CN102911096A - Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene - Google Patents
Method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene Download PDFInfo
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- CN102911096A CN102911096A CN2012104292669A CN201210429266A CN102911096A CN 102911096 A CN102911096 A CN 102911096A CN 2012104292669 A CN2012104292669 A CN 2012104292669A CN 201210429266 A CN201210429266 A CN 201210429266A CN 102911096 A CN102911096 A CN 102911096A
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- isopropyl benzene
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Abstract
The invention discloses a method for synthetizing cumene hydroperoxide by catalytic oxidation of cumene. The method includes steps of adding reactant cumene and solid catalysts into a reactor, mixing the cumene with the solid catalysts, treating mixture ultrasonically to form suspension liquid; heating the suspension liquid to be 70-100 DEG C, leading oxygen gas into the suspension liquid for reacting for 1-12 hours; leading oxidants in a bubbling manner at oxygen rate of 0.5-1.5mL/min by each milliliter of cumene; after finishing reaction, separating reacted mixture to obtain the solid catalysts and liquid mixture containing cumene hydroperoxide; and separating and purifying the liquid mixture to obtain the cumene hydroperoxide. The solid catalysts are carbon materials from one or multiple of carbon nano-tubes, diamond and active carbon. The method has simple operation flow; the non-metal catalysts used in the method are non-corrosive, environment-friendly, low-price and reusable; and cumene conversion rate is high, and the target product, namely the cumene hydroperoxide, has good selectivity.
Description
Technical field
The present invention relates to the synthetic method of isopropyl benzene hydroperoxide, belong to the organic synthesis applied technical field.
Background technology
Phenol is a kind of important Organic Chemicals, mainly for the production of resol, hexanolactam, dihydroxyphenyl propane, hexanodioic acid, aniline, alkylphenol and Whitfield's ointment etc.The synthetic method of phenol is more, mainly contains cumene method, toluol-benzene formic acid method and benzene direct oxidation method.Because production cost is low, product purity is high, cumene method is the main method of producing phenol in the present world wide, and its throughput accounts for more than 90% of Phenol at Home throughput.
Cumene method is produced phenol and is comprised three reactions: (1) benzene and propylene addition synthesizing iso-propylbenzene; (2) under the oxygen effect, the isopropyl benzene peroxidation generates isopropyl benzene hydroperoxide; (3) isopropyl benzene hydroperoxide (CHP) decomposes under acidic conditions and obtains phenol and acetone.Wherein, isopropyl benzene peroxidation efficient is minimum, it is a very important step in the isopropyl benzene legal system phenol process, this reaction is free radical reaction, traditional production technique is as follows: take air as oxygenant, add a small amount of CHP as initiator, temperature of reaction is 110～115 ℃, reaction pressure is 0.4～0.6MPa, usually needs to add alkaline additive (such as NaOH, Na
2CO
3) organic acid that generates of neutralization reaction process.This method needs at high temperature reaction, causes the violent decomposition of CHP, and careless manipulation may set off an explosion; Produced simultaneously by product kind is more, and liquid waste disposal is complicated; The alkali lye corrosive equipment affects mass transfer.In order to eliminate the impact of alkaline matter, the patent of US6956136-B2 replaces alkali lye with a certain proportion of ammonium salt and ammonia water mixture, can obtain preferably selectivity, but temperature of reaction is still very high, and liquid waste disposal is more complicated also.Therefore, the high-performance catalyst of seeking a kind of reaction conditions gentleness is the study hotspot about the cumene oxidation reaction always.
Transition metal can promote the oxidation of isopropyl benzene, shortens decomposition induction time, is a class catalyzer of most study.But transition metal promotes CHP to decompose, and can produce a large amount of by product 2-phenyl-2-propyl alcohol, has reduced the selectivity of CHP.In order to improve the selectivity of CHP, in the patent of CN101235007 and CN1948365, transition metal is prepared into the form of organic complex, the method for metalloporphyrin and polymer xifualkali phthalocyanin bimetal compound catalysis cumene oxidation is disclosed respectively.This method can improve the selectivity of CHP; But the catalyzer preparation is complicated, expensive, and organic coordination compound is poisonous, is not suitable for industrial application.In addition, in the patent of JP8259529-A, disclose and a kind of transition metal has been loaded on method on the gac, temperature of reaction is lower, but the selectivity of CHP is lower.
In the patent of WO200174767-A, used a kind of non-metallic catalyst.It is with the catalyzer of nitrogenous substances (such as HP) as the isopropyl benzene peroxidation, and the CHP selectivity is near 100%, and transformation efficiency is also higher.But this catalyzer is expensive, is difficult to reclaim and recycle, and residual catalyzer also can affect the next experimental result of CHP decomposition phenol processed simultaneously.
