CN103240129B - Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol - Google Patents
Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol Download PDFInfo
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- CN103240129B CN103240129B CN201310177192.9A CN201310177192A CN103240129B CN 103240129 B CN103240129 B CN 103240129B CN 201310177192 A CN201310177192 A CN 201310177192A CN 103240129 B CN103240129 B CN 103240129B
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Abstract
The invention discloses a photocatalyst for synthesizing o-(p-)benzenediol, and a synthetic method for o-(p-)benzenediol. The photocatalyst is prepared by the following steps of: dissolving C.I. pigment yellow 154 into dimethyl sulfoxide solvent, then, adding TiO2 powder into the solution, adding surface active agent Twain-80, and treating under 180-210 DEG C to get the photocatalyst. By photocatalytic reaction, phenol is used as hydroxylation reaction substrate, water and acetonitrile mixture are used as the solvent, H2O2 is used as a hydroxylation reaction reagent, and o-benzenediol and p-benzenediol are synthesized by single step reaction of photocatalytic hydroxylation. In the method disclosed by the invention, hydroxylation reaction is performed just under normal temperature, and high temperature and energy consumption are avoided; the exciting light can be the sunlight which is a clean and cheap reaction driving force, thus, energy is saved; H2O2 can be fully used, and emission of wastewater, waste gas and residue is reduced; phenol conversion rate (more than 62%), product selectivity (more than 86%) and total recovery of catechol and hydroquinone (more than 53) are higher; and the photocatalysis operation process is easier to implement.
Description
Technical field
The invention belongs to light-catalyzed reaction field, proposed especially synthetic neighbour (to) photochemical catalyst of benzenediol and neighbour (to) synthetic method of benzenediol.It is a kind of method of coming synthesizing o-dihydroxybenzene (being called for short CAL) and hydroquinones (being called for short HQE) by light-catalyzed reaction.
Background technology
CAL and HQE are widely used, and are important fine chemical products, can be used for the industries such as medicine, agricultural chemicals, spices, photograph, food, dyestuff, resin and coating.
CAL mainly obtains by hydrolysis such as o-chlorphenol or o-methoxyphenols.HQE production technology has aniline oxidizing process, p-Diisopropylbenzene oxidizing process etc.But the problems such as these existing production methods exist, and cost of material is high, reactions steps is many, complex process, discharge of wastewater is many, production efficiency is low, seriously corroded, equipment are more.
Also can prepare CAL and HQE by the direct hydroxylating of thermocatalytic phenol.
As use Sn
2mCM-41 Pyrogentisinic Acid catalytic hydroxylation, after reaction 24h, phenol conversion is 22.8%, has CAL57.8%, HQE18.4% (Journal of Catalysis, 1999,183:281-291) in product.
If with CoNiAl ternary hydrotalcite class catalyst for phenol hydroxylation, at n (phenol): n (H
2o
2under)=2:1 and 65 DEG C of conditions, phenol conversion 14.2%, CAL and HQE ratio are 3.8 (Journal of Catalysis, 2003,220 (1): 161-171).
Villa uses Fe-Cu-ZSM-5 molecular sieve as catalyst, after reaction 4h, the conversion ratio of phenol reaches 32% left and right, and the ratio of CAL and HQE is 1.5 (Journal of Molecular Catalysis A:Chemistry, 2005,228:233-240).
Taking full-silicon beta zeolite as catalyst, at 80 DEG C of reaction 6h, what the conversion ratio of phenol was 34.6%, CAL is selectively 69.8%, HQE's is selectively 27% (applied chemistry, 2007,24 (7): 290-295).
Also having the CuMgAl of employing houghite is catalyst, and temperature is 60 DEG C, and phenol conversion is up to 42.8% (catalysis journal, 2009,3 (30): 201-206); Zhu Yanjing etc. are with Fe (OH)
3for catalyst, 60～70 DEG C when reaction phenol conversion be 64%, CAL and HQE be selectively 67.5% (petrochemical industry, 2009,7 (38): 739-744).
Although phenol thermocatalytic one one-step hydroxylation reaction can be prepared CAL and HQE, have that reaction temperature is high, reaction time length, big energy-consuming, phenol conversion are low, CAL and HQE yield is low, accessory substance is many, CAL and the selective problem such as low of HQE.Therefore need to develop that low-temp reaction, reaction speed are fast, directly synthetic CAL and the HQE new technology of phenol one-step method hydroxylating of phenol high conversion, CAL and HQE high selectivity.Photocatalysis hydroxylating by phenol is prepared CAL and HQE, reaction carry out at normal temperature, normal pressure, only single step reaction, phenol conversion is high, CAL and HQE yield high, atom utilization is high, is a kind of phenols green synthesis process that has very much using value.
Summary of the invention
Prepare the deficiency of CAL and HQE technique for traditional multistep reaction method, and the phenol conversion that the direct hydroxylating of phenol thermocatalytic exists is low, CAL and HQE productive rate is low, selectively low, reaction temperature is high, the reaction time is long problem of CAL and HQE, the present invention has proposed new photochemical catalyst reaction especially, by the method for synthetic direct phenol hydroxylating CAL and HQE.
