CN104557468B - Method for phenol hydroxylation - Google Patents
Method for phenol hydroxylation Download PDFInfo
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- CN104557468B CN104557468B CN201310522640.4A CN201310522640A CN104557468B CN 104557468 B CN104557468 B CN 104557468B CN 201310522640 A CN201310522640 A CN 201310522640A CN 104557468 B CN104557468 B CN 104557468B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
Abstract
The invention provides a method for phenol hydroxylation. The method comprises the step that a mixture of hydrogen peroxide and acetone, which is obtained in the process of preparing hydrogen peroxide by an isopropanol oxidation method, is contacted with phenol and a catalyst containing a Ti-Si molecular sieve under an oxidation reaction condition. The method for phenol hydroxylation has a high phenol conversion rate and good selectivity for benzenediol. Presumably, the mixture of hydrogen peroxide and acetone, which is prepared by the isopropanol oxidation method, contains some isopropanol which is likely to play a role in promoting reaction, and the ratio of hydrogen peroxide to acetone is proper, so that the selectivity for benzenediol and the effective utilization ratio of hydrogen peroxide can be improved.
Description
Technical field
The present invention relates to a kind of method for hydroxylation of phenol.
Background technology
Hydroquinone and catechol are two kinds of important industrial chemicals and chemical intermediate, have widely
Purposes.Wherein, catechol can be used as rubber sclerosing agent, electroplating additive, skin anticorrosion and bactericidal agent,
Hair dye, photographic developer, color picture antioxidant, fur dyeing developer, paint and the anti-peeling of varnish
Agent etc.；Hydroquinone is mainly used as developing agent, anthraquinone dye, azo dye, synthesis ammonia cosolvent, rubber
The stabilizer of glue age resistor, polymerization inhibitor, coating and essence and antioxidant etc..
By by aromatic hydroxy compound (such as phenol) oxygen or oxygen-containing gas in prior art, cupric is catalyzed
Agent, and optional accelerator oxidation formation benzoquinone, then use reduction reaction to form hydroquinone.But
It is that the method cannot prepare benzoquinone and Benzodiazepines simultaneously.
Last century early eighties, Italy Taramasso in USP4410501, disclose one
Being referred to as the new catalytic oxidation material of HTS (TS-1), hydrocarbon, alcohol, phenol etc. are had very by it
Good selective oxidation.
Use HTS to carry out being catalyzed oxidation as catalyst and can obtain hydroquinone and neighbour simultaneously
Benzodiazepines.But, this preparation method needs the hydrogen peroxide using purity higher, and phenol conversion is still
The leeway being improved.
It is initially to be succeeded in developing by Shell company of the U.S. that isopropanol method prepares the technological process of hydrogen peroxide
, it is to use air or oxygen to aoxidize under conditions of inducing agent exists with isopropanol for raw material,
Generate hydrogen peroxide, and by-product acetone, then utilize vaporizer to separate, eventually pass organic solvent
Extracting and purifying obtains hydrogen peroxide finished product, by-product acetone.Isopropanol oxidation method both can be carried out in the liquid phase,
Also can carry out in the gas phase.This process route better economic benefit, but there is also weak point, example
As more difficult in product separation purification ratio, and the acetone of its coproduction need find consumption market.
In titanium molecular sieve catalysis phenol hydroxylation course of reaction, acetone can be used as solvent, mistake
Hydrogen oxide is as oxidant.But rarely seen utilize that isopropanol oxidation method obtains when preparing hydrogen peroxide containing peroxide
Change hydrogen and acetone mixture prepares the report of Benzodiazepines directly as phenol hydroxylation raw material.
Summary of the invention
It is an object of the invention to provide a kind of employing by containing that isopropanol oxidation method prepares
The mixture of hydrogen oxide and acetone, as oxidant and solvent materials, uses HTS as catalyst
Method for hydroxylation of phenol.
The present inventor finds in long-term research practice, at titanium molecular sieve catalysis phenolic hydroxy
Change in course of reaction, can use that isopropanol oxidation method prepares containing hydrogen peroxide and acetone
Mixed liquor, directly as oxidant and solvent source, is so possible not only to save the separation of hydrogen peroxide and acetone
The step such as refined, and without plus solvent.Effective utilization of hydrogen peroxide during the most surprisingly
Rate is higher and hydroquinone selectivity is higher.Based on this, complete the present invention.
