CN1268502A - Method for hydroxylation of phenol - Google Patents
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- 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
A hydroxylation method of phenol is disclosed and uses hydrogen peroxide as oxidizing agent and MFZ crystal structred titanium-silicon molecular sieve (TS-1) synthesized in microwave radiation field as catalyst, the reactants wt. ratio of titanium silicon molecular sieve: hydrogen peroxide : phenol : solvent=1 : (4-20) : (5-20) : (4-40), reaction takes place under 70-100 deg.C for 2-15 hrs. The said method possesses high benzenediol selectively, in particular, higher hydroquinone selectivity.
Description
The present invention is a kind of about method for hydroxylation of phenol, is the method for the phenol hydroxylation preparing benzenediol of catalyzer about a kind of HTS with the MFI structure (TS-1) specifically.
Traditional is the method for the phenol hydroxylation production dihydroxy-benzene of oxygenant with the hydrogen peroxide, and it is the Rhone-Poulenc method of catalyzer with sulfuric acid and phosphoric acid that employing is arranged, and the transformation efficiency of this method phenol is 5%; Or adopt with Fe
2+And Co
2+The Fenton reagent of preparation is the Brichima method of catalyzer, and the transformation efficiency of this method phenol is 10%.These two kinds of methods are all owing to the decomposition of hydrogen peroxide, and phenol conversion is low, and complex process, and environmental pollution is serious.
In recent years along with the continuous development of catalytic science and new catalytic material, with H
2O
2For developing just rapidly, the environmental friendliness green catalysis oxidation novel process of oxygenant attracts tremendous attention.
J.Chem.Soc.Chem.Commun., reported in 1019 (1996) a kind of with H
2O
2Be oxygenant, La
2CuO
4Phenol hydroxylation reaction method for catalyzer.This method is to be solvent with water, and the hydrogen peroxide consumption is big, and the molar feed ratio of it and phenol is 60: 1, and after 2 hours, the transformation efficiency of phenol is 51% 70 ℃ of reactions, and the ratio of Resorcinol and pyrocatechol is 0.7: 1 in the oxidation products.
Appl.Catal., the phenol hydroxylation reaction method of 93,123 (1993) reports is with H
2O
2Being oxygenant, is catalyzer with the V-Si molecular sieve (VS-2) with different V/ (V+Si) ratio, and water is solvent.Experimental result shows that at V/ (V+Si)=0.0127 o'clock, through 80 ℃ of reactions 8 hours, the transformation efficiency of phenol was 28%, H
2O
2Transformation efficiency be 63%, the ratio of Resorcinol, pyrocatechol and benzoquinones was respectively 44: 52: 4 in the oxidation products.
HTS is the hetero-atom molecular-sieve of early eighties exploitation, and the Application Areas of molecular sieve has greatly been opened up in its appearance, makes molecular sieve enter the catalyzed oxidation field from fractionation by adsorption and acid catalyzed reaction.Its particular structure makes it have very high thermostability, resistance to acid, good catalytic activity and selectivity.Particularly have the TS-1 of MFI crystalline structure and the catalytic oxidation system that hydrogen peroxide is formed, can be applicable to the oxidation of stable hydrocarbon, the reactions such as oxidation, alkene epoxidation, aromatic hydrocarbon hydroxylation, ammoxidation of cyclohexanone of alcohol, traditional relatively oxidizing process, the application of HTS, can make the reaction conditions gentleness, technology is simple and safe, and is environmentally friendly, and transformation efficiency is high and selectivity is good.
Stud.Surf.Sci.Catal., the TS-1 molecular sieve with MFI structure of having reported the exploitation of Enichem company in 37,413 (1988) is used for method for hydroxylation of phenol.The transformation efficiency of this method phenol is 25%, and the transformation efficiency of hydrogen peroxide is 70%, and the selectivity of oxidation products dihydroxy-benzene is 90%, and the ratio of Resorcinol and pyrocatechol is 1: 1.
Stud.Surf.Sci.Catal., the phenol hydroxylation reaction method of 55,53 (1990) middle reports is with H
2O
2Be oxygenant, the TS-1 molecular sieve is a catalyzer, and water is solvent, and 80 ℃ reaction is after 4 hours down, and the transformation efficiency of phenol is 15%, H
2O
2Transformation efficiency be 34%, the ratio of Resorcinol and pyrocatechol is 1: 1 in the oxidation products.
