CN102249863A - Method for preparing benzenediol by phenol hydroxylation - Google Patents
Method for preparing benzenediol by phenol hydroxylation Download PDFInfo
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- CN102249863A CN102249863A CN2011101381844A CN201110138184A CN102249863A CN 102249863 A CN102249863 A CN 102249863A CN 2011101381844 A CN2011101381844 A CN 2011101381844A CN 201110138184 A CN201110138184 A CN 201110138184A CN 102249863 A CN102249863 A CN 102249863A
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- phenol
- benzene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a method for preparing benzenediol by phenol hydroxylation. The method comprises the following steps of: A, sequentially adding catalyst, additive, phenol and solvent into a reactor; and B, adding aqueous solution of hydrogen peroxide into the reaction solution after the phenol is completely dissolved and the temperature of the reaction solution reaches 10 to 80 DEG C, and reacting for 1 to 6 hours to obtain a benzenediol product. By the method, the defects of over long reaction time, high energy consumption, heavy equipment load, low yield and the like in the conventional benzenediol production technology are overcome, and meanwhile, the production efficiency is improved. The benzenediol can be applied to the production process of catalyzing phenol hydroxylation by using a silicon-based porous composite catalyst.
Description
Technical field
The present invention relates to the method that a kind of phenol hydroxylation prepares dihydroxy-benzene, relate to specifically employing phenol hydroxylation reaction add when feeding intake a small amount of quinones (be selected from naphthoquinones, adjacent phenanthrenequione, to phenanthrenequione, adjacent benzoquinones, para benzoquinone, and in the alkyl substituent of these five kinds of quinoness one or more) as the method for additive, thereby quicken the conversion of phenol and the generation of dihydroxy-benzene, and improve the selectivity of dihydroxy-benzene.
Background technology
Dihydroxy-benzene (pyrocatechol and Resorcinol) is important chemical material and chemical intermediate, has wide application field.Pyrocatechol is mainly used in industries such as medicine, agricultural chemicals, spices, resin, coating, is the important source material of Chemicals such as berberine, suprarenin, furans pellet, Propoxur, vanillin food grade,1000.000000ine mesh, safrole, synthetic resins.Resorcinol also is used in anticoagulant, catalytic desulfurizing agent etc. except being used as the photographic developer in sensitization industry, and becomes the important source material of anthraquinone fuel, azoic dyestuff, has also developed new purposes simultaneously aspect liquid crystalline polymers.
Traditional dihydroxy-benzene production technique is eliminated as ortho chloro phenol hydrolysis method, disulfonic acid phenol alkali fusion method, aniline oxidation style, benzoquinones reduction method etc.These preparation methods step that responds is many, the technical process complexity, and shortcoming such as by product is many, and in reaction process, adopt strong acid, highly basic, Cl
2Etc. poisonous, objectionable impurities, equipment corrosion is serious, and quantity of three wastes is big, the energy consumption height.The direct hydroxylation of phenol-hydrogen peroxide prepares the method for dihydroxy-benzene, because technical process is simple, there are not advantages such as environmental pollution in the reaction conditions gentleness, has become the research focus of chemical field since the seventies in 20th century.
