CN102219650A - Method for preparing benzenediol by hydroxylating phenol in water solution at room temperature - Google Patents
Method for preparing benzenediol by hydroxylating phenol in water solution at room temperature Download PDFInfo
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- CN102219650A CN102219650A CN2011101059386A CN201110105938A CN102219650A CN 102219650 A CN102219650 A CN 102219650A CN 2011101059386 A CN2011101059386 A CN 2011101059386A CN 201110105938 A CN201110105938 A CN 201110105938A CN 102219650 A CN102219650 A CN 102219650A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title abstract description 10
- 230000000640 hydroxylating effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 230000033444 hydroxylation Effects 0.000 claims abstract description 12
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000004028 organic sulfates Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 24
- 230000009257 reactivity Effects 0.000 description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- NZRBVZBQFDNAOD-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)O.C(CCCCCCCCCCC)[Na] Chemical compound C(C1=CC=CC=C1)(=O)O.C(CCCCCCCCCCC)[Na] NZRBVZBQFDNAOD-UHFFFAOYSA-N 0.000 description 1
- KXHFAYYFSKKIID-UHFFFAOYSA-N CCCCCCCCCCCCCCCC[K] Chemical compound CCCCCCCCCCCCCCCC[K] KXHFAYYFSKKIID-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- AWWLGINDIYKCJF-UHFFFAOYSA-N hydrogen peroxide phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.OO AWWLGINDIYKCJF-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing benzenediol by hydroxylating phenol in a room-temperature aqueous solution; because the water solubility of phenol at room temperature is poor (the mass concentration is less than 10 percent), the reaction for preparing benzenediol by phenol hydroxylation at room temperature by using water as a solvent cannot be carried out at high concentration. The method comprises the following specific steps: adding a certain amount of phenol (the phenol can not be completely dissolved) into water at room temperature, then respectively adding a certain amount of anionic surfactant until the phenol is completely dissolved, and then sequentially adding catalyst B0.01Cr0.01Fe0.06SiO2.12Then, dropwise adding an oxidant at room temperature while stirring, and reacting to obtain the benzenediol. The method solves the problem of environmental pollution caused by using organic solvent for phenol hydroxylation in industry, and also solves the problems of over-low solubility of phenol and over-low concentration and higher energy consumption in separation by using water as solvent at room temperature.
Description
Technical field
The present invention relates to a kind of method of dihydroxy-benzene, relate in particular to the method that phenol hydroxylation in a kind of room temperature water solution prepares dihydroxy-benzene.
Technical background
As important chemical material and intermediate, dihydroxy-benzene (pyrocatechol and Resorcinol) is widely used in numerous industries such as spices, dyestuff, photographic developer, inhibitor, medicine, agricultural chemicals and coating.
Traditional Resorcinol synthetic method has aniline oxidation style, p-Diisopropylbenzene oxidation style etc., and pyrocatechol then mainly obtains by hydrolysis such as ortho chloro phenol or hydroxyanisoles.In these methods, use strong acid, highly basic, water-soluble metal ion and metal composite etc. is catalyzer more, and equipment corrosion is serious, and quantity of three wastes is big, suitable serious of the pollution that causes.And these traditional preparation process methods step that responds is many, technical process complexity, shortcoming such as by product is many.
Since the seventies in 20th century, be the method for oxygenant phenol hydroxylation synthesizing benzene diphenol with the hydrogen peroxide, because technical process is simple, reaction conditions gentleness, H
2O
2The by product of making the hydroxylation reagent react is a water, and environmental pollution is less, also is a kind of hydroxylating agent that is easy to get, and working conditions is relatively gentleer, helps large-scale industrial production.Its gordian technique is a Study of Catalyst, therefore becomes the research focus of domestic and international investigator's extensive concern.
Up to now, not following hundred kinds of the kinds of catalyzer, gradually to compound, heterogeneous catalyst development, mainly contain inorganic acid, inorganic salt, complex metal oxides, HTS, hetero-atom molecular-sieve etc. from single, homogeneous inorganics and metallo-organic complex.