For realizing object defined above, the invention provides a kind of method for hydroxylation of phenol, wherein, the method
Including: under oxidation reaction condition, by containing of being prepared that hydrogen peroxide obtains by isopropanol oxidation method
Hydrogen oxide contacts with phenol and the catalyst containing HTS with the mixture of acetone.
The method using the present invention carries out phenol hydroxylation, and phenol conversion is high, and hydroquinone selectivity is good,
Speculate and be likely due in the mixture containing hydrogen peroxide and acetone prepared by isopropanol oxidation method, by
In containing part isopropyl alcohol, it may have certain progradation to reaction, and hydrogen peroxide and acetone
Ratio is suitable, such that it is able to improve selectivity and the effective rate of utilization of hydrogen peroxide of hydroquinone.
The method of the present invention, technical process is simple, and raw material is easy to get, environmental friendliness, and low cost produced
Journey is easily controlled, and is especially advantageous for industrialized production and application.Further, the method phenol conversion of the present invention
Higher with the effective rate of utilization of hydrogen peroxide.During commercial Application, can be directly by isopropanol oxidation
It is integrated with the technique of phenol hydroxylation that method prepares the technique of hydrogen peroxide, such that it is able to save substantial amounts of transport
Cost, reduces energy consumption, it is also possible to the development again of the technique preparing hydrogen peroxide for isopropanol oxidation method carries
For power.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method for hydroxylation of phenol, wherein, the method includes: in oxidation reaction
Under the conditions of, mixed containing hydrogen peroxide and acetone that will be prepared that hydrogen peroxide obtains by isopropanol oxidation method
Compound contacts with phenol and the catalyst containing HTS.
With the method for the invention it is preferred in the described mixture containing hydrogen peroxide and acetone, peroxidating
Hydrogen is 0.8-1.2:1, preferably 1:1 with the mol ratio of acetone.
With the method for the invention it is preferred in the described mixture containing hydrogen peroxide and acetone, peroxidating
The total content of hydrogen and acetone is 5-95 mass %, preferably 40-70 weight %, more preferably 50-60 weight
Amount %, remaining is isopropanol.
The method according to the invention, in actual use, can obtain variable concentrations as required
Hydrogen peroxide and acetone mixture, it is also possible to be added as needed on the concentration of acetone regulation hydrogen peroxide.
With the method for the invention it is preferred to the described mixture containing hydrogen peroxide and acetone passes through isopropanol
Dioxygen oxidation method prepares, and prepares the most as follows: by isopropanol at oxygen gas
Under atmosphere (oxygen content of 80-95 volume %, surplus is mainly nitrogen), at 90-140 DEG C, 1.0-3.0MPa
Under carry out oxidation reaction, in course of reaction, in order to reduce the generation of by-product particularly acetic acid, isopropyl
The conversion per pass of alcohol controls, about 15%, to may be incorporated into a small amount of hydrogen peroxide in oxidation reaction process
As accelerator.
The method according to the invention, optional wider range of described oxidation reaction condition, for the present invention,
The effective rate of utilization of selectivity and hydrogen peroxide in order to improve hydroquinone further, the most described oxidation
Reaction condition includes: phenol is 1:0.1-10, preferably 1:0.2-5 with the mol ratio of hydrogen peroxide.
It is further preferred that the temperature of described oxidation reaction is 10-160 DEG C, preferably 30-120 DEG C, the most excellent
Elect 30-90 DEG C as.
To in oxidizing process, the pressure of contact is without particular/special requirement, for the present invention, it is preferable that described for the present invention
The pressure of oxidation reaction is 0.1-2MPa, preferably 0.2-1.5MPa, more preferably 0.5-1.5MPa.
The time of contact in oxidizing process without particular/special requirement, specifically can be adjusted by the present invention according to needs
Whole, for the present invention, it is preferable that the time of described oxidation reaction is 0.1-10 hour, preferably 0.5-5
Hour, more preferably 1-3 hour.
The method according to the invention, when the described catalyst containing HTS is HTS,
The most described oxidation reaction condition also includes: phenol is 1-100:1 with the weight ratio of described HTS,
It is preferably 2-80:1, more preferably 5-80:1.
