CN102249860A - Method for preparing dichlorobenzalcohol diisopropyl benzene by diisopropyl benzene catalytic oxidation - Google Patents
Method for preparing dichlorobenzalcohol diisopropyl benzene by diisopropyl benzene catalytic oxidation Download PDFInfo
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- CN102249860A CN102249860A CN2011101307371A CN201110130737A CN102249860A CN 102249860 A CN102249860 A CN 102249860A CN 2011101307371 A CN2011101307371 A CN 2011101307371A CN 201110130737 A CN201110130737 A CN 201110130737A CN 102249860 A CN102249860 A CN 102249860A
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- dipb
- diisopropylbenzene
- diisopropyl benzene
- dichlorobenzalcohol
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Abstract
The invention discloses a method for preparing dichlorobenzalcohol diisopropyl benzene by diisopropyl benzene catalytic oxidation, belonging to the technical field of dichlorobenzalcohol preparation. The method comprises the following steps: taking a CoO-MgO compound catalyst as the catalyst and air as an oxygen source; oxidizing diisopropyl benzene into diisopropyl benzene dichlorobenzalcohol, wherein the molar weight of the catalyst is 0.001-1 times that of the diisopropyl benzene, the catalytic oxidation temperature is 60-150DEG C, the air flow is 50-200L/(h.mol diisopropyl benzene), and the reaction time is 6-72 hours. In the method disclosed by the invention, a cobalt salt serves as a main catalyst, and MgO serves as a carrier to synthesize the compound catalyst. The oxidization rate of DIPB (diisopropyl benzene) is improved, and isopropyl in the DIPB is oxidized. The method disclosed by the invention can keep the conversion rate of DIPB and the selectivity of DCL (dichlorobenzalcohol diisopropyl benzene) at the higher level.
Description
Technical field
The invention belongs to the preparing technical field of two benzylalcohols, relate to the method that a kind of diisopropylbenzene(DIPB) catalyzed oxidation prepares two benzylalcohol diisopropylbenzene(DIPB)s.
Background technology
Two benzylalcohol diisopropylbenzene(DIPB)s (DCL) are the important organic intermediates of producing di-tert-butyl peroxide diisopropylbenzene(DIPB) etc.At present its main production technique is be raw material with diisopropylbenzene(DIPB) (DIPB), obtains diperoxy hydrogen diisopropylbenzene(DIPB) (DHP) by atmospheric oxidation, and DHP is reduced generation DCL.
The DIPB peroxidation prepares DHP as one of committed step in the DCL synthesis technique, and peroxidation has material impact for yield and the purity of final product DCL.Radical reaction mechanism is followed in this step reaction, decomposition induction time is long, and the side reaction of generation is numerous, and one of by product is exactly DCL.Thereby select a kind of DCL to be had higher optionally catalyzer, and just can realize that one step of DIPB catalyzed oxidation generates DCL, this shortens for the DCL Production Flow Chart, and process modification has great important.
The oxidation of DIPB belongs to free chain reaction, and its oxidation products mainly contains:
For alkylbenzene, especially the catalytic oxidation process of DIPB has had a large amount of research reports.The transformation efficiency of DIPB and the selectivity of target product are to weigh the important indicator of its oxidation effectiveness.What see at present mainly is to utilize alkaline matter to make catalyzer more, for example mineral alkali, alkalimetal oxide and alkaline earth metal oxide etc., and more research is on this basis.
With mineral alkali such as NaOH solution catalyzer as the DIPB oxidation, unavoidably have DCL and generate, existing report in patent EP0323743, EP0322246, US6350921 etc., but DCL occurs as by product, and yield is no more than 4%.
It is that catalyzer is used for the DIPB peroxidation that patent US4153635, US4935551, U4282384, US4282384, US2632774, JP49025653 have reported with alkaline-earth metal oxide or oxyhydroxide.With BaO
2Perhaps alkaline earth metal hydroxides Ca (OH)
2As the catalyzer of DIPB oxidation, but DCL equally as by product, yield is about 3%.
