CN104557468A - Method for phenol hydroxylation - Google Patents
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- CN104557468A CN104557468A CN201310522640.4A CN201310522640A CN104557468A CN 104557468 A CN104557468 A CN 104557468A CN 201310522640 A CN201310522640 A CN 201310522640A CN 104557468 A CN104557468 A CN 104557468A
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- 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
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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
Resorcinol and pyrocatechol are two kinds of important industrial chemicals and chemical intermediate, and tool has been widely used.Wherein, pyrocatechol can be used as rubber stiffening agent, electroplating additive, skin anticorrosion and bactericidal agent, hair dye, photographic developer, color picture antioxidant, fur dyeing developer, paint and the anti-peeling agent of varnish etc.; Resorcinol is mainly used as the stablizer of photographic developer, anthraquinone dye, azoic dyestuff, synthetic ammonia solubility promoter, rubber antioxidant, stopper, coating and essence and oxidation inhibitor etc.
Pass through aromatic hydroxy compound (as phenol) oxygen or oxygen-containing gas in prior art, copper containing catalyst, and optional promotor oxidation forms benzoquinones, then adopts reduction reaction to form Resorcinol.But the method cannot prepare benzoquinones and dihydroxy-benzene simultaneously.
Last century early eighties, Italian Taramasso is in USP4410501, and disclose the new catalytic oxidation material that one is called as HTS (TS-1), it has good selective oxidation to hydrocarbon, alcohol, phenol etc.
Use HTS to carry out catalyzed oxidation as catalyzer can obtain Resorcinol and pyrocatechol simultaneously.But this preparation method needs the hydrogen peroxide using purity higher, and the leeway that phenol conversion is still improved.
The technical process that isopropanol method prepares hydrogen peroxide is succeeded in developing by Shell company of the U.S. at first, it is that raw material uses air or oxygen to be oxidized under inducer existent condition with Virahol, Hydrogen Peroxide, and by-product acetone, then vaporizer is utilized to be separated, eventually pass organic solvent extraction purification and obtain 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 operational path better economic benefit, but also there is weak point, and such as product separation purification ratio is more difficult, and the acetone of its coproduction needs to find consumption market.
In titanium molecular sieve catalysis phenol hydroxylation reaction process, acetone can be adopted as solvent, and hydrogen peroxide is as oxygenant.But rarely seen utilize isopropanol oxidation legal system for obtain during hydrogen peroxide containing hydrogen peroxide and acetone mixture directly as phenol hydroxylation raw material to prepare the report of dihydroxy-benzene.
Summary of the invention
The object of the present invention is to provide the mixture containing hydrogen peroxide and acetone that a kind of employing is prepared by isopropanol oxidation method as oxygenant and solvent materials, adopt HTS as the method for hydroxylation of phenol of catalyzer.
The present inventor finds in long-term research practice, in titanium molecular sieve catalysis phenol hydroxylation reaction process, the mixed solution containing hydrogen peroxide and acetone that isopropanol oxidation method can be adopted to prepare is directly as oxygenant and solvent source, so not only can save the steps such as the separation and purification of hydrogen peroxide and acetone, and without the need to plus solvent.In special surprisingly process, the effective rate of utilization of hydrogen peroxide is higher and Resorcinol selectivity is higher.Based on this, complete the present invention.
For realizing aforementioned object, the invention provides a kind of method for hydroxylation of phenol, wherein, the method comprises: under oxidation reaction condition, by the mixture containing hydrogen peroxide and acetone of being prepared by isopropanol oxidation method that hydrogen peroxide obtains and phenol and the catalyst exposure containing HTS.
Method of the present invention is adopted to carry out phenol hydroxylation, phenol conversion is high, Resorcinol selectivity is good, supposition may be due to isopropanol oxidation method prepare containing in the mixture of hydrogen peroxide and acetone, due to containing part isopropyl alcohol, it may have certain prograding to reaction, and the ratio of hydrogen peroxide and acetone is suitable, thus can improve the selectivity of Resorcinol and the effective rate of utilization of hydrogen peroxide.