Be that the catalyzer representative is the suitability for industrialized production technology of the hydrogen peroxide phenol hydroxylation synthesizing benzene diphenol of French Rhone-Poulenc company, the exploitation of the emerging product of Japanese Ube Co., Ltd. with the inorganic acid.The Rhone-Poulenc method is with HClO
4Be catalyzer, H
3PO
4Be promotor, 70% hydrogen peroxide is an oxygenant, three placed in-line preparation methods of reactor.Since use the severe corrosive mineral acid, equipment material and requirement for anticorrosion height, and the requirement of high-strength hydrogen peroxide safe class is high, so this Technology difficulty is big, the shortcoming that exists some to be difficult to overcome.The Ube method is to be catalyzer with sulfuric acid, vitriol or tetra-sodium, and 60% hydrogen peroxide and ketogenesis ketone peroxide are as the technology of oxidant production dihydroxy-benzene.This technology is two step method, the flow process complexity, and ketone is volatile, and environmental pollution is serious, and the phenol internal circulating load is too big.Inorganic salt are that the representative of catalyzer is the Brichima method, with molysite and cobalt salt mixture is catalyzer, 60% hydrogen peroxide is an oxygenant, though reaction process is more superior than above two kinds of methods, but still need high-strength hydrogen peroxide, and have the shortcoming that homogeneous reaction itself is difficult to overcome, now replaced by the Enichem method.The eighties in 20th century, industrialized Enichem method was that TS-1 is applied to the actual Chemical Manufacture of dihydroxy-benzene, and its remarkable advantage is that catalyzer is easy to separate, dihydroxy-benzene selectivity height, pollutes few.It on the molecular sieve catalyst development history milestone.Defectives such as but HTS cost height, catalyst recovery require high, use the lower concentration hydrogen peroxide and make dehydration energy consumption height, and the slurry bed periodical operation is loaded down with trivial details await continuing to improve.
At present, the mankind are faced with global crises such as energy shortage, environmental pollution, ecological damage, impel Sustainable development to become the fundamental way and the basic strategy of solution mankind itself's crisis and development world economy.When continually developing new forms of energy, it is particularly important that save energy just seems.Though it is varied to be applied to the phenol hydroxylation catalyst for reaction, processing condition are also being continued to optimize, and still have problems such as temperature of reaction is higher, the reaction times is long, energy consumption is high, machine utilization is heavy, yield is not high in commercial process.Yet overcome the problems referred to above is not and to optimize technology two aspects and to set about research from improved catalysts, also should more be absorbed in reaction itself and further investigate, and pass through the suitability for industrialized production of other more simple method improvement phenol hydroxylations.
Summary of the invention
The objective of the invention is to prepare deficiencies such as the dihydroxy-benzene temperature of reaction is higher, the reaction times is long, energy consumption is high, machine utilization is heavy, the dihydroxy-benzene productive rate is low and provide a kind of phenol hydroxylation to prepare the method for dihydroxy-benzene in order to improve existing hydrogen peroxide oxidation phenol, thereby quicken the phenol hydroxylation reaction process, and improve the dihydroxy-benzene selectivity.
For addressing the above problem, the technical solution used in the present invention is as follows:
A kind of phenol hydroxylation prepares the method for dihydroxy-benzene, and its concrete steps are: A adds catalyzer, additive, phenol and solvent successively in reactor; B treats that phenol dissolves fully, and reacting liquid temperature arrives 10～80 ℃, adds aqueous hydrogen peroxide solution in reaction solution, and reaction 1～6h obtains the dihydroxy-benzene product.
In the alkyl substituent that preferred above-mentioned additive is quinones or quinones one or both; More preferably naphthoquinones, adjacent phenanthrenequione, to any one or two kinds in phenanthrenequione, adjacent benzoquinones, para benzoquinone, α-(1,4) naphthoquinones, β-(1,2) naphthoquinones or amphi-(2, the 6) naphthoquinones.
Preferable additives throwing amount is 0.1～5% of a catalyst quality; The consumption of preferred hydrogen peroxide is that the mol ratio of phenol and hydrogen peroxide is 1～10: 1.
Above-mentioned being reflected under the normal pressure gets final product, and preferred reaction pressure is 0.1～0.5MPa.
Innovation part of the present invention is to have added additive in reaction, quicken hydrogen peroxide and generated free radical, quicken the phenol hydroxylation reaction process, thereby add fast response, and improved the dihydroxy-benzene product selectivity, and catalyzer of the present invention all can for Pyrogentisinic Acid's hydroxylation has the catalyzer of catalytic performance; Preferred catalyst is silica-based composite porous; Ga more preferably
0.01Fe
0.06SiO
2.105, Co
0.01Fe
0.06SiO
2.10, B
0.01Gr
0.01Fe
0.06SiO
2.12, FSM-16, TS-1 or Fe-SBA-15; Catalyst consumption is 0.5～10% of a phenol quality.