Appl.Catal., 58, (1990) L1-L4 and J.Mol.Catal., the phenol hydroxylation reaction of 71,373 (1992) middle reports is with H
2O
2Be oxygenant, the TS-2 molecular sieve with MEL structure is a catalyzer, and acetone is solvent, and reaction is after 24 hours down at 69 ℃, and the transformation efficiency of phenol is 27%, H
2O
2Transformation efficiency be 70%, the ratio of Resorcinol, pyrocatechol and benzoquinones is 50: 49: 1 in the oxidation products.
Because the economic worth of Resorcinol is higher, so the yield of Resorcinol is high more naturally good more in the product of oxidation generation.But in the oxidation products of above-mentioned phenol hydroxylation, the mole of Resorcinol and pyrocatechol is selected than generally only between 0.4～1, and mole selection ratio of not seeing Resorcinol and pyrocatechol is at the report more than 1.
USP4,778,666 have disclosed the method that in microwave radiation field hydrothermal crystallizing prepares aluminosilicate molecular sieves.The direct provocative reaction mixture of microwave in microwave radiation field molecule has increased internal energy of molecular, thereby has accelerated the molecular sieve crystallization rate, shortened crystallization time, be evenly distributed owing to heat energy simultaneously, thereby the gained molecular sieve crystallinity has been good, and grain-size is less, has better activity.
Purpose of the present invention is exactly that a kind of and phenol hydroxylation catalysis process that Resorcinol selectivity higher good than prior art dihydroxy-benzene selectivity is provided on the basis of above-mentioned prior art.
We found through experiments, and when the HTS for preparing in microwave radiation field is used as the phenol hydroxylation catalyst for reaction, can improve the selectivity of Resorcinol and pyrocatechol.
Method provided by the invention is to be oxygenant with the hydrogen peroxide, in microwave radiation field synthetic have the MFI structure HTS (TS-1) in the presence of, phenol is reacted in solvent.
Employed solvent can be water, alcohol, ketone or hydrogen peroxide in this method, wherein preferred acetone.The temperature of reaction that adopts is 70～90 ℃; Along with the increase in reaction times, the transformation efficiency of phenol increases to some extent, but owing to the increase with the reaction times, tar yield also can increase to some extent, so the reaction times was generally preferred 4～8 hours 2～15 hours; The weight batching ratio of reactant is a HTS: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: solvent=1: 4～20: 5～50: 4～40, preferred 1: 6～12: 18～24: 14～18.
The HTS with MFI structure (TS-1) that present method adopts prepares through following step: prepare the reaction mixture that can be used for synthesis of titanium silicon molecular sieve (TS-1); Above-mentioned reaction mixture is positioned over carries out crystallization in the microwave radiation field.Microwave frequency in the microwave radiation field is 600～50000MHz, preferred 900～30000MHz, more preferably 900～4500MHz; Reaction system pressure is 0.4～2MPa, preferred 0.5～1.5MPa; Crystallization time is 5 hours～3 days, preferred 5～40 hours.
The reaction mixture that is used for synthesis of titanium silicon molecular sieve (TS-1), can be by prior art, the preparation of method disclosed in USP4410501, CN1167082A or other pertinent literatures is about to a certain amount of silicon source, titanium source, organic bases and mixes, and forms the hydrolysate of silicon and titanium.The mole compositing range of its reaction mixture is:
The general range preferable range
SiO
2/TiO
2??????????????5～200?????????????????20～60
OH
-/SiO
2???????????????0.1～1.0???????????????0.15～0.6
H
2O/SiO
2???????????????20～200????????????????60～100
Me/SiO
2?????????????????0～0.5?????????????????0
RN
+/SiO
2???????????????0.1～2.0???????????????0.15～0.6
Said silicon source is selected from silica gel, silicon sol or tetraalkyl silicon ester, preferred tetraalkyl silicon ester, more preferably tetraethyl silicane acid esters.
Said titanium source is the compound of hydrolyzable titanium, as TiCl
4, TiOCl
2And tetraalkyl titanate, preferred tetraalkyl titanate, more preferably tetrabutyl titanate ester.
Me represents alkalimetal ion, refers to sodium or potassium herein.
RN
+The nitrogen organic cation that expression is obtained by organic bases, wherein said organic bases are selected from fat amine compound, alcamine compound, quaternary amine alkali compounds or two or more mixture among them, preferred quaternary amine alkali compounds.Said quaternary amine alkali compounds is the alkyl quaternary amine bases compound that contains 1～4 carbon atom, wherein preferred TPAOH.