Method of the present invention, technological process is simple, and raw material is easy to get, environmental friendliness, and cost is low, and production process easily controls, and is beneficial to very much suitability for industrialized production and application.Further, the effective rate of utilization of method phenol conversion of the present invention and hydrogen peroxide is higher.In industrial application process, can directly by isopropanol oxidation legal system for the technique of hydrogen peroxide and the technique of phenol hydroxylation integrated, thus a large amount of transportation cost can be saved, reduce energy consumption, also can provide power for isopropanol oxidation legal system for the development again of the technique of hydrogen peroxide.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method for hydroxylation of phenol, wherein, the method comprises: under oxidation reaction condition, by the mixture containing hydrogen peroxide and acetone of being prepared by isopropanol oxidation method that hydrogen peroxide obtains and phenol and the catalyst exposure containing HTS.
According to method of the present invention, contain preferably in the mixture of hydrogen peroxide and acetone, the mol ratio of hydrogen peroxide and acetone is 0.8-1.2:1, is preferably 1:1.
According to method of the present invention, contain preferably in the mixture of hydrogen peroxide and acetone, the total content of hydrogen peroxide and acetone is 5-95 quality %, and be preferably 40-70 % by weight, be more preferably 50-60 % by weight, all the other are Virahol.
According to method of the present invention, in actual use, hydrogen peroxide and the acetone mixture of different concns can be obtained as required, also can add the concentration of the adjusted hydrogen oxide of acetone as required.
According to method of the present invention, preferably the described mixture containing hydrogen peroxide and acetone is prepared by Virahol dioxygen oxidation method, concrete example is as prepared as follows: by Virahol at the oxygen atmosphere (oxygen content of 80-95 volume %, surplus is mainly nitrogen) under, at 90-140 DEG C, 1.0-3.0MPa under carry out oxidizing reaction, in reaction process, in order to reduce the generation of by product particularly acetic acid, the per pass conversion of Virahol controls about 15%, can also introduce a small amount of hydrogen peroxide as promotor in oxidation reaction process.
According to method of the present invention, the range of choices of described oxidation reaction condition is wider, for the present invention, in order to the effective rate of utilization of the selectivity and hydrogen peroxide that improve Resorcinol further, preferred described oxidation reaction condition comprises: the mol ratio of phenol and hydrogen peroxide is 1:0.1-10, is preferably 1:0.2-5.
More preferably, the temperature of described oxidizing reaction is 10-160 DEG C, is preferably 30-120 DEG C, more preferably 30-90 DEG C.
The present invention is to the pressure contacted in oxidising process without particular requirement, and for the present invention, preferably, the pressure of described oxidizing reaction is 0.1-2MPa, is preferably 0.2-1.5MPa, more preferably 0.5-1.5MPa.
The present invention, specifically can adjust according to needs without particular requirement the time contacted in oxidising process, and for the present invention, preferably, the time of described oxidizing reaction is 0.1-10 hour, was preferably 0.5-5 hour, more preferably 1-3 hour.
According to method of the present invention, when the described catalyzer containing HTS is HTS, preferred described oxidation reaction condition also comprises: the weight ratio of phenol and described HTS is 1-100:1, is preferably 2-80:1, more preferably 5-80:1.
According to method of the present invention, when the described catalyzer containing HTS is shaping titanium-silicon molecular sieve catalyst, preferred described oxidation reaction condition also comprises: carry out in fixed-bed reactor, and total liquid hourly space velocity is 0.1-100h
-1, be preferably 1-10h
-1.
According to method of the present invention, in order to improve effective rate of utilization and the Resorcinol selectivity of phenol conversion and hydrogen peroxide further, preferred method of the present invention also comprises: by before the described mixture containing hydrogen peroxide and acetone and phenol and the catalyst exposure containing HTS, is mixed by the described mixture containing hydrogen peroxide and acetone contact with the inorganic acid aqueous solution containing halogen.
According to method of the present invention, the range of choices of the kind of the described inorganic acid aqueous solution containing halogen is wider, such as, can be hydrochloric acid, Hydrogen bromide, hydrofluoric acid, hydroiodic acid HI etc., is preferably hydrochloric acid and/or Hydrogen bromide.
According to method of the present invention, preferably the concentration of the described inorganic acid aqueous solution containing halogen is 30-40 % by weight.
According to method of the present invention, in order to the effective rate of utilization of the selectivity and hydrogen peroxide that improve Resorcinol further, be preferably 0.00001-0.1:1 containing the mineral acid of halogen and the mol ratio of hydrogen peroxide, be more preferably 0.0001-0.01:1.