The mixing solutions of the arbitrary proportion of organic solvent that above-mentioned solvent is water, dissolve each other with water or water and the organic solvent that dissolves each other with water; The described organic solvent that dissolves each other with water is ketone, alcohols or the amine that dissolves each other with water; The add-on of solvent gets final product for the solubilizing reaction thing.
The mass concentration of preferred above-mentioned aqueous hydrogen peroxide solution is 10～70%; Aqueous hydrogen peroxide solution can add successively or divide for several times and add, and also can drip continuously.
Beneficial effect:
The present invention has just added a spot of quinones in the phenol hydroxylation reaction when feeding intake, do not increase other loaded down with trivial details operation, the reaction conditions gentleness, and easily-controlled operation, but quickened the phenol hydroxylation reaction process, and make the dihydroxy-benzene selectivity raise.
The present invention will be further described below by embodiment, but usage range of the present invention is not limited in following explanation.
Embodiment
[Comparative Examples 1]
Catalyzer Ga
0.01Fe
0.06SiO
2.105(by patent 1 preparation, patent publication No.: CN101480613A), phenol 1g, catalyzer 0.05g, the hydrogen peroxide mass concentration is 30%, phenol/hydrogen peroxide (pure)=3: 1 (mol ratio), the 15mL solvent, wherein solvent is acetone=1: 4 (volume ratio), 20 ℃ of temperature of reaction, the reaction pressure normal pressure, reaction times and the results are shown in Table one.
[Comparative Examples 2]
Experimental procedure and method by contrast 1 are carried out the phenol hydroxylation reaction, and different is that the catalyzer that adds is Co
0.01Fe
0.06SiO
2.10(by patent 1 preparation, patent publication No.: CN101480613A), solvent is a deionized water, reaction times and the results are shown in Table one.
[Comparative Examples 3]
Carry out the phenol hydroxylation reaction by contrast 2 experimental procedure and method, different is that temperature of reaction is 10 ℃, and hydrogen peroxide concentration is 50%, reaction times and the results are shown in Table one.
[Comparative Examples 4]
Experimental procedure and method by contrast 1 are carried out the phenol hydroxylation reaction, and different is that the catalyzer that adds is B
0.01Gr
0.01Fe
0.06SiO
2.12(by patent 1 preparation, patent publication No.: CN101480613A), 15mL solvent, methanol=1: 1 (volume ratio) wherein, reaction times and the results are shown in Table one.
[Comparative Examples 5]
Catalyzer FSM-16 is (according to patent 2 preparations, patent publication No.: CN101204667) 0.2g, phenol 0.02mol, the 20mL deionized water is as solvent, slowly dropwise the 0.02mol hydrogen peroxide is splashed into reaction system by dropping funnel, the hydrogen peroxide mass concentration is 30%, 60 ℃ of temperature of reaction, reaction times and the results are shown in Table one.
[Comparative Examples 6]
The catalyzer of this example is the TS-1 molecular sieve.
Prepare the TS-1 molecular sieve according to the method described in the document (Zeolites, 1992, Vol.12:943～950.).Specific as follows: that the positive tetraethyl orthosilicate of 22.5g is mixed with the 7.0g TPAOH, add 59.8g distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1h, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add lentamente by 1.1g tetrabutyl titanate and the formed solution of 5.0g anhydrous isopropyl alcohol, the gained mixture is stirred 3h at 75 ℃, obtain the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature is placed 72h under 170 ℃ temperature, obtains the mixture of crystallization product, this mixture is filtered, washs, and, obtain the former powder of TS-1 in 110 ℃ of dry 60min, this former powder in 550 ℃ of roasting temperature 3h, is obtained the TS-1 molecular sieve.