The representative that with the inorganic acid is catalyzer is the suitability for industrialized production technology of the hydrogen peroxide phenol hydroxylation synthesizing benzene diphenol of French Rhone-Poulenc company exploitation.This method is with HClO
4Be catalyzer, H
3PO
4Be promotor, the hydrogen peroxide of massfraction 70% is an oxygenant.Since use the deep-etching mineral acid, equipment material and requirement for anticorrosion height, the aftertreatment complexity, energy consumption is big, and environmental pollution is serious, 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.
Inorganic salt are that the representative of catalyzer is that the Brichima of Subsidiary Company of Italian Enichem company is a catalyzer with molysite and cobalt salt mixture, the hydrogen peroxide of massfraction 60% 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 Enichem method adopts 30%H
2O
2Be oxygenant, 60～90 ℃ of temperature of reaction, solvent is water or acetone, phenol: H
2O
2Be 3: 1 (mol ratio), phenol conversion is 25% behind the reaction 5h, and the selectivity of dihydroxy-benzene reaches 94%, pyrocatechol: Resorcinol is 1: 1.This technology is the model of present green chemical industry of generally acknowledging in the world, but the TS-1 catalyzer is synthetic complicated, costs an arm and a leg, the synthetic method difference, and its catalytic activity differs greatly; And this flow process has adopted organic solvent-acetone, and environment is polluted, and temperature of reaction is also higher, is further improved.
This seminar as catalyzer, is a solvent with water or organism with the iron-containing meso material, is 30%H with volume ratio under the room temperature
2O
2Be oxygenant (number of patent application is 200910029011.1) that phenol hydroxylation performance and TS-1 are close.
Adopt water as solvent, than more environmental protection of organic solvent, more cheap; And the reaction at room temperature carry out more safer than high temperature, energy consumption is littler.But because phenol solubleness in water lower (less than 10%) at room temperature, caused that the reaction system phenol concentration is low, sepn process energy consumption height, be unfavorable for large-scale industrialization production.
Summary of the invention
The objective of the invention is to propose the method that phenol hydroxylation in a kind of room temperature water solution prepares dihydroxy-benzene.
Technical scheme of the present invention is: adding a certain amount of anion surfactant, to improve under the room temperature phenol water-soluble, and making with water is that solvent room temperature phenol hydroxylation prepares the dihydroxy-benzene reaction and can carry out under high density.
Concrete technical scheme of the present invention is as follows: phenol hydroxylation prepares the method for dihydroxy-benzene in a kind of room temperature water solution; Its concrete steps are as follows: the calculated amount phenol that will reach 15%-60% under the room temperature by the phenol solution mass concentration of calculating adds (phenol can not dissolve fully) in the entry, add anion surfactant then respectively and all dissolve until phenol, wherein the phenol solution mass concentration reaches 15%-60%; Then add catalyst B successively
0.01Cr
0.01Fe
0.06SiO
2.12After, dropping oxidizing agent while stirring under the room temperature obtains dihydroxy-benzene after the reaction.
Preferred above-mentioned anion surfactant is an organic carboxylate, and structural formula is C
nH
mCOOM; Perhaps be organic sulfonate, structural formula is C
nHmSO
3M; Perhaps be organic sulfate, structural formula is C
nH
mOSO
3M; N=6～20 wherein, m=5～33, M is a basic metal.
The add-on of preferred anionic tensio-active agent is 10: 1～1: 2 for the mass ratio of control phenol and anion surfactant.
Preferred described room temperature is 5 ℃～35 ℃.The preferred above-mentioned dropping oxidizing agent afterreaction time is 0.5～5h.
The add-on of preferred described catalyzer is 1: 0.005～0.04 for the mass ratio of control phenol and catalyzer.
Preferred described oxygenant is that tertbutyl peroxide or massfraction are 10%～50% H
2O
2The mol ratio of oxygenant and phenol is 3: 1～1: 3.
Preferred described oxygenant rate of addition is 0.1～10mL/h.
The application number that catalyzer described in the present invention is preferably inventor application is the B in 200910029011.1 patents
0.01Cr
0.01Fe
0.06SiO
2.12
Beneficial effect:
The present invention has substantive distinguishing features and marked improvement, and it is possible that feasible phenol hydroxylation reaction industry at ambient temperature changes into.Concrete advantage is as follows:
(1) solvent has replaced organic solvent with water, can not pollute environment.
(2) improved that phenol is water-soluble under the room temperature can carry out reaction under high density.