The hydroxylacion method of phenol provided by the invention, because the HTS (TS-1) of having used synthetic in the microwave radiation field to have the MFI structure is catalyzer, thereby the selectivity of dihydroxy-benzene is absolutely approaching in the oxidation products, and the mole number of the Resorcinol that is possessed of higher values is about 1.2～1.9 times of pyrocatechol, and this ratio is apparently higher than prior art.
Below will the present invention is further illustrated with embodiment, but protection scope of the present invention is not subjected to the restriction of these embodiment.
Fig. 1 is the x-ray diffraction spectra according to the TS-1 molecular sieve of the method preparation of embodiment among the USP4410501 1.
Fig. 2～7 are the X-ray diffractogram of the TS-1 molecular sieve for preparing in microwave radiation field.
The preparation of the HTS of embodiment 1～6 explanation in microwave radiation field.
Embodiment 7～19 explanation present method are used for the effect of phenol hydroxylation reaction.
Comparative Examples 1
Method according to embodiment among the USP4410501 1 prepares the TS-1 molecular sieve with MFI structure, and its x-ray diffraction spectra is seen Fig. 1.
Embodiment 1
Toward the positive tetraethyl orthosilicate (chemical pure of 35ml, Tianjin chemical reagent factory) adds 1.5ml tetraethyl titanate (chemical pure in, Great Wall, Beijing chemical reagent factory), the powerful stirring down, slowly splash into 38ml TPAOH (TPAOH, 20% aqueous solution, the Tokyo system of changing into) solution dropwises, and continues to stir after one hour, slowly be warming up to about 80 ℃ and continue and stirred 5 hours, obtain transparent even colloidal solution, this colloidal solution is put into the autoclave with microwave radiation field, set microwave frequency 900MHz, reaction pressure 0.5MPa reacted 24 hours.Take out crystallization product, suction filtration, washing, drying obtain the TS-1 molecular sieve, and sample number into spectrum is W-1.W-1 was through 550 ℃ of roastings 6 hours, and its x-ray diffraction spectra is seen Fig. 2.
Embodiment 2
With 30ml TPAOH (TPAOH, 20% solution, Tokyo changes into) arrive 60ml with distilled water diluting, be as cold as about 5 ℃, the powerful stirring down slowly splashes into the positive tetraethyl orthosilicate of 35ml (chemical pure, Tianjin chemical reagent factory), dropwise and continue to stir, obtain the hydrating solution (A solution) of positive tetraethyl orthosilicate; Get 8ml TPAOH (20% aqueous solution) again, arrive 40ml with distilled water diluting, be cooled to about 5 ℃, the powerful stirring down, slowly splash into and contain 1.5ml tetrabutyl titanate (chemical pure, Great Wall, Beijing chemical reagent factory) and the mixed solution of 4ml anhydrous isopropyl alcohol, dropwise and continue to stir, obtain the hydrating solution (B solution) of tetrabutyl titanate; Under brute force stirs, (B solution) is slowly splashed in (A solution), dripping off the back continues to stir half an hour at about about 10 ℃, be warming up to about 80 ℃ then and continue and stirred 3 hours, obtain transparent colloidal solution, this colloidal solution is put into the autoclave with microwave radiation field, set microwave frequency 2450MHz, reaction pressure 0.8MPa reacted 5 hours.Take out crystallization product, suction filtration, washing, drying obtain the TS-1 molecular sieve, and sample number into spectrum is W-2.W-2 was through 550 ℃ of roastings 6 hours, and its X-ray diffraction (XRD) spectrogram is seen Fig. 3.
Embodiment 3
With 30ml TPAOH (TPAOH, 20% solution, Tokyo changes into) arrive 60ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into the positive tetraethyl orthosilicate of 35ml (chemical pure, Tianjin chemical reagent factory) and drip off back continuation stirring, obtain the hydrating solution (A solution) of positive tetraethyl orthosilicate; Get 8ml TPAOH (20% solution) again, arrive 40ml with distilled water diluting, be as cold as about 5 ℃, under brute force stirs, slowly splash into and contain 1.5ml tetrabutyl titanate (chemical pure, Great Wall, Beijing chemical reagent factory) and the mixed solution of 4ml Virahol, drip off the back and continue to stir, obtain the hydrating solution (B solution) of tetrabutyl titanate; Under strong stirring, (B solution) is slowly splashed in (A solution), drip off the back after half an hour is stirred in about about 10 ℃ continuation, be warming up to about 80 ℃ and continue and stirred 3 hours, obtain transparent colloidal solution, this colloidal solution is put into the autoclave with microwave radiation field, set microwave frequency 3600MHz, reaction pressure 1.0MPa reacted 13 hours.Take out crystallization product, suction filtration, washing, drying obtain the TS-1 molecular sieve, and sample number into spectrum is W-3.W-3 was through 550 ℃ of roastings 6 hours, and its X-ray diffraction (XRD) spectrogram is seen Fig. 4.