In view of the deficiency that above-mentioned all kinds of catalyzer exist, the catalyzer that develop a kind of low price, is easy to separate, have the reusable edible of better low temperature active is still the emphasis of cumene oxidation research.
In recent years, carbon material is because preparation is simple, low price, environmental friendliness and have catalytic activity, by extensive concern.As carbon material can well Oxidation Ethylbenzene, hexanaphthene etc. carries out free radical reaction.Up to the present, also do not see take carbon nanotube as heterogeneous catalyst, oxygen or air are oxygenant, and the catalyzed oxidation isopropyl benzene prepares the open report of CHP technique.
Summary of the invention
The object of the invention is to overcome the deficiency of existing preparation CHP technique, provide that a kind of flow process is simple, the novel process of operational safety, eco-friendly synthetic CHP.
Purpose of the present invention is achieved through the following technical solutions:
A kind of isopropyl benzene catalyzed oxidation is produced the method for isopropyl benzene hydroperoxide, may further comprise the steps:
(1) reactant isopropyl benzene and solid catalyst are joined in the reactor mix, supersound process forms suspension again; Described solid catalyst is carbon material, and carbon material is one or more in carbon nanotube, diamond and the gac; Solid catalyst and isopropyl benzene weight ratio are 0.006～0.024: 1;
(2) suspension with gained is heated to 70～100 ℃, passes into oxygen, reacts 1～12h under the normal pressure; Oxygenant passes in the bubbling mode, and by every milliliter of isopropyl benzene, oxygen gas flow rate is 0.5～1.5mL/min;
(3) after the reaction of step (2) finishes, reaction mixture is separated the liquid mixture that obtains solid catalyst and contain isopropyl benzene hydroperoxide.
(4) with the liquid mixture separating-purifying in the step (3), obtain the product isopropyl benzene hydroperoxide.
For further realizing the object of the invention, the described solid catalyst of step (3) is used for step (1), as the solid catalyst raw material.
Described solid catalyst and isopropyl benzene weight ratio are preferably 0.006～0.012: 1.
Described temperature of reaction is preferably 80～90 ℃.The described reaction times is preferably 8～10h.
Described solid catalyst is preferably carbon nanotube.
The present invention is take oxygen as oxygenant, and with the active ingredient of carbon material as heterogeneous catalyst, catalysis isopropyl benzene peroxidation prepares CHP.
The present invention compared with prior art has the following advantages:
(1) temperature of reaction of the present invention is lower, has not only reduced the energy consumption in the reaction process, has also improved the safety coefficient of reaction.
(2) the present invention with nonmetal-carbon material as catalyzer, but catalyzer separates with the product direct filtration; Simultaneously carbon material has wide material sources, low price, and environmental friendliness, the advantage such as can be recycled.
(3) the used carbon material of the present invention is higher to cumene oxidation catalytic reaction activity, and selectivity is better.
Description of drawings
Fig. 1 is the chromatography of gases figure of embodiment 2 products.
Embodiment
The present invention will be further described below in conjunction with embodiment and accompanying drawing, but protection scope of the present invention is not limited to the scope of embodiment statement.
Measurement and calculation method (normalization method) about isopropyl benzene transformation efficiency (%) and CHP selectivity (%) among the following embodiment is as follows:
(1) separates the liquid mixture that rear gained contains CHP, take by weighing two parts (each 0.8g).A copy of it is with the content of iodometric determination CHP: add m in iodine flask
1G reaction gained liquid mixture adds the 20mL glacial acetic acid solution, adds 2gNaHCO again
3Pressed powder shakes gently and makes pressed powder and liquid mixing even; Then add the saturated KI solution of 10mL, immerse when reaction extremely no longer produces bubble basically in 60 ℃ of oil baths, take out and use water cooling, add 100mL distilled water; Be c with concentration
1, the standard Na of the mol/L of unit (such as 0.15mol/L)
2S
2O
3Standardization of solution to solution is light yellow, adds 2mL Starch Indicator (massfraction is 5%), continues to be titrated to solution and becomes oyster white by blueness, is titration end point, writes down the standard Na of consumption
2S
2O
3Liquor capacity is VmL.