Carry out the phenol hydroxylation reaction by the experimental procedure of Comparative Examples 1 and method, different is that the catalyzer that adds is the TS-1 molecular sieve, and catalyzer 0.08g, solvent are deionized water, and temperature of reaction is 40 ℃, reaction times and the results are shown in Table one.
[Comparative Examples 7]
The catalyzer of this example is the Fe-SBA-15 molecular sieve.
Prepare Fe-SBA-15 according to the method described in (J.Phys.Chem.B, 2006, Vol.110:26114～26121.).Concrete grammar is as follows: in the hydrochloric acid soln of 70ml, control pH value is 1.5, obtains solution A with 2g P123 surfactant dissolves.3.2mL TMOS and iron nitrate (Fe/Si=0.03) be dissolved in the 5ml deionized water, obtain solution B, the about 10min of solution B stirring at room obtains settled solution.Solution B is added drop-wise in the solution A, and 40 ℃ of following vigorous stirring 20h transfer to 100 ℃ of aging 24h in the water heating kettle then.The solid of gained after filtration, washing and in 60 ℃ of following dry 15h, at 500 ℃ of dry 10h down, promptly get Fe-SBA-15 at last.
Carry out the phenol hydroxylation reaction by the experimental procedure of Comparative Examples 1 and method, different is that the catalyzer that adds is Fe-SBA-15, and solvent is a deionized water, and temperature of reaction is 25 ℃, reaction times and the results are shown in Table one.
Embodiment 1, and phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 1, and difference is to select a-(1,4) naphthoquinones as additive, and the throwing amount is 0.5% of a catalyst quality, reaction times and the results are shown in Table one.
Embodiment 2, phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 2, difference be to select para benzoquinone and to the mixture of phenanthrenequione as additive, para benzoquinone/to phenanthrenequione=1: 1 (mol ratio), total throwing amount is 2% of a catalyst quality, reaction times and the results are shown in Table one.
Embodiment 3, and phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 3, and difference is to select adjacent benzoquinones as additive, and the throwing amount is 1% of a catalyst quality, reaction times and the results are shown in Table one.
Embodiment 4, phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 4, difference be to select adjacent phenanthrenequione and to the mixture of phenanthrenequione as additive, adjacent phenanthrenequione/to phenanthrenequione=1: 2 (mol ratio), total throwing amount is 0.5% of a catalyst quality, reaction times and the results are shown in Table one.
Embodiment 5, and phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 5, and difference is to select β-(1,2) naphthoquinones as additive, and the throwing amount is 04% of a catalyst quality, reaction times and the results are shown in Table one.
Embodiment 6, phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 6, and the mixture that difference is to select adjacent benzoquinones and adjacent phenanthrenequione is as additive, adjacent benzoquinones/adjacent phenanthrenequione=3: 1 (mol ratio), total throwing amount is 0.3% of a catalyst quality, reaction times and the results are shown in Table one.
Embodiment 7, phenol hydroxylation prepares dihydroxy-benzene reaction to be undertaken by example 7, and the mixture that difference is to select adjacent benzoquinones and para benzoquinone is as additive, adjacent benzoquinones/para benzoquinone=2: 1 (mol ratio), total throwing amount is 0.8% of a catalyst quality, reaction times and the results are shown in Table one.
The contrast of table one catalytic activity
Claims (7)
1. a phenol hydroxylation prepares the method for dihydroxy-benzene, and its concrete steps are: A adds catalyzer, additive, phenol and solvent successively in reactor; B treats that phenol dissolves fully, and reacting liquid temperature arrives 10～80 ℃, adds aqueous hydrogen peroxide solution in reaction solution, and reaction 1～6h obtains the dihydroxy-benzene product.
2. according to the method for preparing dihydroxy-benzene according to the described a kind of phenol hydroxylation of claim 1, it is characterized in that described additive be naphthoquinones, adjacent phenanthrenequione, to phenanthrenequione, adjacent benzoquinones, para benzoquinone, α-(1,4) naphthoquinones, β-(1,2) any one in naphthoquinones or amphi-(2, the 6) naphthoquinones or two kinds.