Embodiment 4
With 30ml TPAOH (TPAOH, 20% solution, Tokyo changes into) arrive 60ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into the positive tetraethyl orthosilicate of 35ml (chemical pure, Tianjin chemical reagent factory) and drip off back continuation stirring, make positive tetraethyl orthosilicate hydrolysis (A solution); Get 8ml TPAOH (20% solution) again, arrive 40ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into and include 1.5ml tetrabutyl titanate (chemical pure, Great Wall, Beijing chemical reagent factory) and the mixed solution of 4ml Virahol, drip off the back and continue to stir, make tetrabutyl titanate hydrolysis 10 minutes (B solution); Under strong stirring, (B solution) is slowly splashed in (A solution), drip off the back after half an hour is stirred in about about 10 ℃ continuation, be warming up to about 80 ℃ and continue and stirred 3 hours, remove the disadvantageous Virahol of crystallization, obtain transparent colloidal solution this colloidal solution is put into the autoclave with microwave radiation field, set microwave frequency 4500MHz, reaction pressure 1.1MPa reacted 20 hours.Take out crystallization product, suction filtration, washing, drying obtain the TS-1 molecular sieve, and sample number into spectrum is W-4.W-4 was through 550 ℃ of roastings 6 hours, and its X-ray diffraction (XRD) spectrogram is seen Fig. 5.
Embodiment 5
With 30ml TPAOH (TPAOH, 20% solution, Tokyo changes into) arrive 60ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into the positive tetraethyl orthosilicate of 35ml (chemical pure, Tianjin chemical reagent factory) and drip off back continuation stirring, obtain the hydrating solution (A solution) of positive tetraethyl orthosilicate; Get 8ml TPAOH (20% solution) again, arrive 40ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into and include 1.5ml tetrabutyl titanate (chemical pure, Great Wall, Beijing chemical reagent factory) and the mixed solution of 4ml Virahol, drip off the back and continue to stir, obtain the hydrating solution (B solution) of tetrabutyl titanate; Under strong stirring, (B solution) is slowly splashed in (A solution), drip the back after half an hour is stirred in about about 10 ℃ continuation, be warming up to about 80 ℃ and continue and stirred 3 hours, obtain transparent colloidal solution, this colloidal solution is put into the autoclave with microwave radiation field, set microwave frequency 2450MHz, reaction pressure 1.3MPa reacted 29 hours.Take out crystallization product, suction filtration, washing, drying obtain the TS-1 molecular sieve, and sample number into spectrum is W-5.W-5 was through 550 ℃ of roastings 6 hours, and its X-ray diffraction (XRD) spectrogram is seen Fig. 6.
Embodiment 6
With 30ml TPAOH (TPAOH, 20% solution, Tokyo changes into) arrive 60ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into the positive tetraethyl orthosilicate of 35ml (chemical pure, Tianjin chemical reagent factory) and drip off back continuation stirring, obtain the hydrating solution (A solution) of positive tetraethyl orthosilicate; Get 8ml TPAOH (20% solution) again, arrive 40ml with distilled water diluting, be as cold as about 5 ℃, under strong stirring, slowly splash into and include 1.5ml tetrabutyl titanate (chemical pure, Great Wall, Beijing chemical reagent factory) and the mixed solution of 4ml Virahol, drip off the back and continue to stir, obtain the hydrating solution (B solution) of tetrabutyl titanate; Under strong stirring, (B solution) is slowly splashed in (A solution), drip the back after half an hour is stirred in about about 10 ℃ continuation, be warming up to about 80 ℃ and continue and stirred 3 hours, obtain transparent colloidal solution, this colloidal solution is put into the autoclave with microwave radiation field, set microwave frequency 2450MHz, reaction pressure 1.5MPa reacted 24 hours.Take out crystallization product, suction filtration, washing, drying obtain the TS-1 molecular sieve, and sample number into spectrum is W-6.W-6 was through 550 ℃ of roastings 6 hours, and its X-ray diffraction (XRD) spectrogram is seen Fig. 7.