(3) reduce catalyst levels, saved cost.
(4) mode of employing dropping oxidizing agent, safer than disposable adding, product selectivity is higher, and catalytic performance is better.
Embodiment
[example 1] takes by weighing 2.5g phenol and joins in the 10ml water, stirs to add Sodium Benzoate down and all dissolves until phenol, continues to add 0.075g catalyzer, massfraction and be 30% hydrogen peroxide 5.55mL, 5 ℃ of stirring in water bath 5 hours.The oxygenant rate of addition is 1.5mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 2] step is identical with example 1, and different is that temperature of reaction is 15 ℃, stirred 4 hours.The amount and the reactivity worth of its each component see Table 1.
[example 3] step is identical with example 1, and the amount that different is adds phenol is that 4.29g, 0.086g catalyzer, massfraction are that 30% hydrogen peroxide 2.38mL, temperature of reaction are 20 ℃, to stir 4 hours, oxygenant rate of addition be 0.6mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 4] takes by weighing 6.67g phenol and joins in the 10ml water, stirs to add the dodecyl Sodium Benzoate down and all dissolves until phenol, continues to add the 0.13g catalyzer, massfraction is 40% hydrogen peroxide 5.92mL, 25 ℃ of stirring in water bath 2 hours.The oxygenant rate of addition is 3mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 5] step is identical with example 4, and the amount that different is adds phenol is that 10g, 0.07g catalyzer, massfraction are that 20% hydrogen peroxide 5.55mL, temperature of reaction are that 30 ℃, churning time are that 1.5 hours, oxygenant rate of addition are 4mL/h.。The amount and the reactivity worth of its each component see Table 1.
[example 6] takes by weighing 4.29g phenol and joins in the 10ml water, stirring down, the adding sodium laurylsulfonate all dissolves until phenol, continue to add the 0.086g catalyzer, massfraction is 30% hydrogen peroxide 1.58mL, 30 ℃ of stirring in water bath 1 hour, the oxygenant rate of addition is 2mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 7] step is identical with example 6, and the amount that different is adds phenol is that 10g, 0.2g catalyzer, massfraction are 30% hydrogen peroxide 3.7mL, 30 ℃ of stirring in water bath 1 hour, and the oxygenant rate of addition is 4mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 8] takes by weighing 10g phenol and joins in the 10ml water, stirring down, the adding sodium cetanesulfonate all dissolves until phenol, continue to add the 0.2g catalyzer, massfraction is 30% hydrogen peroxide 3.7mL, 35 ℃ of stirring in water bath 0.5 hour, the oxygenant rate of addition is 8mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 9] step is identical with example 8, and temperature of reaction that different is is that 25 ℃, reaction times are that 1 hour, oxygenant rate of addition are 4mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 10] step is with example 8, and different is that the adding oxygenant is tertbutyl peroxide 3.24mL, and the oxygenant rate of addition is 4mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 11] step is with example 8, and different is that the solubilizing agent that adds is the hexadecyl potassium sulfonate, and temperature of reaction is that 25 ℃, reaction times are that 1 hour, oxygenant rate of addition are 4mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 12] step is with example 8, and different is that the solubilizing agent that adds is sodium lauryl sulphate, and temperature of reaction is that 25 ℃, reaction times are that 1 hour, oxygenant rate of addition are 4mL/h.The amount and the reactivity worth of its each component see Table 1.
[example 13] step is with example 8, and different is that the solubilizing agent that adds is Sodium palmityl sulfate, and temperature of reaction is that 25 ℃, reaction times are that 1 hour, oxygenant rate of addition are 4mL/h.The amount and the reactivity worth of its each component see Table 1.
Table 1
Can find by the example in the table 1:
(1) reactivity worth in contrast application number 200910029011.1 patents, the present invention has improved that phenol is water-soluble under the room temperature can carry out reaction under high density; Reduce catalyst levels, saved cost; Adopt the mode of dropping oxidizing agent, safer than disposable adding, product selectivity is higher, and catalytic performance is better.
(2) the traditional Enichem method of contrast, the present invention has reduced temperature of reaction, makes reaction more energy-conservation safer; Solvent has replaced organic solvent with water, can not pollute environment.
