CN102381932B - Phenol oxidation method - Google Patents
Phenol oxidation method Download PDFInfo
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- CN102381932B CN102381932B CN 201010267479 CN201010267479A CN102381932B CN 102381932 B CN102381932 B CN 102381932B CN 201010267479 CN201010267479 CN 201010267479 CN 201010267479 A CN201010267479 A CN 201010267479A CN 102381932 B CN102381932 B CN 102381932B
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Abstract
The invention discloses a phenol oxidation method, which is characterized by adoption of ozone or gas mixture of ozone and dilution gases as an oxidant, and reaction with the molar ratio of phenol, ozone and solvent being 1: (0.1-10): (1-150) at the temperature of 0-180 DEG C and under the pressure of 0.1-3.0MPa. By adopting the method, the selectivity of benzoquinone is high, and the selectivity of hydroquinone is greatly improved particularly under conditions with a titanium catalyst.
Description
Technical field
The invention relates to a kind of method of oxidation of phenol, further say about a kind of and take the method for ozone as the oxygenant oxidation of phenol.
Background technology
Benzoquinones is often referred to para benzoquinone, is golden yellow prism, can distil and can, with steam distillation, be dissolved in hot water, ethanol and ether.Benzoquinones has the strong trend that reverts back to benzene ring structure, and oxygenizement can be captured iodine from the acidic solution of potassiumiodide, and itself is reduced into Resorcinol.Benzoquinones is the raw material of organic synthesis industry, is the important intermediate of dyestuff, medicine, agricultural chemicals etc., and its reduzate Resorcinol is reductive agent, can make the photographic developer of egative film and the stopper of polyreaction.
Para benzoquinone can be by sodium chlorate and the preparation of sulfuric acid oxidation Resorcinol; Industrial can being made by aniline or oxidation of phenol, but energy consumption is high, unstable product quality; The benzene direct electrolytic oxidation also can make benzoquinones, but current consumption is large, and efficiency is low.
Resorcinol and pyrocatechol are two kinds of important industrial chemicals and chemical intermediate, have purposes widely.Pyrocatechol can be used as the anti-peeling agent of rubber stiffening agent, electroplating additive, skin anticorrosion and bactericidal agent, hair dye, photographic developer, color picture antioxidant, fur dyeing developer, paint and varnish.Resorcinol is mainly used in stablizer, the oxidation inhibitor of photographic developer, anthraquinone dye, azoic dyestuff, synthetic ammonia solubility promoter, rubber antioxidant, stopper, coating and essence.
Summary of the invention
The purpose of this invention is to provide a kind of technique simple, oxidation of phenol method with low cost, that the benzoquinones selectivity is good.
The invention discloses a kind of method of oxidation of phenol, it is characterized in that take that ozone or ozone and diluent gas gas mixture are oxygenant, be under 0～180 ℃ and the pressure condition that is 0.1～3.0MPa in temperature, react under the ratio that is 1: 0.1～10.0: 1～150 according to the mol ratio of phenol, ozone and solvent.
Ozone has another name called three atomic oxygens, is commonly called as " good fortune oxygen, super oxygen, the oxygen of living ", and molecular formula is O
3.Ozone at normal temperatures and pressures, is nattier blue gas, with a kind of the stench taste of fish is arranged, and can be decomposed into voluntarily oxygen at normal temperatures, so ozone can not store, and general situ production, used immediately.In method provided by the invention, said oxidant, ozone can be that pure ozone can be also gas mixture, generally refers to the gas mixture of ozone and oxygen.Certainly, can adopt as required other gas dilution ozone, said diluent gas can be the rare gas elementes such as nitrogen, argon gas, helium, neon, can be also carbonic acid gas, air etc.
In method provided by the invention, the mol ratio of phenol, ozone and solvent is preferably 1: 0.2～and 5: 1～100, temperature of reaction is preferably 20～160 ℃, and reaction pressure is preferably 0.3～2.5MPa.
In method provided by the invention, said solvent is selected from alcohols or nitrile or carboxylic-acid or their mixing such as formic acid, acetic acid such as the ketone such as acetone, butanone or acetonitrile such as water or methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, is preferably acetone, water or their mixing.
Method provided by the invention can be reacted under the existence of catalyst-free, also can be selected from titanium-containing zeolite, amorphous silicon titanium or TiO
2titanium-containing catalyst exist under, in the ozone air speed, be 10～10000h
-1under condition, reacted, the ozone air speed is preferably 10～5000h
-1.The contriver is surprised to find that, when with titanium-containing zeolite, amorphous silicon titanium or TiO
2while existing, products distribution changes, and the selectivity of dihydroxy-benzene increases substantially.Said titanium-containing zeolite can be as TS-1, Ti-MCM-41 etc., and preferred TS-1 wherein, the molar ratio of titanium-containing catalyst and phenol is 1: 0.1～200, preferably 1: 1～100, wherein catalyzer is in titanium oxide.