Patent JP95-3011055 has reported from HHP being the method that raw material generates DCL.The MIBK solution that will contain HHP in the presence of hydrogen, is catalyzer with palladium-aluminum oxide, and reaction conditions is 90 ℃ of pressure 6atm temperature, obtains DCL, but present method is under high pressure-temperature, and MIBK is volatile, so there is potential safety hazard.Patent US6350921 report is the continuous processing of raw material production DHP and DCLD with DIPB, DIPB generates DHP and HHP respectively after oxidation, utilize reciprocating plate column that the two is separated, decomposing H HP obtains DCL under alkaline condition, and the yield of last DCL is more than 90%.The actual still two-step reaction of these two kinds of methods generates DCL, does not play the effect of shortening reaction process.
People such as Osamu Fukuda have reported the effect of N-hydroxyphthalimide (NHPI) in the catalyzed oxidation isopropyl benzene at document (Adv.Synth.Catal.2001.343).With the acetonitrile is solvent, and NHPI is that catalyzer adds reaction system, reacts after 75 hours and handles oxidation liquid with excessive triphenyl phosphorus, and the yield that obtains dimethyl benzyl alcohol is 77%.People such as Francesco Minisci are at document (Organic Process Research﹠amp; Development 2004,8,163-168) reported the effect of NHPI and Co (OAc) 4H2O in oxidation 2,6 diisopropylnaphthalenes.With the two is that the yield of two benzylalcohols is 87% behind the catalyst reaction.
Correlation technique before the present invention report is analyzed as can be seen, and selection of catalysts influences very big for the result of peroxidation and the feasibility of industrial applications.For example, when mineral alkali, alkalimetal oxide or alkaline earth metal oxide etc. were used for the oxidation of DIPB, the oxidation depth of DIPB was not enough, and the selectivity of DCL is not high, occurs as just by product; NHPI and cobalt salt are used for the oxidation of DIPB, though the selectivity of DCL is higher, because the solubleness of NHPI in DIPB is very low, general needs use acetonitrile etc. are unfavorable for the popularization of industrial application as solvent.
Summary of the invention
The purpose of this invention is to provide the method that a kind of catalyzed oxidation DIPB prepares DCL, cobalt salt is loaded on the solid alkali catalyzer as oxidizing reaction, improve the rate of oxidation of DIPB, make sec.-propyl wherein all oxidized, and DCL has had higher selectivity in the product.
The invention provides the method that a kind of catalyzed oxidation diisopropylbenzene(DIPB) prepares diisopropylbenzene(DIPB) two benzylalcohols, this method has comprised following steps: cobalt salt is loaded to preparation CoO-MgO composite catalyst on the solid alkali, and be catalyzer, air is an oxygen source, and diisopropylbenzene(DIPB) is oxidized to diisopropylbenzene(DIPB) two benzylalcohols.The molar weight of catalyzer is 0.001-1 a times of diisopropylbenzene(DIPB) molar weight, is preferably 0.002-0.2 doubly.The temperature of catalyzed oxidation is 60-150 ℃, is preferably 90-130 ℃, and air flow quantity is 50-200L/ (a hmol diisopropylbenzene(DIPB)), is preferably 70-150L/ (hmol diisopropylbenzene(DIPB)), and the reaction times is 6-72 hour, is preferably 12-36 hour.