The method according to the invention, when the titanium silicon molecule that the described catalyst containing HTS is molding
During sieve catalyst, the most described oxidation reaction condition also includes: carry out in fixed bed reactors, total liquid
Time air speed be 0.1-100h-1, preferably 1-10h-1。
The method according to the invention, in order to improve effective utilization of phenol conversion and hydrogen peroxide further
The method of rate and hydroquinone selectivity, the preferably present invention also includes: by described containing hydrogen peroxide
Before contacting with phenol and the catalyst containing HTS with the mixture of acetone, contained described
Hydrogen oxide contacts with the inorganic acid aqueous solution mixing containing halogen with the mixture of acetone.
The method according to the invention, the optional scope of the kind of the described inorganic acid aqueous solution containing halogen is relatively
Width, such as, can be hydrochloric acid, hydrobromic acid, Fluohydric acid., hydroiodic acid etc., preferably hydrochloric acid and/or hydrobromic acid.
With the method for the invention it is preferred to the concentration of the described inorganic acid aqueous solution containing halogen is 30-40
Weight %.
The method according to the invention, in order to improve the selectivity of hydroquinone and having of hydrogen peroxide further
Effect utilization rate, the mol ratio of the mineral acid and hydrogen peroxide that preferably comprise halogen is 0.00001-0.1:1, more
It is preferably 0.0001-0.01:1.
The method according to the invention, in order to improve the selectivity of hydroquinone and having of hydrogen peroxide further
Effect utilization rate, the temperature preferably mixing contact is 20-100 DEG C, preferably 20-80 DEG C, more preferably 20-40
℃。
The method according to the invention, in order to improve the selectivity of hydroquinone and having of hydrogen peroxide further
Effect utilization rate, preferably mixing contact pressure is 0-2.0MPa, preferably 0-0.5MPa.
The method according to the invention, in order to improve the selectivity of hydroquinone and having of hydrogen peroxide further
Effect utilization rate, the time preferably mixing contact is more than 0.1h, more preferably 0.1-5h, preferably 2-4h.
The method according to the invention, the described catalyst containing HTS can be HTS basis
Body, it is also possible to for the preformed catalyst of HTS, or be HTS and remaining catalysis material
Mixture, the preferably described catalyst containing HTS is HTS itself.
Heretofore described HTS can be MFI structure HTS (such as TS-1),
The HTS (such as TS-2) of MEL structure, the HTS (such as Ti-Beta) of BEA structure,
The HTS (such as Ti-MCM-22) of MWW structure, the titanium silicon molecule of two-dimentional hexagonal mesoporous structure
Sieve (such as Ti-MCM-41, Ti-SBA-15), the HTS (such as Ti-MOR) of MOR structure,
The HTS of the HTS (such as Ti-TUN) of TUN structure and other structures (as
Ti-ZSM-48) at least one in.
Under preferable case, described HTS is the HTS of MFI structure, MEL structure
One or more in the HTS of HTS and BEA structure, more preferably MFI
The HTS of structure, the most described HTS is MFI structure, and HTS crystal grain is
Hollow-core construction, the radical length of the chamber portion of this hollow-core construction is 5-300 nanometer, and described titanium silicon divides
Son sieve is at 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time records under conditions of being 1 hour is at least
70 milligrams per gram, deposit between adsorption isotherm and the desorption isotherm of the nitrogen absorption under low temperature of this HTS
At hysteresis loop.Having the HTS of aforementioned structure, those skilled in the art are commonly referred to hollow titanium silicon
Molecular sieve HTS, discloses in CN1301599A the most in detail.
In the present invention, described HTS is commercially available, it is also possible to prepare, and prepares institute
The method stating HTS is the most known to those skilled in the art, as document (Zeolites, 1992,
Vol.12 the 943-950 page) described in method, the present invention does not repeats them here.
The method that the present invention provides, can use intermittently operated, it would however also be possible to employ continuous operation, the present invention
To this without particular/special requirement.Feed way can also be any suitable way well known by persons skilled in the art,
During as used andnon-continuous operation manner, the catalyst containing HTS can joined in reactor
After, it is continuously added to the described mixture containing hydrogen peroxide and acetone and reacts with phenol.And closing
When formula tank reactor carries out intermittent reaction, can by the catalyst containing HTS, contained
Hydrogen oxide and the mixture of acetone and phenol are simultaneously introduced in still and carry out haptoreaction.