Oxidation of phenol method provided by the invention, make oxygenant with ozone, and in unstripped gas, without adding any inhibitor or initiator, the benzoquinones selectivity is high, and the ozone effective rate of utilization is high.Under titanium-containing catalyst exists, the selectivity of dihydroxy-benzene is improved largely.The present invention, with respect to traditional method, has overcome the problems such as traditional processing technology complexity, equipment corrosion and noxious emission.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment, reagent used is commercially available analytical reagent.
The NLO-15 type oxygen source ozone producer that ozone used is produced by Fujian New Continent Environmental Protection Technology Co., Ltd provides, and ozone concn is adjustable, and maximum volume concentration can reach 80% (all the other are oxygen).
In an embodiment:
Embodiment 1
In temperature, being that 60 ℃ and pressure are under 0.5MPa, is oxygenant with ozone (15% volume ratio, all the other are oxygen), by phenol, ozone and solvent acetone according to being reacted under the mol ratio of 1: 1: 1.The result of reacting 2 hours is as follows: phenol conversion is 32%; The ozone effective rate of utilization is 36%; The benzoquinones selectivity is 95%, dihydroxy-benzene selectivity 4%.
Embodiment 2
In temperature, being that 20 ℃ and pressure are under 1.5MPa, is oxygenant with ozone (30% volume ratio, all the other are air), by phenol, ozone and solvent methanol according to being reacted under the mol ratio of 1: 1: 5.The result of reacting 2 hours is as follows: phenol conversion is 15%; The ozone effective rate of utilization is 47%; The benzoquinones selectivity is 90%, dihydroxy-benzene selectivity 8%.
Embodiment 3
In temperature, being that 80 ℃ and pressure are under 0.2MPa, is oxygenant with ozone (5% volume ratio, all the other are oxygen), by phenol, ozone and solvent acetonitrile according to being reacted under the mol ratio of 1: 2: 10.The result of reacting 2 hours is as follows: phenol conversion is 42%; The ozone effective rate of utilization is 31%; The benzoquinones selectivity is 92%, dihydroxy-benzene selectivity 6%.
Embodiment 4
In temperature, being that 40 ℃ and pressure are under 0.1MPa, is oxygenant with ozone (15% volume ratio, all the other are oxygen), by phenol, ozone and solvent Virahol according to being reacted under the mol ratio of 1: 4: 50.The result of reacting 2 hours is as follows: phenol conversion is 25%; The ozone effective rate of utilization is 36%; The benzoquinones selectivity is 86%, dihydroxy-benzene selectivity 12%.
Embodiment 5
Reaction process and the result of the present embodiment explanation under catalyzer exists.
Take TS-1 as catalyzer (by prior art (Zeolites, the method described in 1992, Vol.12 943-950 page) preparation, titanium oxide content is 2.4%), and the molar ratio of catalyzer and phenol is 1: 100, and the ozone volume space velocity is 20h
-1, other reaction conditions is with embodiment 4.The result of reacting 2 hours is as follows: phenol conversion is 26%; The ozone effective rate of utilization is 39%; The benzoquinones selectivity is 77%, dihydroxy-benzene selectivity 21%.
Embodiment 6
In temperature, being that 50 ℃ and pressure are under 1.0MPa, is oxygenant with ozone (10% volume ratio, all the other are air), by phenol, ozone and aqueous solvent according to being reacted under the mol ratio of 1: 0.2: 2.The result of reacting 2 hours is as follows: phenol conversion is 22%; The ozone effective rate of utilization is 38%; The benzoquinones selectivity is 87%, dihydroxy-benzene selectivity 12%.
Embodiment 7
Reaction process and the result of the present embodiment explanation under catalyzer exists.
With TiO
2for catalyzer (commercially available, Detitanium-ore-type), the molar ratio of catalyzer and phenol is 1: 2, and the ozone volume space velocity is 5000h
-1, other reaction conditions is with embodiment 6.The result of reacting 2 hours is as follows: phenol conversion is 24%; The ozone effective rate of utilization is 40%; The benzoquinones selectivity is 73%, dihydroxy-benzene selectivity 25%.