Embodiment 7～14
The foregoing description 1～6 prepared TS-1 molecular sieve respectively 2 is restrained according to the TS-1 molecular sieve: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: acetone=1: 8: 20: 16 weight ratio, the there-necked flask of putting into a band prolong is evenly mixed, be warming up to temperature of reaction, whipped state is the reaction some hrs down, the product of gained its composition of gas chromatographic analysis, reaction conditions and analytical results are listed in table 1.In table 1:
Embodiment 15
The foregoing description 6 prepared TS-1 molecular sieves 2 are restrained according to the TS-1 molecular sieve: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: acetone=1: 12: 20: 16 weight ratio, the there-necked flask of putting into a band prolong is evenly mixed, be warming up to 80 ℃, whipped state reacted 10 hours down, the product of gained its composition of gas chromatographic analysis, analytical results sees Table 1.
Embodiment 16
The foregoing description 6 prepared TS-1 molecular sieves 2 are restrained according to the TS-1 molecular sieve: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: acetone=1: 4: 20: 16 weight ratio, the there-necked flask of putting into a band prolong is evenly mixed, be warming up to 80 ℃, whipped state reacted 6 hours down, the product of gained its composition of gas chromatographic analysis, analytical results sees Table 1.
Embodiment 17
The foregoing description 6 prepared TS-1 molecular sieves 2 are restrained according to the TS-1 molecular sieve: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: acetone=1: 12: 20: 16 weight ratio, the there-necked flask of putting into a band prolong is evenly mixed, be warming up to 80 ℃, whipped state reacted 6 hours down, the product of gained its composition of gas chromatographic analysis, analytical results sees Table 1.
Embodiment 18
The foregoing description 6 prepared TS-1 molecular sieves 2 are restrained according to the TS-1 molecular sieve: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: acetone=1: 12: 18: 18 weight ratio, the there-necked flask of putting into a band prolong is evenly mixed, be warming up to 85 ℃, whipped state reacted 7 hours down, the product of gained its composition of gas chromatographic analysis, analytical results sees Table 1.
Embodiment 19
The foregoing description 6 prepared TS-1 molecular sieves 2 are restrained according to the TS-1 molecular sieve: hydrogen peroxide (the 30 heavy % aqueous solution): phenol: acetone=1: 7: 24: 14 weight ratio, the there-necked flask of putting into a band prolong is evenly mixed, be warming up to 80 ℃, whipped state reacted 6 hours down, the product of gained its composition of gas chromatographic analysis, analytical results sees Table 1.
Table 1
| Embodiment | The TS-1 numbering | Reaction conditions | Phenol conversion (mol%) | Dihydroxy-benzene selectivity (mol%) | The mol ratio of Resorcinol and pyrocatechol |
| ????7 | ??W-1 | 70 ℃, 6 hours | ????15.7 | ????99 | ????1.2∶1.0 |
| ????8 | ??W-1 | 80 ℃, 6 hours | ????17.4 | ????99 | ????1.3∶1.0 |
| ????9 | ??W-2 | 80 ℃, 6 hours | ????7.9 | ????99 | ????1.3∶1.0 |
| ????10 | ??W-3 | 80 ℃, 6 hours | ????16.8 | ????99 | ????1.5∶1.0 |
| ????11 | ??W-4 | 80 ℃, 6 hours | ????19.8 | ????99 | ????1.6∶1.0 |
| ????12 | ??W-5 | 80 ℃, 6 hours | ????21.1 | ????99 | ????1.8∶1.0 |
| ????13 | ??W-6 | 80 ℃, 6 hours | ????20.9 | ????99 | ????1.8∶1.0 |
| ????14 | ??W-6 | 80 ℃, 4 hours | ????18.1 | ????100 | ????1.7∶1.0 |
| ????15 | ??W-6 | 80 ℃, 10 hours | ????21.4 | ????99 | ????1.6∶1.0 |
| ????16 | ??W-6 | 80 ℃, 6 hours | ????13.3 | ????100 | ????1.8∶1.0 |
| ????17 | ??W-6 | 80 ℃, 6 hours | ????27.3 | ????97 | ????1.7∶1.0 |
| ????18 | ??W-6 | 85 ℃, 7 hours | ????27.4 | ????100 | ????1.9∶1.0 |
| ????19 | ??W-6 | 80 ℃, 6 hours | ????17.1 | ????97 | ????1.6∶1.0 |
Claims (10)
1, a kind of is the phenol hydroxylation method of oxygenant with the hydrogen peroxide, it is characterized in that in microwave radiation field synthetic have the MFI structure HTS in the presence of, phenol and hydrogen peroxide are reacted in solvent.