Claims (8)
1. phenol hydroxylation prepares the method for dihydroxy-benzene in the room temperature water solution; Its concrete steps are as follows: the calculated amount that will reach 15%-60% under the room temperature by the phenol solution mass concentration of calculating adds phenol in the entry, adds anion surfactant then respectively and all dissolves until phenol; Then add catalyst B successively
0.01Cr
0.01Fe
0.06SiO
2.12After, dropping oxidizing agent while stirring under the room temperature obtains dihydroxy-benzene after the reaction.
2. in accordance with the method for claim 1, it is characterized in that described anion surfactant is an organic carboxylate, structural formula is C
nH
mCOOM; Perhaps be organic sulfonate, structural formula is C
nHmSO
3M; Perhaps be organic sulfate, structural formula is C
nH
mOSO
3M; N=6～20 wherein, m=5～33, M is a basic metal.
3. in accordance with the method for claim 1, the add-on that it is characterized in that described anion surfactant is 10: 1～1: 2 for the mass ratio of control phenol and anion surfactant.
4. in accordance with the method for claim 1, it is characterized in that described room temperature is 5 ℃～35 ℃.
5. in accordance with the method for claim 1, the add-on that it is characterized in that described catalyzer is 1: 0.005～0.04 for the mass ratio of control phenol and catalyzer.
6. in accordance with the method for claim 1, it is characterized in that described oxygenant is that tertbutyl peroxide or massfraction are 10%～50% H
2O
2The mol ratio of oxygenant and phenol is 3: 1～1: 3.
7. in accordance with the method for claim 1, it is characterized in that described oxygenant rate of addition is 0.1～10mL/h.
8. in accordance with the method for claim 1, it is characterized in that the described reaction times is 0.5～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101059386A CN102219650A (en) | 2011-04-27 | 2011-04-27 | Method for preparing benzenediol by hydroxylating phenol in water solution at room temperature |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101059386A CN102219650A (en) | 2011-04-27 | 2011-04-27 | Method for preparing benzenediol by hydroxylating phenol in water solution at room temperature |
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|---|---|
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Cited By (3)
| 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 |
| CN106861712A (en) * | 2017-01-09 | 2017-06-20 | 南京工业大学 | Catalyst for preparing benzenediol by phenol hydroxylation and preparation and application thereof |
| CN111196751A (en) * | 2018-11-19 | 2020-05-26 | 中国科学院青岛生物能源与过程研究所 | Method for catalytically synthesizing dichlorophen by adopting surfactant catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533766A (en) * | 1983-03-11 | 1985-08-06 | Degussa Aktiengesellschaft | Process for the production of dihydroxybenzenes |
| CN101480613A (en) * | 2009-01-20 | 2009-07-15 | 南京工业大学 | Catalyst for preparing benzenediol by oxidizing phenol with hydrogen peroxide at room temperature and preparation method thereof |
-
2011
- 2011-04-27 CN CN2011101059386A patent/CN102219650A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4533766A (en) * | 1983-03-11 | 1985-08-06 | Degussa Aktiengesellschaft | Process for the production of dihydroxybenzenes |
| CN101480613A (en) * | 2009-01-20 | 2009-07-15 | 南京工业大学 | Catalyst for preparing benzenediol by oxidizing phenol with hydrogen peroxide at room temperature and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘惠平: "含铁催化剂在苯及苯酚H2O2羟基化催化反应中的研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 * |
| 高丹丹等: "表面活性剂对苯酚的增溶作用", 《大连民族学院学报》 * |
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 |
| CN106861712A (en) * | 2017-01-09 | 2017-06-20 | 南京工业大学 | Catalyst for preparing benzenediol by phenol hydroxylation and preparation and application thereof |
| CN106861712B (en) * | 2017-01-09 | 2019-08-30 | 南京工业大学 | Catalyst for preparing benzenediol by phenol hydroxylation and preparation and application thereof |
| CN111196751A (en) * | 2018-11-19 | 2020-05-26 | 中国科学院青岛生物能源与过程研究所 | Method for catalytically synthesizing dichlorophen by adopting surfactant catalyst |
| CN111196751B (en) * | 2018-11-19 | 2022-09-09 | 中国科学院青岛生物能源与过程研究所 | Method for catalytically synthesizing dichlorophen by adopting surfactant catalyst |
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