Embodiment 8
Being 120 ℃ in temperature is under 1.0MPa with pressure, with ozone (10% volume ratio, all the other carbon dioxide and oxygens that are the equal-volume ratio), is oxygenant, with TiO
2for catalyzer (0.5 gram), by phenol, ozone and solvent butanone according to being reacted under the mol ratio of 1: 0.5: 20.The result of reacting 2 hours is as follows: phenol conversion is 63%; The ozone effective rate of utilization is 24%; The benzoquinones selectivity is 81%, dihydroxy-benzene selectivity 17%.
Embodiment 9
In temperature, being that 100 ℃ and pressure are under 2.0MPa, is oxygenant with ozone (10% volume ratio, all the other are the volume ratio helium of 7: 10 and oxygen), by phenol, ozone and solvent acetic acid according to being reacted under the mol ratio of 1: 2: 60.The result of reacting 2 hours is as follows: phenol conversion is 48%; The ozone effective rate of utilization is 27%; The benzoquinones selectivity is 86%, dihydroxy-benzene selectivity 12%.
Claims (8)
1. the method for an oxidation of phenol generation benzoquinones, is characterized in that take that ozone or ozone and diluent gas gas mixture are oxygenant, is being selected from titanium-containing zeolite, amorphous silicon titanium or TiO
2catalyzer exist under, in temperature, be that 0～180 ℃ and pressure are 0.1～3.0MPa, the ozone air speed is 10～10000h
-1condition under, the ratio that is 1: 0.1～10: 1～150 according to the mol ratio of phenol, ozone and solvent is reacted.
2. according to the method for claim 1, it is characterized in that said diluent gas is selected from oxygen, nitrogen, argon gas, helium, neon, carbonic acid gas or air.
3. according to the method for claim 1, the mol ratio that it is characterized in that phenol, ozone and solvent is 1: 0.2～5: 1～100, and the ozone air speed is 10～5000h
-1.
4. according to the method for claim 1, it is characterized in that temperature of reaction is 20～160 ℃, reaction pressure is 0.3～2.5MPa.
5. according to the method for claim 1 or 3, it is characterized in that said solvent is selected from one or more the mixture in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile, formic acid, acetic acid.
6. according to the method for claim 1, said titanium-containing zeolite is selected from TS-1, and said ozone air speed is 10～5000h
-1.
7. according to the method for claim 1 or 6, wherein, the molar ratio of catalyzer and phenol is 1: 0.1～200, and wherein catalyzer is in titanium oxide.
8. according to the method for claim 7, the molar ratio of said catalyzer and phenol is 1: 1～100, and wherein catalyzer is in titanium oxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010267479 CN102381932B (en) | 2010-08-31 | 2010-08-31 | Phenol oxidation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010267479 CN102381932B (en) | 2010-08-31 | 2010-08-31 | Phenol oxidation method |
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| CN102381932A CN102381932A (en) | 2012-03-21 |
| CN102381932B true CN102381932B (en) | 2013-12-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279231A (en) * | 1999-06-30 | 2001-01-10 | 中国石油化工集团公司 | Process for refining coarse phenol containing sulfur |
| CN101445428A (en) * | 2009-01-05 | 2009-06-03 | 南京大学 | Simple and convenient method for preparing phenyl hydroxide by ozone oxidization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050171390A1 (en) * | 2003-12-17 | 2005-08-04 | Usfilter Corporation | Wet oxidation process and system |
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- 2010-08-31 CN CN 201010267479 patent/CN102381932B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279231A (en) * | 1999-06-30 | 2001-01-10 | 中国石油化工集团公司 | Process for refining coarse phenol containing sulfur |
| CN101445428A (en) * | 2009-01-05 | 2009-06-03 | 南京大学 | Simple and convenient method for preparing phenyl hydroxide by ozone oxidization |
Non-Patent Citations (6)
| Title |
|---|
| Eino Mvula等.Ozonolysis of phenols in aqueous solution.《Org.Biomol.Chem.》.2003,第1卷(第10期),第1749-1756页. |
| Ozonolysis of phenols in aqueous solution;Eino Mvula等;《Org.Biomol.Chem.》;20030414;第1卷(第10期);第1749-1756页 * |
| TiO2/AC催化臭氧氧化处理水中的苯酚;吴桂萍等;《环境科学与技术》;20070228;第30卷(第2期);第23-25页 * |
| 吴桂萍等.TiO2/AC催化臭氧氧化处理水中的苯酚.《环境科学与技术》.2007,第30卷(第2期),第23-25页. |
| 洪浩峰等.臭氧催化氧化处理苯酚废水研究.《环境科学与技术》.2010,第33卷(第6E期),第301-304页. |
| 臭氧催化氧化处理苯酚废水研究;洪浩峰等;《环境科学与技术》;20100630;第33卷(第6E期);第301-304页 * |
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