contains siloxanes; Then silica-base material is added dry toluene, add a certain amount of NaOH again, after the dispersed with stirring; Add more than an amount of above-mentioned ionic liquid stirring and refluxing 10h; Filter, washing, drying in vacuum obtains solid base catalyst.
R-chloropropyl trimethoxyl silane and N-methylimidazole are dissolved in toluene, reflux 24 hours, preparation ionic liquid chlorination 1-methyl-3-(3-trimethyl oxygen silicon base) propyl imidazole; Get chlorination 1-methyl-3-(3-trimethyl oxygen silicon base) propyl imidazole, toluene, NaOH, hybrid mesoporous silica-base material in reaction vessel; Reflux stirred more than 10 hours, suction filtration, washed with dichloromethane; 60 ℃ of vacuum drying get immobilized alkaline ionic liquid catalyst of the present invention.
The prepared solid base catalyst that obtains is applied in the oxidation reaction system of diisopropylbenzene (DIPB), after reaction a period of time, sample analysis is estimated this catalyst through the conversion ratio of diisopropylbenzene (DIPB) in the analytic sample and the selectivity of hydroperoxide.
Solid base catalyst of the present invention is easy to separate, and economy can be recycled, and does not have Na
+Residual, keep the high efficiency advantage of alkali ionic liquid.
The specific embodiment
Comparative Examples 1
Comparative Examples 1 is the base catalysis method for oxidation that adopts usually
Getting the 40g diisopropylbenzene (DIPB) is put in the there-necked flask of taking back stream device, stirring; Adding the 4gNaOH aqueous solution (mass percentage concentration 2%) is catalyst; 95 ℃ of reaction temperatures, bubbling air 160ml/min reacts after 24 hours; The conversion ratio of diisopropylbenzene (DIPB) is 30%, and the selectivity of hydroperoxide is 90%.Catalyst and reactant liquor are lumped together, can't separate.
Embodiment 1
The preparation of SBA-15: under 35 ℃, add mol ratio 41TEOS: 0.7P123: 240HCl: 8330H
2O stirs 20h, is warmed up to 80 ℃ then, and still aging 48h filters, and water washing after the drying, 48 hour is removed template with the absolute ethyl alcohol soxhlet extraction to there not being Cl-.80 ℃ of vacuum drying 20h promptly get SBA-15.
Preparation of catalysts: under nitrogen protection; 31ml r-chloropropyl trimethoxyl silane and 20mlN-methylimidazole are dissolved in 70ml toluene; Reflux 24 hours has thick yellow liquid to be sunken to bottom, and upper toluene is inclined and; Use the fresh toluene cyclic washing, revolve steaming and obtain yellow ionic liquid chlorination 1-methyl-3-(the 3-trimethyl oxygen silicon base) propyl imidazole of thickness.Its reaction equation is following:
Get chlorination 1-methyl-3-(3-trimethyl oxygen silicon base) propyl imidazole (5mmol), toluene (25ml), NaOH (5mmol); Pure silicon SBA-15 (1g) is in flask, and 105 ℃ of reflux stirred suction filtration 12 hours; Washed with dichloromethane, 60 ℃ of vacuum drying get immobilized alkali ionic liquid A.
Oxidation reaction: get the 40g isopropylbenzene and be put in the there-necked flask of taking back stream device, stirring, add the catalyst A of the above-mentioned preparation of 0.2g, 120 ℃ of reaction temperatures; Bubbling air 200ml/min; Reacted 16 hours, the conversion ratio of isopropylbenzene is 95%, and the selectivity of hydrogen phosphide cumene is 85%.Catalyst reclaims through isolated by filtration.
Embodiment 2
The preparation of MCM-41: get 6gCTAB and 50mlH
2O, heating for dissolving stirs slowly adding Na
2SiO
39H
2O.Stir, use 10%H
2SO
4Regulating PH is 10, puts into agitated reactor behind the stirring 30min, still aging 3d under 100 ℃.Filtration washing, in 100 ℃ of vacuum drying 12h, the white powder that obtains roasting 5h in 550 ℃ of air removes surfactant, promptly gets MCM-41.
Preparation of catalysts: get chlorination 1-methyl-3-(3-trimethyl oxygen silicon base) propyl imidazole (5mmol), toluene (25ml), NaOH (5mmol); Pure silicon MCM-41 (1g) is in flask; 105 ℃ of reflux stirred suction filtration, washed with dichloromethane 12 hours; 60 ℃ of vacuum drying get immobilized alkali ionic liquid B.
Oxidation reaction: get the 40g m-Diisopropylbenzene and be put in the there-necked flask of taking back stream device, stirring, add the 3.6g catalyst B, 95 ℃ of reaction temperatures; Bubbling air 160ml/min; Reacted 30 hours, the conversion ratio of diisopropylbenzene (DIPB) is 97%, the selectivity 32% of DHP; The selectivity of HHP is 36%, and the selectivity of DCL is 18%.Catalyst reclaims through isolated by filtration.
Embodiment 3
Get the 40g m-Diisopropylbenzene and be put in the there-necked flask of taking back stream device, stirring, add the 3.6g catalyst A, 95 ℃ of reaction temperatures; Bubbling air 160ml/min; Reacted 30 hours, the conversion ratio of diisopropylbenzene (DIPB) is 95%, the selectivity 37% of DHP; The selectivity of HHP is 34%, and the selectivity of DCL is 16%.