According to method of the present invention, in order to the effective rate of utilization of the selectivity and hydrogen peroxide that improve Resorcinol further, the temperature of preferably mixing contact is 20-100 DEG C, is preferably 20-80 DEG C, is more preferably 20-40 DEG C.
According to method of the present invention, in order to the effective rate of utilization of the selectivity and hydrogen peroxide that improve Resorcinol further, preferably mixing contact pressure is 0-2.0MPa, is preferably 0-0.5MPa.
According to method of the present invention, in order to the effective rate of utilization of the selectivity and hydrogen peroxide that improve Resorcinol further, the time of preferably mixing contact is more than 0.1h, is more preferably 0.1-5h, is preferably 2-4h.
According to method of the present invention, the described catalyzer containing HTS can be HTS itself, also can be the preformed catalyst of HTS, or be the mixture of HTS and all the other catalytic materials, preferably the described catalyzer containing HTS is HTS itself.
HTS described in the present invention can be the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of the hexagonal mesoporous structure of two dimension is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structures.
Under preferable case, described HTS is one or more in the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, the more preferably HTS of MFI structure, more preferably described HTS is MFI structure, HTS crystal grain is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Have the HTS of aforementioned structure, those skilled in the art are commonly referred to hollow HTS HTS, disclose in detail in CN1301599A.
In the present invention, described HTS can be commercially available, and also can prepare, the method preparing described HTS has been conventionally known to one of skill in the art, as document (Zeolites, 1992, Vol.12 943-950 page) described in method, the present invention does not repeat them here.
Method provided by the invention, can adopt periodical operation, also can adopt operate continuously, the present invention to this without particular requirement.Feed way also can be any suitable way well known by persons skilled in the art, during as adopted andnon-continuous operation manner, catalyzer containing HTS can joined after in reactor, the mixture and the phenol that contain hydrogen peroxide and acetone described in adding continuously react.And when carrying out rhythmic reaction in closed tank reactor, the catalyzer containing HTS, mixture containing hydrogen peroxide and acetone and phenol can be added in still simultaneously carry out contact reacts.
In the present invention, the reactor that fixed-bed reactor, slurry bed reactor etc. are conventional can be adopted when continuous mode carries out, when carrying out in fixed-bed reactor, the mixture containing hydrogen peroxide and acetone and phenol can add continuously by feed way after loading catalyzer; And when carrying out in slurry bed reactor, catalyzer can be added and add mixture containing hydrogen peroxide and acetone continuously and phenol reacts afterwards; The present invention, does not repeat at this all without particular requirement one by one to this.
Method provided by the invention, eliminates isopropanol oxidation method carries out rectifying step to hydrogen peroxide and acetone, improves the economic benefit of process.Simultaneously without the need to plus solvent, acetone can react rear recovery, also can directly continue to use as solvent, and PROCESS COUPLING, efficiency improves.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.In embodiment, if no special instructions, used reagent is commercially available analytical reagent.(hydrogen peroxide and acetone mol ratio are about 1:1 for used hydrogen peroxide and acetone mixture, hydrogen peroxide and acetone total content are 58 % by weight, all the other are Virahol) directly take from isopropanol oxidation technological process (120 DEG C, under 15MPa, (oxygen concentration is 85 volume % for Virahol and oxygen atmosphere, all the other are nitrogen) be obtained by reacting, Virahol consumption 500g), without any process.
The method preparation described in document (Zeolites, 1992, Vol.12 943rd ~ 950 pages) pressed by HTS (TS-1) catalyzer used, and titaniferous amount is 2.5 % by weight.(Hunan Jianchang Petrochemical Co., Ltd produces the Industrial products of HTS described in hollow HTS HTS former powder system Chinese patent CN1301599A used, be MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180nm; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the condition of adsorption time 1h is 78mg/g), titaniferous amount is 2.5 % by weight.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant, the selectivity of product on this basis.
In an embodiment:
Embodiment 1
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 1:2 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 20:1, is 30 DEG C in temperature, and pressure is react under the condition of 1.5MPa.
The result of reaction 2h is as follows: phenol conversion is 37%, and effective utilization ratio of hydrogen peroxide is 81%, and pyrocatechol selectivity is 48%, and Resorcinol selectivity is 47%.