Preparation of catalysts adopts coprecipitation method, with Na
2CO
3Be precipitation agent.Accurately take by weighing cobalt salt and magnesium nitrate respectively and be dissolved in the deionized water, fully mix.Cobalt salt includes but not limited to cobalt naphthenate, Xiao Suangu, cobalt chloride, Cobaltous diacetate.The material of cobalt salt and magnesium nitrate the amount ratio, be 1: 100-1: 1.The Na of preparation 1mol/L concentration
2CO
3As precipitation agent.Under vigorous stirring, with Na
2CO
3The aqueous solution is added drop-wise to constant pressure funnel in the nitrate aqueous solution that had before prepared, and is 9.0 up to the pH of solution value, continue to stir 1min-30min after, at room temperature left standstill aging complete back suction filtration, and repeatedly remove Na 1-12 hour with deionized water wash
+Ion etc.Filter cake is dried under 80-120 ℃ of condition and is spent the night.Dried catalyzer can obtain the CoO-MgO composite catalyst after 500 ℃ of-600 ℃ of following roasting 6-12 hours.
The support of the catalyst that the present invention adopts is solid alkali MgO.MgO is representative alkaline earth metal oxide and solid alkali, is commonly used for the specific surface area that carrier improves catalyzer, also is used as catalyzer and is applied to many reactions.On the other hand, MgO can improve the speed of DIPB oxidation, its principal product is DHP, its catalytic mechanism is that chemisorption takes place at hydrogen atom and the alkali center, alkaline-earth metal catalyst surface that DIPB passes through on the sec.-propyl tertiary carbon, c h bond on the cumyl tertiary carbon has weakened, generate hydroperoxide thereby help sec.-propyl, the active centre of alkaline earth metal oxide may be the electronegative lattice oxygen of metal oxide surface.
Transistion metal compound, especially Co class catalyzer are not only active good, also have DCL selectivity preferably.Most metal ions has Decomposition to the DIPB hydrogen peroxide, and the mechanism of Co ionic catalysis decomposing D HP is as follows
Co
+++ROOH→RO·+Co
++++OH
-
Co
++++ROOH?→ROO·+Co
+++H
+
And the clean reaction after top two reaction formula additions is exactly:
Co
++++ROOH?→ROO·+Co
+++H
+
Co
++
+ROOH→RO·+Co
+++
+OH
-
2ROOH?→RO·+ROO·+H
2O
The Decomposition that this shows Co ion pair alkylbenzene hydrogen peroxide is clearly.So with the cobalt salt is Primary Catalysts, is carrier with MgO, then the reaction scheme of DIPB is DIPB → DHP → DCL.
In the commercial run of DIPB oxidation, often add some basic solutions (NaOH or Na in addition
2CO
3The aqueous solution etc.) acid that produces produces by product with the peroxide breakdown that prevents to generate in and in the oxidising process, as ketone, and single benzylalcohol etc.
The invention effect: it is Primary Catalysts that method of the present invention adopts with the cobalt salt, with MgO is carrier, synthetic composite catalyst, improved the rate of oxidation of DIPB, can make the transformation efficiency of DIPB and the selectivity of DCL all remain on a higher level sec.-propyl among the DIPB all oxidized (being embodied in the raising of transformation efficiency) method of the present invention; Implement catalysed oxidation processes of the present invention, reaction system does not need to use extra organic solvent, has realized that the DIPB oxidation step generates DCL, has simplified technological operation, has optimized the enforcement environment, has improved the comprehensive cost effectiveness of this skilled industry application.
Embodiment
Below describe implementation process of the present invention and effect in detail by specific embodiment, but protection domain is not subjected to the restriction of embodiment.
The reaction system of catalyzed oxidation is one and has two mouthfuls of glass reactors that stir condensation, adopts mechanical stirring that whole reaction system is uniformly dispersed, and air enters reactive system by gas distributor.
Reaction DIPB transformation efficiency and product D CL yield are analyzed by high-efficient liquid phase chromatogram HPLC.