Claim in addition a liquid mixture, quality is m
2G adds m
3G(0.4g) mark in toluene is done, after shaking up, add excessive triphenylphosphine reduction, add the 2mL dilution in acetonitrile, then the amount of substance of using chromatography of gases (150 ℃ of column temperatures, sampler and detector temperature are 280 ℃) to measure isopropyl benzene, methyl phenyl ketone and 2-phenyl-2-propyl alcohol in every gram liquid mixture is respectively n
1, n
2And n
3(mol).
The amount of substance of CHP is in every gram liquid mixture of iodometric determination:
n
CHP（mol）=c
1xVx0.5/(m
1x1000)
The transformation efficiency of isopropyl benzene (%)=100x (n
2+ n
3)/(n
1+ n
2+ n
3)
The selectivity of CHP (%)=100xn
CHP/ (n
2+ n
3)
The productive rate of CHP (%)=100xn
CHP/ (n
1+ n
2+ n
3).
10.0mL isopropyl benzene (density is 8.4g/mL) and 100mg carbon nanotube (catalyst carbon nanotube and isopropyl benzene weight ratio are 0.012: 1) are joined in the there-necked flask, supersound process 2min(frequency 40kHz, 30 ℃, but also supersound process 5min), form mixing suspension.Then under magnetic agitation, place oil bath to be heated to predetermined temperature of reaction (such as table 1) this mixing suspension after, pass into oxygen with 10mL/min speed under the normal pressure, reaction 8h.After reaction finished, the gained mixed solution obtained after filtration solid catalyst and contains the liquid mixture of CHP.To the liquid mixture analysis, measure the transformation efficiency of isopropyl benzene and the selectivity of CHP and the results are shown in Table 1, can find out, temperature raises and is conducive to the oxidation of isopropyl benzene, reach 100 ℃ but work as temperature, CHP decomposes acceleration, when transformation efficiency significantly improves, the CHP selectivity is lower, and temperature of reaction is preferably 80～90 ℃.
Table 1 temperature of reaction is on the impact of isopropyl benzene peroxidation
| |
1 | 2 | 3 | 4 |
| Temperature of reaction (℃) | 70 | 80 | 90 | 100 |
| Isopropyl benzene transformation efficiency (%) | 16.3 | 24.1 | 35.4 | 49.6 |
| CHP selectivity (%) | 87.9 | 88.4 | 83.7 | 78.6 |
10.0mL isopropyl benzene (density is 8.4g/mL) and 100mg carbon nanotube (catalyst levels carbon nanotube and isopropyl benzene weight ratio are 0.012: 1) are joined in the there-necked flask supersound process 2min(frequency 40kHz, 30 ℃), form mixing suspension.Then under magnetic agitation, place oil bath to be heated to 80 ℃ of temperature of reaction this mixed solution, then pass into oxygen with 10mL/min speed, react certain hour (seeing Table 2) under the normal pressure.After reaction finished, the gained mixed solution can obtain after filtration solid catalyst and contain the liquid mixture of CHP.Liquid mixture is analyzed, measured the transformation efficiency of isopropyl benzene and the selectivity of CHP and the results are shown in Table 2.In the analytical table data as can be known, along with the increase in reaction times, the CHP selectivity is on a declining curve, therefore in the time range of table 2 research, 8～10h is more excellent.
Table 2 reaction times is on the impact of cumene oxidation reaction
| |
5 | 6 | 7 |
| Reaction times (h) | 4 | 6 | 10 |
| Isopropyl benzene transformation efficiency (%) | 10.9 | 19.0 | 31.5 |
| CHP selectivity (%) | 91.6 | 89.2 | 84.0 |
Embodiment 8～9
10.0mL isopropyl benzene (density is 8.4g/mL) and 100mg carbon nanotube (catalyst carbon nanotube and isopropyl benzene weight ratio are 0.012: 1) are joined in the there-necked flask ultrasonic 2min(frequency 40kHz, 30 ℃), form mixing suspension.Under magnetic agitation, place oil bath to be heated to 80 ℃ of temperature of reaction this mixed solution afterwards, then pass into oxygen reaction 8h with given pace (seeing Table 3) under the normal pressure.After reaction finished, the gained mixed solution can obtain after filtration solid catalyst and contain the liquid mixture of CHP.Liquid mixture is analyzed, measured the transformation efficiency of isopropyl benzene and the selectivity of CHP and the results are shown in Table 3.Comparing embodiment 8,2,9 illustrates that oxygen gas flow rate affects not quite the result in the scope of research.