In the present invention, fixed bed reactors, slurry bed reactor etc. when continuation mode is carried out, can be used normal
Reactor, when carrying out in fixed bed reactors, feed way will be able to contain loading after catalyst
Hydrogen peroxide and the mixture of acetone and phenol is had to be continuously added to；And carry out in slurry bed reactor
Time, can be continuously added to after being added by catalyst enter containing hydrogen peroxide and the mixture of acetone and phenol
Row reaction；This all without particular/special requirement, is repeated the most one by one by the present invention at this.
The method that the present invention provides, eliminates isopropanol oxidation method and hydrogen peroxide and acetone is carried out rectification
Step, improve process economic benefit.Simultaneously without plus solvent, acetone can reclaim after reacting,
Can also continue directly to use as solvent, PROCESS COUPLING, efficiency improves.
The present invention will be further described by below example, but and be not so limited the interior of the present invention
Hold.In embodiment, if no special instructions, used reagent is commercially available analytical reagent.Used
To hydrogen peroxide and acetone mixture (hydrogen peroxide and acetone mol ratio are about 1:1, hydrogen peroxide and
Acetone total content is 58 weight %, and remaining is isopropanol) directly take from the technical process of isopropanol oxidation
(120 DEG C, under 15MPa, (oxygen concentration is 85 volume % to isopropanol, and remaining is with oxygen atmosphere
Nitrogen) reaction obtain, isopropanol consumption 500g), without any process.
HTS (TS-1) catalyst used press document (Zeolites, 1992, Vol.12 the
Page 943～950) described in method prepare, titaniferous amount is 2.5 weight %.Hollow titanium silicon used
Industrial products (the lake of HTS described in molecular sieve HTS former powder system Chinese patent CN1301599A
Nan Jian feldspathization limited company produces, and is MFI structure through X-ray diffraction analysis, this molecular sieve
Nitrogen absorption under low temperature adsorption isotherm and desorption isotherm between there is hysteresis loop, crystal grain is hollow crystal grain
And the radical length of chamber portion is 15-180nm；This sieve sample at 25 DEG C, P/P0=0.10, inhale
The benzene adsorbance recorded under conditions of attached time 1h is 78mg/g), titaniferous amount is 2.5 weight %.
In the present invention, use gas chromatogram to carry out the analysis of each composition in system, entered by correction normalization method
Row quantitatively, all can refer to prior art and carries out, and calculates the conversion ratio of reactant, product on this basis
The evaluation indexes such as selectivity.
In an embodiment:
Embodiment 1
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 1:2, and phenol is 20:1 with the weight ratio of catalyst, is 30 DEG C in temperature,
Pressure is to react under conditions of 1.5MPa.
The result of reaction 2h is as follows: phenol conversion is 37%, and effective utilization ratio of hydrogen peroxide is 81%,
Catechol selectivity is 48%, and hydroquinone selectivity is 47%.
Embodiment 2
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 1:2, and phenol is 40:1 with the weight ratio of catalyst, is 30 DEG C in temperature,
Pressure is to react under conditions of 1.5MPa.
The result of reaction 2h is as follows: phenol conversion is 45%, and effective utilization ratio of hydrogen peroxide is 84%,
Catechol selectivity is 47%, and hydroquinone selectivity is 50%.
Embodiment 3
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 1:1.5, and phenol is 80:1 with the weight ratio of catalyst, is 60 DEG C in temperature,
Pressure is to react under conditions of 1.0MPa.
The result of reaction 2h is as follows: phenol conversion is 87%, and effective utilization ratio of hydrogen peroxide is 80%,
Catechol selectivity is 45%, and hydroquinone selectivity is 52%.
Embodiment 4
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 1:4, and phenol is 2:1 with the weight ratio of catalyst, is 40 DEG C in temperature,
Pressure is to react under conditions of 0.5MPa.
The result of reaction 2h is as follows: phenol conversion is 79%, and effective utilization ratio of hydrogen peroxide is 83%,
Catechol selectivity is 50%, and hydroquinone selectivity is 48%.
Embodiment 5
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 1:3, and phenol is 5:1 with the weight ratio of catalyst, is 90 DEG C in temperature,
Pressure is to react under conditions of 1.0MPa.
The result of reaction 2h is as follows: phenol conversion is 98%, and effective utilization ratio of hydrogen peroxide is 79%,
Catechol selectivity is 45%, and hydroquinone selectivity is 54%.
Embodiment 6
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 5:1, and phenol is 10:1 with the weight ratio of catalyst, is 40 DEG C in temperature,
Pressure is to react under conditions of 0.5MPa.