2, according to the process of claim 1 wherein that the microwave frequency of said microwave radiation field is 600～50000MHz.
3, according to the method for claim 2, wherein the microwave frequency of said microwave radiation field is 900～30000MHz.
4, according to the method for claim 3, wherein the microwave frequency of said microwave radiation field is 900～4500MHz.
5, according to the process of claim 1 wherein said HTS: hydrogen peroxide: phenol: the weight ratio of solvent is 1: 4～20: 5～50: 4～40.
6, according to the method for claim 5, wherein said HTS: hydrogen peroxide: phenol: the weight ratio of solvent is 1: 6～12: 18～24: 14～18.
7, according to the method for arbitrary claim in the claim 1,5 and 6, wherein said solvent is water, alcohol, ketone or hydrogen peroxide.
8, according to the method for claim 7, wherein said solvent is an acetone.
9, according to the process of claim 1 wherein that said hydroxylating temperature is 70～90 ℃.
10, according to the process of claim 1 wherein that the said hydroxylating time is 2～15 hours.
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|---|---|---|---|
| CN99103272A CN1076724C (en) | 1999-03-30 | 1999-03-30 | Method for hydroxylation of phenol |
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|---|---|---|---|
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|---|---|---|---|---|
| CN1104405C (en) * | 2000-10-11 | 2003-04-02 | 吉林大学 | Tar-free catalytic oxidation of arene utilizing coupling reaction |
| WO2006038893A1 (en) * | 2004-10-06 | 2006-04-13 | Agency For Science, Technology And Research | Oxidation of phenolic compound with hydrogen peroxide generated in the presence of the phenolic compound |
| CN101792370A (en) * | 2010-03-17 | 2010-08-04 | 大连理工大学 | Method for synthesizing phenol from benzene by special micro-channel type titanium silicon-palladium double-layer membrane reactor |
| CN108246362A (en) * | 2018-01-16 | 2018-07-06 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications of bulky grain TS-1 Titanium Sieve Molecular Sieve |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4778666A (en) * | 1986-12-04 | 1988-10-18 | Mobil Oil Corporation | Crystallization method employing microwave radiation |
-
1999
- 1999-03-30 CN CN99103272A patent/CN1076724C/en not_active Expired - Fee Related
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| CN1104405C (en) * | 2000-10-11 | 2003-04-02 | 吉林大学 | Tar-free catalytic oxidation of arene utilizing coupling reaction |
| WO2006038893A1 (en) * | 2004-10-06 | 2006-04-13 | Agency For Science, Technology And Research | Oxidation of phenolic compound with hydrogen peroxide generated in the presence of the phenolic compound |
| CN101792370A (en) * | 2010-03-17 | 2010-08-04 | 大连理工大学 | Method for synthesizing phenol from benzene by special micro-channel type titanium silicon-palladium double-layer membrane reactor |
| CN101792370B (en) * | 2010-03-17 | 2012-12-26 | 大连理工大学 | Method for synthesizing phenol from benzene by special micro-channel type titanium silicon-palladium double-layer membrane reactor |
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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 |
| CN108658732B (en) * | 2017-03-30 | 2021-11-16 | 中国石油化工股份有限公司 | Process for preparing benzenediol |
| CN109721071A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and hydroxylating method produced by this method |
| CN109721071B (en) * | 2017-10-31 | 2020-10-27 | 中国石油化工股份有限公司 | Method for producing titanium-silicon molecular sieve, titanium-silicon molecular sieve produced by method and hydroxylation reaction method |
| CN108246362A (en) * | 2018-01-16 | 2018-07-06 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications of bulky grain TS-1 Titanium Sieve Molecular Sieve |
| WO2021128792A1 (en) * | 2019-12-27 | 2021-07-01 | 中国科学院大连化学物理研究所 | Catalyst for improving para-selectivity of phenol hydroxylation reaction product, preparation method therefor and application thereof |
| CN116178112A (en) * | 2022-12-09 | 2023-05-30 | 天津大学 | Ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method and application |
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