Table 3 oxygen gas flow rate is on the impact of isopropyl benzene peroxidation
| Embodiment | 8 | 9 |
| Oxygen gas flow rate (mL/min) | 5 | 15 |
| Isopropyl benzene transformation efficiency (%) | 22.2 | 26.4 |
| CHP selectivity (%) | 86.6 | 83.8 |
Embodiment 10～13
The carbon nanotube (seeing Table 4) of 10.0mL isopropyl benzene (density is 8.4g/mL) and certain mass is joined in the there-necked flask ultrasonic 3min(frequency 40kHz, 30 ℃), form mixing suspension.Then under magnetic agitation, place oil bath to be heated to 80 ℃ of temperature of reaction this mixed solution, then pass into oxygen with 10mL/min speed, react 8h under the normal pressure.After reaction finished, the gained mixed solution can obtain after filtration solid catalyst and contain the liquid mixture of CHP.Liquid mixture is analyzed, measured the transformation efficiency of isopropyl benzene and the selectivity of CHP and the results are shown in Table 4.Comparing embodiment 10,2,11,12,13, reaction has preferably catalytic activity to cumene oxidation can obviously to find out carbon nanotube, and catalyzer and isopropyl benzene weight ratio are when 0.006～0.012:1 simultaneously, and the selectivity of CHP is higher.
Table 4 catalyst levels is on the impact of isopropyl benzene peroxidation
| Embodiment | 10 | 11 | 12 | 13 |
| Catalyzer and isopropyl benzene weight ratio | 0 | 0.006 | 0.018 | 0.024 |
| Isopropyl benzene transformation efficiency (%) | 2.7 | 17.8 | 31.0 | 34.5 |
| CHP selectivity (%) | 99.2 | 90.8 | 81.3 | 76.2 |
Embodiment 14～15
With 10mL isopropyl benzene (density is 8.4g/mL) and 100mg solid carbon catalyst activity charcoal or diamond (catalyst activity charcoal and isopropyl benzene weight ratio are 0.012: 1), join in the there-necked flask, ultrasonic 2min(frequency 40kHz, 30 ℃), form mixing suspension.Then under magnetic agitation, place oil bath to be heated to 80 ℃ of temperature of reaction this mixed solution, then pass into oxygen with 10mL/min speed, react 8h under the normal pressure.After reaction finished, the gained mixed solution can obtain after filtration solid catalyst and contain the liquid mixture of CHP.Liquid mixture is analyzed, measured the transformation efficiency of isopropyl benzene and the selectivity of CHP and the results are shown in Table 5.More different carbon materials, carbon nanometer pipe catalytic cumene oxidation active best, the diamond catalytic activity is minimum.
The different carbon materials of table 5 are on the impact of isopropyl benzene peroxidation
| Embodiment | 14 | 15 |
| Catalyst type | Gac | Diamond |
[0054]?
| Isopropyl benzene transformation efficiency (%) | 21.8 | 9.3 |
| CHP selectivity (%) | 83.5 | 84.4 |
Stability embodiment
(1) with 10.0mL isopropyl benzene (density is 8.4g/mL) and the ultrasonic 2min(frequency 40kHz of 100mg carbon nanotube (catalyst levels and isopropyl benzene weight ratio are 0.012: 1), 30 ℃), form mixing suspension.Then under magnetic agitation, place oil bath to be heated to 80 ℃ of temperature of reaction this mixed solution, then pass into oxygen with 10mL/min speed, react 8h under the normal pressure.After reaction finished, the gained mixed solution can obtain after filtration solid catalyst and contain the liquid mixture of CHP.Liquid mixture is analyzed, measured the productive rate (mol%) of CHP; The gained solid catalyst is in 110 ℃ of lower dry 12h.
(2) with the dried carbon nanotube of step (1) as catalyzer, under the condition identical with step (1), react, measure productive rate with identical method.So this catalyst recirculation is used four times, measuredly be the results are shown in Table 6.Reuse four times, the productive rate of CHP changes little, illustrates that carbon nanotube can recycle, thereby can reduce the cost of catalyzer.
Table 6 catalyst stability experimental result
| Access times | 0 | 1 | 2 | 3 |
| CHP productive rate (mol, %) | 20.7 | 23.2 | 24.7 | 21.3 |
Claims (6)
1. an isopropyl benzene catalyzed oxidation is produced the method for isopropyl benzene hydroperoxide, it is characterized in that may further comprise the steps:
(1) reactant isopropyl benzene and solid catalyst are joined in the reactor mix, supersound process forms suspension again; Described solid catalyst is carbon material, and carbon material is one or more in carbon nanotube, diamond and the gac; Solid catalyst and isopropyl benzene weight ratio are 0.006～0.024: 1;
(2) suspension with gained is heated to 70～100 ℃, passes into oxygen, reacts 1～12h under the normal pressure; Oxygenant passes in the bubbling mode, and by every milliliter of isopropyl benzene, oxygen gas flow rate is 0.5～1.5mL/min;
(3) after the reaction of step (2) finishes, reaction mixture is separated the liquid mixture that obtains solid catalyst and contain isopropyl benzene hydroperoxide;
(4) with the liquid mixture separating-purifying in the step (3), obtain the product isopropyl benzene hydroperoxide.