The result of reaction 2h is as follows: phenol conversion is 14%, and effective utilization ratio of hydrogen peroxide is 89%,
Catechol selectivity is 48%, and hydroquinone selectivity is 49%.
Embodiment 7
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 3:1, and phenol is 100:1 with the weight ratio of catalyst, is 40 DEG C in temperature,
Pressure is to react under conditions of 0.5MPa.
The result of reaction 4h is as follows: phenol conversion is 21%, and effective utilization ratio of hydrogen peroxide is 77%,
Catechol selectivity is 45%, and hydroquinone selectivity is 52%.
Embodiment 8
By aforementioned containing hydrogen peroxide and the mixed liquor of acetone, phenol and catalyst (TS-1) according to phenol with
The mol ratio of hydrogen peroxide is 2:1, and phenol is 60:1 with the weight ratio of catalyst, is 30 DEG C in temperature,
Pressure is to react under conditions of 1.5MPa.
The result of reaction 2h is as follows: phenol conversion is 14%, and effective utilization ratio of hydrogen peroxide is 79%,
Catechol selectivity is 46%, and hydroquinone selectivity is 48%.
Embodiment 9
Identical with the method for embodiment 1, except for the difference that, TS-1 by etc. weight HTS replace.
The result of reaction 2h is as follows: phenol conversion is 45%, and effective utilization ratio of hydrogen peroxide is 87%,
Catechol selectivity is 47%, and hydroquinone selectivity is 51%.
Embodiment 10
Identical with the method for embodiment 1, except for the difference that, TS-1 by etc. the Ti-MCM-41(of weight be
Method system by prior art: Corma etc., Chem.Commun., 1994, described in 147-148
Standby, titanium oxide content is 3%) replace.
The result of reaction 2h is as follows: phenol conversion is 23%, and effective utilization ratio of hydrogen peroxide is 65%,
Catechol selectivity is 58%, and hydroquinone selectivity is 37%.
Embodiment 11
Identical with the method for embodiment 1, except for the difference that, TS-1 by etc. the Ti-Beta(of weight for by existing
There are technology: Takashi Tatsumi etc., in J.Chem.Soc., Chem.Commun.1997,677-678
Prepared by described method, titanium oxide content is 2.6%) replace.
The result of reaction 2h is as follows: phenol conversion is 29%, and effective utilization ratio of hydrogen peroxide is 75%,
Catechol selectivity is 48%, and hydroquinone selectivity is 45%.
Embodiment 12
Identical with the method for embodiment 1, except for the difference that, by described mixed containing hydrogen peroxide and acetone
Before compound contacts with phenol and the catalyst containing HTS, by described containing hydrogen peroxide and third
The mixture of ketone contacts with the mixed in hydrochloric acid that concentration is 40 weight %, and HCl with the mol ratio of hydrogen peroxide is
0.005:1, the condition of mixing contact includes: temperature is 40 DEG C, and pressure is normal pressure, and the time is 2h.
The result of reaction 2h is as follows: phenol conversion is 41%, and effective utilization ratio of hydrogen peroxide is 83%,
Catechol selectivity is 47%, and hydroquinone selectivity is 49%.
Embodiment 13
Identical with the method for embodiment 1, except for the difference that, by described mixed containing hydrogen peroxide and acetone
Before compound contacts with phenol and the catalyst containing HTS, by described containing hydrogen peroxide and third
The mixture of ketone contact with the mixing of hydrobromic acid that concentration is 30 weight %, HBr and hydrogen peroxide mole
Ratio is 0.001:1, and the condition of mixing contact includes: temperature is 20 DEG C, and pressure is normal pressure, and the time is 4h.
The result of reaction 2h is as follows: phenol conversion is 44%, and effective utilization ratio of hydrogen peroxide is 85%,
Catechol selectivity is 48%, and hydroquinone selectivity is 49%.
Comparative example 1
Identical with the method for embodiment 1, except for the difference that, with hydrogen peroxide as hydrogen peroxide source, with industry
Acetone is as solvent, replace the mixed liquor containing hydrogen peroxide and acetone as oxidant and solvent source, its
His reaction condition is the most identical.
The result of reaction 2h is as follows: phenol conversion is 27%, and effective utilization ratio of hydrogen peroxide is 74%,
Catechol selectivity is 42%, and hydroquinone selectivity is 37%.