Embodiment 2
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 1:2 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 40:1, is 30 DEG C in temperature, and pressure is react under the condition of 1.5MPa.
The result of reaction 2h is as follows: phenol conversion is 45%, and effective utilization ratio of hydrogen peroxide is 84%, and pyrocatechol selectivity is 47%, and Resorcinol selectivity is 50%.
Embodiment 3
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 1:1.5 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 80:1, is 60 DEG C in temperature, and pressure is react under the condition of 1.0MPa.
The result of reaction 2h is as follows: phenol conversion is 87%, and effective utilization ratio of hydrogen peroxide is 80%, and pyrocatechol selectivity is 45%, and Resorcinol selectivity is 52%.
Embodiment 4
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 1:4 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 2:1, is 40 DEG C in temperature, and pressure is react under the condition of 0.5MPa.
The result of reaction 2h is as follows: phenol conversion is 79%, and effective utilization ratio of hydrogen peroxide is 83%, and pyrocatechol selectivity is 50%, and Resorcinol selectivity is 48%.
Embodiment 5
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 1:3 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 5:1, is 90 DEG C in temperature, and pressure is react under the condition of 1.0MPa.
The result of reaction 2h is as follows: phenol conversion is 98%, and effective utilization ratio of hydrogen peroxide is 79%, and pyrocatechol selectivity is 45%, and Resorcinol selectivity is 54%.
Embodiment 6
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 5:1 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 10:1, is 40 DEG C in temperature, and pressure is react under the condition of 0.5MPa.
The result of reaction 2h is as follows: phenol conversion is 14%, and effective utilization ratio of hydrogen peroxide is 89%, and pyrocatechol selectivity is 48%, and Resorcinol selectivity is 49%.
Embodiment 7
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 3:1 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 100:1, is 40 DEG C in temperature, and pressure is react under the condition of 0.5MPa.
The result of reaction 4h is as follows: phenol conversion is 21%, and effective utilization ratio of hydrogen peroxide is 77%, and pyrocatechol selectivity is 45%, and Resorcinol selectivity is 52%.
Embodiment 8
By the aforementioned mixed solution containing hydrogen peroxide and acetone, phenol and catalyzer (TS-1) are 2:1 according to the mol ratio of phenol and hydrogen peroxide, and the weight ratio of phenol and catalyzer is 60:1, is 30 DEG C in temperature, and pressure is react under the condition of 1.5MPa.
The result of reaction 2h is as follows: phenol conversion is 14%, and effective utilization ratio of hydrogen peroxide is 79%, and pyrocatechol selectivity is 46%, and Resorcinol selectivity is 48%.
Embodiment 9
Identical with the method for embodiment 1, unlike, TS-1 by etc. the HTS of weight replace.
The result of reaction 2h is as follows: phenol conversion is 45%, and effective utilization ratio of hydrogen peroxide is 87%, and pyrocatechol selectivity is 47%, and Resorcinol selectivity is 51%.
Embodiment 10
Identical with the method for embodiment 1, unlike, TS-1 by etc. the Ti-MCM-41(of weight for by prior art: Corma etc., Chem.Commun., the method preparation described in 1994,147-148, 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%, and pyrocatechol selectivity is 58%, and Resorcinol selectivity is 37%.
Embodiment 11
Identical with the method for embodiment 1, unlike, TS-1 by etc. the Ti-Beta(of weight for by prior art: Takashi Tatsumi etc., J.Chem.Soc., method preparation described in Chem.Commun.1997,677-678, 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%, and pyrocatechol selectivity is 48%, and Resorcinol selectivity is 45%.
Embodiment 12
Identical with the method for embodiment 1, unlike, by the described mixture containing hydrogen peroxide and acetone and phenol and contain HTS catalyst exposure before, the mixed in hydrochloric acid being 40 % by weight by the described mixture containing hydrogen peroxide and acetone and concentration contacts, the mol ratio of HCl and hydrogen peroxide is 0.005:1, the condition of mixing contact comprises: 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%, and pyrocatechol selectivity is 47%, and Resorcinol selectivity is 49%.