2. the method for described isopropyl benzene catalyzed oxidation synthesizing iso-propylbenzene hydrogen peroxide according to claim 1, it is characterized in that: the described solid catalyst of step (3) is used for step (1), as the solid catalyst raw material.
3. the method for described isopropyl benzene catalyzed oxidation synthesizing iso-propylbenzene hydrogen peroxide according to claim 1, it is characterized in that: described solid catalyst and isopropyl benzene weight ratio are 0.006～0.012: 1.
4. the method for described isopropyl benzene catalyzed oxidation synthesizing iso-propylbenzene hydrogen peroxide according to claim 1, it is characterized in that: described temperature of reaction is 80～90 ℃.
5. the method for described isopropyl benzene catalyzed oxidation synthesizing iso-propylbenzene hydrogen peroxide according to claim 1, it is characterized in that: the described reaction times is 8～10h.
6. the method for described isopropyl benzene catalyzed oxidation synthesizing iso-propylbenzene hydrogen peroxide according to claim 1, it is characterized in that: described solid catalyst is carbon nanotube.
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| CN104402789A (en) * | 2014-11-21 | 2015-03-11 | 华南理工大学 | Method and reactor for catalyzing cumene oxidation by utilizing structured carbon nano-tube catalyst |
| CN104402843A (en) * | 2014-12-01 | 2015-03-11 | 中石化上海工程有限公司 | Method for reducing energy consumption of oxidation unit of epoxy propane device |
| CN105669383A (en) * | 2016-03-10 | 2016-06-15 | 张殿豪 | Method for removing acid in phenol-acetone device decomposition liquid |
| CN106268807A (en) * | 2015-09-25 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of cumene oxidation catalysts and its preparation method and application |
| CN110437117A (en) * | 2019-09-10 | 2019-11-12 | 万华化学集团股份有限公司 | A kind of method that cumene oxidation prepares cumene hydroperoxide |
| CN113600191A (en) * | 2021-08-30 | 2021-11-05 | 浙江工业大学 | Copper (II) doped chitosan carbon material and preparation method and application thereof |
| CN113651308A (en) * | 2021-08-31 | 2021-11-16 | 浙江工业大学 | Azalea leaf derived carbon material and preparation method and application thereof |
| CN114522680A (en) * | 2022-02-22 | 2022-05-24 | 广州大学 | MnO for cumene oxidation2Preparation method of/CNTs catalyst |
| CN115636738A (en) * | 2022-10-17 | 2023-01-24 | 华南理工大学 | Method for preparing diphenyl ketone from diphenylmethane |
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| CN104402789A (en) * | 2014-11-21 | 2015-03-11 | 华南理工大学 | Method and reactor for catalyzing cumene oxidation by utilizing structured carbon nano-tube catalyst |
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| CN110437117A (en) * | 2019-09-10 | 2019-11-12 | 万华化学集团股份有限公司 | A kind of method that cumene oxidation prepares cumene hydroperoxide |
| CN110437117B (en) * | 2019-09-10 | 2021-07-23 | 万华化学集团股份有限公司 | Method for preparing cumene hydroperoxide by oxidizing cumene |
| CN113600191A (en) * | 2021-08-30 | 2021-11-05 | 浙江工业大学 | Copper (II) doped chitosan carbon material and preparation method and application thereof |
| CN113651308A (en) * | 2021-08-31 | 2021-11-16 | 浙江工业大学 | Azalea leaf derived carbon material and preparation method and application thereof |
| CN114522680A (en) * | 2022-02-22 | 2022-05-24 | 广州大学 | MnO for cumene oxidation2Preparation method of/CNTs catalyst |
| CN114522680B (en) * | 2022-02-22 | 2023-10-27 | 广州大学 | MnO for cumene oxidation 2 Preparation method of CNTs catalyst |
| CN115636738A (en) * | 2022-10-17 | 2023-01-24 | 华南理工大学 | Method for preparing diphenyl ketone from diphenylmethane |
| CN115636738B (en) * | 2022-10-17 | 2024-01-09 | 华南理工大学 | Method for preparing diphenyl ketone from diphenyl methane |
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