Embodiment 1
With Na
2CO
3Be precipitation agent, accurately take by weighing Xiao Suangu 0.5g respectively, magnesium nitrate 4.4g is dissolved in the 100ml deionized water, fully mix.The Na of preparation 1mol/L concentration
2CO
3As precipitation agent.Under vigorous stirring, with Na
2CO
3The aqueous solution is added drop-wise to constant pressure funnel in the nitrate aqueous solution that had before prepared, and is 9.0 up to the pH of solution value, continue to stir 5min after, at room temperature left standstill aging complete back suction filtration, and repeatedly remove Na+ ion etc. 3 hours with deionized water wash.Filter cake is dried under 100 ℃ of conditions and is spent the night.Dried catalyzer, is positioned in the moisture eliminator in order to using after 8 hours 530 ℃ of following roastings.
Get 40gDIPB and be put in the reactor, add the 0.4g catalyzer, add the Na of 3g2%
2CO
3The aqueous solution, 100 ℃ of temperature of reaction, bubbling air 160ml/min reacted after 45 hours, and the transformation efficiency of DIPB is 78%, and the selectivity of DCL is 65%.
Embodiment 2
Get 40gDIPB and be put in the reactor, add the 0.8g catalyzer of embodiment 1, add the Na of 3g2%
2CO
3The aqueous solution, 120 ℃ of temperature of reaction, bubbling air 200ml/min reacted after 36 hours, and the transformation efficiency of diisopropylbenzene(DIPB) is 75%, and the selectivity of DCL is 70%.
Embodiment 3
Get 40gDIPB and be put in the reactor, add the 0.4g catalyzer of embodiment 1, add the Na of 3g2%
2CO
3The aqueous solution, 140 ℃ of temperature of reaction, bubbling air 200ml/min reacted after 30 hours, and the transformation efficiency of diisopropylbenzene(DIPB) is 80%, and the selectivity of DCL is 75%.
Claims (5)
1. the preparation method of a CoO-MgO composite catalyst is characterized in that, may further comprise the steps: adopt coprecipitation method, with Na
2CO
3Be precipitation agent, take by weighing cobalt salt and magnesium nitrate respectively and be dissolved in the deionized water, fully mix, the material of cobalt salt and magnesium nitrate the amount ratio be 1: 100-1: 1; The Na of preparation 1mol/L concentration
2CO
3As precipitation agent, under vigorous stirring, with Na
2CO
3The aqueous solution is added drop-wise in the above-mentioned nitrate aqueous solution, is 9.0 up to the pH of solution value, continue to stir 1min-30min after, at room temperature left standstill aging complete back suction filtration, and remove Na 1-12 hour with deionized water wash
+Ion; Filter cake is dried under 80-120 ℃ of condition and is spent the night, and dried catalyzer can obtain the CoO-MgO composite catalyst after 500 ℃ of-600 ℃ of following roasting 6-12 hours.
2. according to the method for claim 1, it is characterized in that described cobalt salt comprises cobalt naphthenate, Xiao Suangu, cobalt chloride, Cobaltous diacetate.
3. a catalyst oxidation diisopropylbenzene(DIPB) that adopts claim 1 preparation prepares the method for diisopropylbenzene(DIPB) two benzylalcohols, it is characterized in that may further comprise the steps: air is an oxygen source, and diisopropylbenzene(DIPB) is oxidized to diisopropylbenzene(DIPB) two benzylalcohols; The molar weight of catalyzer is 0.001-1 a times of diisopropylbenzene(DIPB) molar weight, and the temperature of catalyzed oxidation is 60-150 ℃, and air flow quantity is 50-200L/ (a hmol diisopropylbenzene(DIPB)), and the reaction times is 6-72 hour.
4. according to the method for claim 3, it is characterized in that the molar weight of catalyzer is 0.002-0.2 a times of diisopropylbenzene(DIPB) molar weight, the temperature of catalyzed oxidation is 90-130 ℃, and air flow quantity is 70-150L/ (a hmol diisopropylbenzene(DIPB)), and the reaction times is 12-36 hour.