Embodiment 13
Identical with the method for embodiment 1, unlike, by the described mixture containing hydrogen peroxide and acetone and phenol and contain HTS catalyst exposure before, the Hydrogen bromide being 30 % by weight by the described mixture containing hydrogen peroxide and acetone and concentration mixes and contacts, the mol ratio of HBr and hydrogen peroxide is 0.001:1, the condition of mixing contact comprises: 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%, and pyrocatechol selectivity is 48%, and Resorcinol selectivity is 49%.
Comparative example 1
Identical with the method for embodiment 1, unlike, take hydrogen peroxide as hydrogen peroxide cource, using industrial acetone for as solvent, replace mixed solution containing hydrogen peroxide and acetone as oxygenant and solvent source, other reaction conditionss are all identical.
The result of reaction 2h is as follows: phenol conversion is 27%, and effective utilization ratio of hydrogen peroxide is 74%, and pyrocatechol selectivity is 42%, and Resorcinol selectivity is 37%.
As can be seen from above embodiment, method Resorcinol selectivity of the present invention is high, and effective utilization ratio of hydrogen peroxide is high.Particularly under proper condition, after the mixed solution containing hydrogen peroxide and acetone and the inorganic acid aqueous solution containing halogen isopropanol oxidation method prepared mix and contact, more obviously, namely Resorcinol selectivity is high, and effective utilization ratio of hydrogen peroxide is high for effect.
More than describe the preferred embodiment of the present invention in detail, but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to 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 characterized in that, the method comprises: under oxidation reaction condition, by the mixture containing hydrogen peroxide and acetone of being prepared by isopropanol oxidation method that hydrogen peroxide obtains and phenol and the catalyst exposure containing HTS.
2. method according to claim 1, wherein, described containing in the mixture of hydrogen peroxide and acetone, the mol ratio of hydrogen peroxide and acetone is 0.8-1.2:1.
3. method according to claim 1 and 2, wherein, described containing in the mixture of hydrogen peroxide and acetone, the total content of hydrogen peroxide and acetone is 40-70 quality %, and all the other are Virahol.
4. according to the method in claim 1-3 described in any one, wherein, the described mixture containing hydrogen peroxide and acetone is prepared by Virahol dioxygen oxidation method.
5. method according to claim 1, wherein, the method also comprises: by before the described mixture containing hydrogen peroxide and acetone and phenol and the catalyst exposure containing HTS, is mixed by the described mixture containing hydrogen peroxide and acetone contact with the inorganic acid aqueous solution containing halogen.
6. method according to claim 5, wherein, the mineral acid containing halogen and the mol ratio of hydrogen peroxide are 0.00001-0.1:1, and the condition of mixing contact comprises: temperature is 20-100 DEG C, and pressure is 0-2.0MPa, and the time is more than 0.1h.
7. method according to claim 6, wherein, the mineral acid containing halogen and the mol ratio of hydrogen peroxide are 0.0001-0.01:1, and the condition of mixing contact comprises: temperature is 20-80 DEG C, and pressure is 0-0.5MPa, and the time is 0.1-5h.
8. method according to claim 1, wherein, the described catalyzer containing HTS is HTS or shaping titanium-silicon molecular sieve catalyst.
9. the method according to claim 1,5 or 8, wherein, described HTS is at least one in the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of BEA structure, the HTS of MWW structure, the HTS of MOR structure, the HTS of TUN structure and two-dimentional hexagonal structure.
10. method according to claim 9, wherein, described HTS is the HTS of MFI structure, and described HTS crystal grain is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
11. methods according to claim 1, wherein, described oxidation reaction condition comprises: described catalyzer is HTS, the weight ratio of phenol and described HTS is 1-100:1, the mol ratio of phenol and hydrogen peroxide is 1:0.1-10, the temperature of contact is 10-160 DEG C, and pressure is 0.1-2MPa, and the time is 0.1-10 hour.
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| CN108658732A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | The method for preparing benzenediol |
| CN110759353A (en) * | 2018-07-27 | 2020-02-07 | 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 |
| WO2021047057A1 (en) * | 2019-09-14 | 2021-03-18 | 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658732A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | The method for preparing benzenediol |
| 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 |
| CN110759353A (en) * | 2018-07-27 | 2020-02-07 | 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 |
| WO2021047057A1 (en) * | 2019-09-14 | 2021-03-18 | 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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