Embodiment 4
Get the 40g isopropylbenzene and be put in the there-necked flask of taking back stream device, stirring, add the 3.6g catalyst B, 120 ℃ of reaction temperatures, bubbling air 160ml/min reacted 24 hours, and the conversion ratio of isopropylbenzene is 95%, the selectivity 80% of CHP.
Embodiment 5
Get the 40g isopropyl naphthalene and be put in the there-necked flask of taking back stream device, stirring, add the 3.6g catalyst B, 100 ℃ of reaction temperatures, bubbling air 160ml/min reacted 24 hours, and the conversion ratio of isopropyl naphthalene is 85%, the selectivity 80% of hydrogen peroxide isopropyl naphthalene.
Claims (6)
1. catalyst that is used for alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing; It is characterized in that alkaline ionic liquid catalyst
is planted in the catalyst that forms on the hybrid mesoporous silica-base material admittedly.
2. the described a kind of catalyst that is used for alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing of claim 1; It is characterized in that its structural formula is
3. the described a kind of catalyst that is used for alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing of claim 1 is characterized in that hybrid mesoporous silica-base material is selected from multiple micropore, mesoporous or multilevel hole material.
4. the described a kind of catalyst that is used for alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing of claim 1 is characterized in that hybrid mesoporous silica-base material is SBA-15 or MCM-41.
5. the described a kind of Preparation of catalysts method that is used for alkylaromatic hydrocarbon catalytic oxidation preparing hydrogen peroxide thing of claim 1; It is characterized in that; R-chloropropyl trimethoxyl silane and N-methylimidazole are dissolved in toluene; Reflux 24 hours, preparation ionic liquid chlorination 1-methyl-3-(3-trimethyl oxygen silicon base) propyl imidazole; Get chlorination 1-methyl-3-(3-trimethyl oxygen silicon base) propyl imidazole, toluene, NaOH, hybrid mesoporous silica-base material in reaction vessel, reflux stirred more than 10 hours, suction filtration, washed with dichloromethane, 60 ℃ of vacuum drying.
6. utilize the method for the described catalyst oxidation of alkyl of claim 1 aromatic hydrocarbons preparing hydrogen peroxide thing; It is characterized in that; As oxygen source, the adding quality of catalyst is 1%～2.5% of an alkylaromatic hydrocarbon with air, and the reaction temperature of catalytic oxidation is 80～150 ℃; Air mass flow is 25～120L/ (a hmol alkylaromatic hydrocarbon), and the reaction time is 15～36 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911096A (en) * | 2012-10-31 | 2013-02-06 | 华南理工大学 | Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene |
| CN104655697A (en) * | 2015-02-04 | 2015-05-27 | 沈阳师范大学 | Preparation method and application of electroactive ionic liquid-based mesoporous silicon modified electrode |
| CN105146755A (en) * | 2015-07-10 | 2015-12-16 | 湖北中烟工业有限责任公司 | Method for preparing polysiloxane ionic liquid additives for cigarette filters |
| CN107626349A (en) * | 2017-09-27 | 2018-01-26 | 三峡大学 | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid |
| CN116375938A (en) * | 2023-04-06 | 2023-07-04 | 烟台大学 | Preparation of imidazolium inner salt polymer catalyst and application of catalyst in preparation of hydrogen peroxide |
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| CN101538020A (en) * | 2008-03-21 | 2009-09-23 | 北京化工大学 | Method for producing hydroperoxides by catalytic oxidation of aromatic hydrocarbons containing isopropyl |
| CN101724619A (en) * | 2009-12-24 | 2010-06-09 | 南京工业大学 | Application of functionalized ionic liquid modified mesoporous molecular sieve in enzyme immobilization |
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Cited By (9)
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| CN102911096A (en) * | 2012-10-31 | 2013-02-06 | 华南理工大学 | Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene |
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| CN104655697B (en) * | 2015-02-04 | 2017-05-31 | 沈阳师范大学 | A kind of preparation method and application of electroactive ionic liquid base mesoporous silicon modified electrode |
| CN105146755A (en) * | 2015-07-10 | 2015-12-16 | 湖北中烟工业有限责任公司 | Method for preparing polysiloxane ionic liquid additives for cigarette filters |
| CN105146755B (en) * | 2015-07-10 | 2019-01-11 | 湖北中烟工业有限责任公司 | A kind of preparation method of polysiloxanes ionic liquid cigarette filter-tip additive agent |
| CN107626349A (en) * | 2017-09-27 | 2018-01-26 | 三峡大学 | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid |
| CN107626349B (en) * | 2017-09-27 | 2020-04-24 | 三峡大学 | Catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid and method for preparing benzyl alcohol, benzaldehyde and benzoic acid |
| CN116375938A (en) * | 2023-04-06 | 2023-07-04 | 烟台大学 | Preparation of imidazolium inner salt polymer catalyst and application of catalyst in preparation of hydrogen peroxide |
| CN116375938B (en) * | 2023-04-06 | 2023-10-20 | 烟台大学 | Preparation of imidazolium inner salt polymer catalyst and application of catalyst in preparation of hydrogen peroxide |
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Application publication date: 20120926 |