5. according to the method for claim 3, it is characterized in that, also add NaOH or Na
2CO
3The acid that produces produces by product with the peroxide breakdown that prevents to generate in the aqueous solution and in the oxidising process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101307371A CN102249860A (en) | 2011-05-19 | 2011-05-19 | Method for preparing dichlorobenzalcohol diisopropyl benzene by diisopropyl benzene catalytic oxidation |
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|---|---|---|---|
| CN2011101307371A CN102249860A (en) | 2011-05-19 | 2011-05-19 | Method for preparing dichlorobenzalcohol diisopropyl benzene by diisopropyl benzene catalytic oxidation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492857A (en) * | 2016-10-19 | 2017-03-15 | 常州大学 | A kind of preparation method of cobalt oxide compound phosphoric acid yttrium catalyst |
| CN107297202A (en) * | 2017-06-14 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of preparation method and application of nano-MgO catalyst |
| CN114073983A (en) * | 2020-08-17 | 2022-02-22 | 万华化学集团股份有限公司 | Diisopropylbenzene oxidation catalyst, preparation method thereof and method for preparing diisopropylbenzene dibenzyl alcohol by using diisopropylbenzene oxidation catalyst |
| CN114685243A (en) * | 2022-04-01 | 2022-07-01 | 大连理工大学 | Green and efficient preparation method of 2-phenyl-2-propanol series compounds |
Citations (2)
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|---|---|---|---|---|
| EP0267759A2 (en) * | 1986-11-07 | 1988-05-18 | Kureha Kagaku Kogyo Kabushiki Kaisha | Oxidation process of aromatic compounds |
| CN101121686A (en) * | 2007-06-29 | 2008-02-13 | 上海华谊丙烯酸有限公司 | Air overoxidation method used for alkyl substitution arene |
-
2011
- 2011-05-19 CN CN2011101307371A patent/CN102249860A/en active Pending
Patent Citations (2)
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|---|---|---|---|---|
| EP0267759A2 (en) * | 1986-11-07 | 1988-05-18 | Kureha Kagaku Kogyo Kabushiki Kaisha | Oxidation process of aromatic compounds |
| CN101121686A (en) * | 2007-06-29 | 2008-02-13 | 上海华谊丙烯酸有限公司 | Air overoxidation method used for alkyl substitution arene |
Non-Patent Citations (3)
| Title |
|---|
| SHIGERU TSUTSUMI等: "Hydroxylation of Alkylbenzenes", 《JOURNAL OF THE FUEL SOCIETY OF JAPAN》 * |
| SHUAI XU等: "Catalytic activity of Cu/MgO in liquid phase oxidation of cumene", 《KOREAN J. CHEM. ENG.》 * |
| 李兰冬等: "Co/MgO 催化剂上N2O 催化分解的研究", 《第十一届全国青年催化会议论文集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492857A (en) * | 2016-10-19 | 2017-03-15 | 常州大学 | A kind of preparation method of cobalt oxide compound phosphoric acid yttrium catalyst |
| CN107297202A (en) * | 2017-06-14 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of preparation method and application of nano-MgO catalyst |
| CN114073983A (en) * | 2020-08-17 | 2022-02-22 | 万华化学集团股份有限公司 | Diisopropylbenzene oxidation catalyst, preparation method thereof and method for preparing diisopropylbenzene dibenzyl alcohol by using diisopropylbenzene oxidation catalyst |
| CN114073983B (en) * | 2020-08-17 | 2023-05-30 | 万华化学集团股份有限公司 | Diisopropylbenzene oxidation catalyst and preparation method thereof, and method for preparing diisopropylbenzene dibenzyl alcohol by using diisopropylbenzene oxidation catalyst |
| CN114685243A (en) * | 2022-04-01 | 2022-07-01 | 大连理工大学 | Green and efficient preparation method of 2-phenyl-2-propanol series compounds |
| CN114685243B (en) * | 2022-04-01 | 2023-02-07 | 大连理工大学 | Green and efficient preparation method of 2-phenyl-2-propanol series compounds |
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Application publication date: 20111123 |