3. a kind of phenol hydroxylation according to claim 1 prepares the method for dihydroxy-benzene, it is characterized in that described additive throwing amount is 0.1～5% of a catalyst quality; Catalyst levels is 0.5～10% of a phenol quality; The consumption of described hydrogen peroxide is that the mol ratio of phenol and hydrogen peroxide is 1～10: 1.
4. a kind of phenol hydroxylation according to claim 1 prepares the method for dihydroxy-benzene, it is characterized in that described catalyzer is silica-based composite porous.
5. a kind of phenol hydroxylation according to claim 4 prepares the method for dihydroxy-benzene, it is characterized in that described catalyzer is Ga
0.01Fe
0.06SiO
2.105, Co
0.01Fe
0.06SiO
2.10, B
0.01Gr
0.01Fe
0.06SiO
2.12, FSM-16, TS-1 or Fe-SBA-15.
6. a kind of phenol hydroxylation according to claim 1 prepares the method for dihydroxy-benzene, it is characterized in that described solvent is a water, the organic solvent that dissolves each other with water or both mixing solutionss.
7. a kind of phenol hydroxylation according to claim 1 prepares the method for dihydroxy-benzene, and the mass concentration that it is characterized in that described aqueous hydrogen peroxide solution is 10～70%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627532A (en) * | 2012-03-19 | 2012-08-08 | 长春工业大学 | Use of copper alginate |
| CN106045820A (en) * | 2016-07-04 | 2016-10-26 | 中石化炼化工程（集团）股份有限公司 | Method for producing phenol and/or dihydroxybenzene by means of catalytic distillation |
| CN106861712A (en) * | 2017-01-09 | 2017-06-20 | 南京工业大学 | For the catalyst and its preparation and use of phenol hydroxylation preparing benzenediol |
| CN112774726A (en) * | 2020-12-29 | 2021-05-11 | 上海华谊新材料有限公司 | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125642A (en) * | 1994-12-28 | 1996-07-03 | 中国科学院长春应用化学研究所 | Phenol hydroxylated synthetic o-dihydroxybenzene (catechol) and P-benzenediol (hydroquinone) catalyzer |
| CN101239890A (en) * | 2008-01-17 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing pyrocatechol/hydrochinone by phenol hydroxylation |
| CN101480613A (en) * | 2009-01-20 | 2009-07-15 | 南京工业大学 | Catalyst for producing benzenediol by oxygenizing phenyl hydrate with hydrogen peroxide at room temperature and preparation method thereof |
-
2011
- 2011-05-26 CN CN201110138184.4A patent/CN102249863B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125642A (en) * | 1994-12-28 | 1996-07-03 | 中国科学院长春应用化学研究所 | Phenol hydroxylated synthetic o-dihydroxybenzene (catechol) and P-benzenediol (hydroquinone) catalyzer |
| CN101239890A (en) * | 2008-01-17 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing pyrocatechol/hydrochinone by phenol hydroxylation |
| CN101480613A (en) * | 2009-01-20 | 2009-07-15 | 南京工业大学 | Catalyst for producing benzenediol by oxygenizing phenyl hydrate with hydrogen peroxide at room temperature and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627532A (en) * | 2012-03-19 | 2012-08-08 | 长春工业大学 | Use of copper alginate |
| CN106045820A (en) * | 2016-07-04 | 2016-10-26 | 中石化炼化工程（集团）股份有限公司 | Method for producing phenol and/or dihydroxybenzene by means of catalytic distillation |
| CN106861712A (en) * | 2017-01-09 | 2017-06-20 | 南京工业大学 | For the catalyst and its preparation and use of phenol hydroxylation preparing benzenediol |
| CN106861712B (en) * | 2017-01-09 | 2019-08-30 | 南京工业大学 | Catalyst and its preparation and use for phenol hydroxylation preparing benzenediol |
| CN112774726A (en) * | 2020-12-29 | 2021-05-11 | 上海华谊新材料有限公司 | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof |
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