By above embodiment it can be seen that the method hydroquinone selectivity of the present invention is high, and peroxide
Change hydrogen effective rate of utilization high.The most under proper condition, by prepared by isopropanol oxidation method containing
After hydrogen oxide contacts with the inorganic acid aqueous solution mixing containing halogen with the mixed liquor of acetone, effect is brighter
Aobvious, i.e. hydroquinone selectivity is high, and effective utilization ratio of hydrogen peroxide is high.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to the scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a method for hydroxylation of phenol, it is characterised in that the method includes: at oxidation reaction bar
Under part, by prepared that hydrogen peroxide obtains by isopropanol oxidation method containing hydrogen peroxide and the mixing of acetone
Thing and phenol and the catalyst containing HTS contacts, wherein, by described containing hydrogen peroxide with
Before the mixture of acetone contacts with phenol and the catalyst containing HTS, first contained described
Hydrogen oxide contacts with the inorganic acid aqueous solution mixing containing halogen with the mixture of acetone.
Method the most according to claim 1, wherein, described mixed containing hydrogen peroxide and acetone
In compound, hydrogen peroxide is 0.8-1.2:1 with the mol ratio of acetone.
Method the most according to claim 1 and 2, wherein, described containing hydrogen peroxide with acetone
Mixture in, the total content of hydrogen peroxide and acetone is 40-70 mass %, and remaining is isopropanol.
Method the most according to claim 1 and 2, wherein, described containing hydrogen peroxide with acetone
Mixture prepared by isopropanol dioxygen oxidation method.
Method the most according to claim 3, wherein, described mixed containing hydrogen peroxide and acetone
Compound is prepared by isopropanol dioxygen oxidation method.
Method the most according to claim 1, wherein, the mineral acid containing halogen and hydrogen peroxide
Mol ratio be 0.00001-0.1:1, mixing contact condition include: temperature is 20-100 DEG C, and pressure is
0-2.0MPa, the time is more than 0.1h.
Method the most according to claim 6, wherein, the mineral acid containing halogen and hydrogen peroxide
Mol ratio be 0.0001-0.01:1, mixing contact condition include: temperature is 20-80 DEG C, and pressure is
0-0.5MPa, the time is 0.1-5h.
Method the most according to claim 1, wherein, the described catalyst containing HTS
For HTS or the titanium-silicon molecular sieve catalyst of molding.
9. according to the method described in claim 1,5 or 7, wherein, described HTS is MFI
The HTS of structure, the HTS of MEL structure, the HTS of BEA structure, MWW
The HTS of structure, the HTS of MOR structure, the HTS of TUN structure and two
At least one in the HTS of dimension hexagonal structure.
Method the most according to claim 9, wherein, described HTS is MFI structure
HTS, described HTS crystal grain is hollow-core construction, the chamber portion of this hollow-core construction
Radical length is 5-300 nanometer, and described HTS is at 25 DEG C, P/P0=0.10, adsorption time is
The benzene adsorbance recorded under conditions of 1 hour is at least 70 milligrams per gram, the cryogenic nitrogen of this HTS
Hysteresis loop is there is between adsorption isotherm and the desorption isotherm of absorption.
11. methods according to claim 1, wherein, described oxidation reaction condition includes: described
Catalyst is HTS, and the weight ratio of phenol and described HTS is 1-100:1, phenol with
The mol ratio of hydrogen peroxide is 1:0.1-10, and the temperature of contact is 10-160 DEG C, and pressure is 0.1-2MPa,
Time is 0.1-10 hour.
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| CN108658732B (en) * | 2017-03-30 | 2021-11-16 | 中国石油化工股份有限公司 | Process for preparing benzenediol |
| CN107051579A (en) * | 2017-06-06 | 2017-08-18 | 江西师范大学 | A kind of method that use Ti MWW molecular screen membranes prepare benzenediol |
| CN110759353B (en) * | 2018-07-27 | 2023-04-07 | 中国石油化工股份有限公司 | Tin-titanium-silicon molecular sieve, preparation method and application thereof, and phenol oxidation method |
| CN112499597A (en) * | 2019-09-14 | 2021-03-16 | 南京延长反应技术研究院有限公司 | System and process for preparing hydrogen peroxide based on isopropanol method |
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| RU2356831C1 (en) * | 2008-01-14 | 2009-05-27 | Алексей Николаевич Савельев | Method of obtaining hydrogen peroxide through oxidation of isopropanol |
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