Adopt organic pigment/TiO
2compound is photochemical catalyst, under UV-irradiation, has successfully synthesized CAL and HQE by the direct hydroxylating of phenol one step, conversion ratio and selectively all higher.Overcome former traditional handicraft and polluted the shortcomings such as large, long flow path, complex process, accessory substance are many.The photocatalysis hydroxylating of phenol carries out at normal temperature, normal pressure, and conversion ratio is high, yield is high, reaction speed is fast, atom utilization is high, and industrial application value is large.
Technical scheme of the present invention is as follows:
A photochemical catalyst of synthetic CAL and HQE, is dissolved in C.I. pigment yellow 154 in solvent dimethyl sulfoxide (DMSO), then adds wherein TiO
2powder, then add surfactant Tween-80, stir and form the yellow slurries that are suspended; This is suspended to slurries system and transfers in closed container, at 180～210 DEG C, process 2～4h; Naturally cool to room temperature.Gained suspension is carried out to isolated by filtration, after filtration cakes torrefaction is complete, obtain light yellow complex catalyst; With PY154/TiO
2catalyst explanation.
The material mass ratio of raw material is:
TiO
2: C.I. pigment yellow 154=1:0.05～0.1;
TiO
2: dimethyl sulfoxide (DMSO)=1:13～20;
TiO
2: Tween-80=1:0.05～0.15.
The method that adopts the synthetic CAL of catalyst of the present invention and HQE, by light-catalyzed reaction, taking phenol as hydroxylating substrate, water and acetonitrile mixture are solvent, use H
2o
2for hydroxylating reagent, photocatalysis hydroxylating single step reaction has synthesized CAL and HQE.
The quality proportioning of reaction mass is:
Phenol: H
2o
2=1:1.1～2.5;
Phenol: acetonitrile=1:5～10;
Phenol: catalyst=1:0.07～0.3;
Phenol: H
2o=1:20～45.
The synthetic reaction time of photocatalysis hydroxylating single step reaction is 2～4h.
The UV-irradiation that photocatalysis hydroxylating single step reaction is 365nm with wavelength when synthetic always.
Photocatalysis hydroxylating temperature: reaction temperature is little on the impact of hydroxylating result, and operation just can at normal temperatures conventionally.
The present invention adopts photochemical catalyst, and taking phenol as hydroxylating substrate, water and acetonitrile mixture are solvent, use H
2o
2for hydroxylating reagent, photocatalysis hydroxylating single step reaction has synthesized CAL and HQE.Reaction equation is as follows:
After photocatalysis hydroxylating, sample, product does liquid-phase chromatographic analysis, determines CAL and HQE growing amount, calculates phenol conversion, product yield and reaction selectivity.Computational methods are as follows:
The present invention is synthetic a kind of new photochemical catalyst and the synthetic CAL of hydroxylating and HQE technology.Adopting water-acetonitrile mixture is solvent, with H
2o
2for hydroxylating reagent, at PY154/TiO
2under compound photocatalysis, direct phenol single step reaction method is converted into CAL and HQE.Can there is hydroxylating in normal temperature, do not need high temperature power consumption; Exciting light may be sunshine, is clean and cheap reacting driving force, saves the energy; H
2o
2can make full use of, solvent is recyclable, and three wastes discharge amount is few; Reaction speed is fast; Phenol conversion (more than 62%), selectivity of product (more than 86%), CAL and HQE total recovery (more than 53%) are higher; Photocatalysis operating procedure is more easily implemented.
Detailed description of the invention
Below catalyst P Y154/TiO
2prepare example.
Embodiment 1
Material proportion is:
TiO
2: C.I. pigment yellow 154=1:0.09(mass ratio);
TiO
2: dimethyl sulfoxide (DMSO)=1:16(mass ratio);
TiO
2: Tween-80=1:0.12(mass ratio);
In beaker, add 0.9g C.I. pigment yellow 154, then add 160g dimethyl sulfoxide (DMSO), stir, make its dissolving.Add wherein again 10g TiO
2(trade names P25), and add 1.2g Tween-80, stir until form yellow and be suspended uniformly slurries.This is suspended to slurries system and forwards in stainless steel autoclave, at 190 DEG C, constant temperature is processed 4h.After finishing dealing with, naturally cool to room temperature.Gained is suspended to slurries and carries out isolated by filtration, and gained filter cake is repeatedly washed with distilled water, until filtrate is colourless.Then gained sediment is placed in to drying box and is dried at 100 DEG C, dry be ground to powder after completely, obtain light yellow PY154/TiO
2catalyst, this catalyst can be used for following photochemical catalyst hydroxylating.For simplicity, this catalyst is designated as to PYT-A.
Embodiment 2
Material proportion is:
TiO
2: C.I. pigment yellow 154=1:0.05(mass ratio);
TiO
2: dimethyl sulfoxide (DMSO)=1:13(mass ratio);
TiO
2: Tween-80=1:0.05(mass ratio);
In beaker, add 0.5g C.I. pigment yellow 154, then add 130g dimethyl sulfoxide (DMSO), stir, make its dissolving.Add wherein again 10g TiO
2(trade names P25), and add 0.5g Tween-80, stir until form yellow and be suspended uniformly slurries.This is suspended to slurries system and forwards in stainless steel autoclave, at 210 DEG C, constant temperature is processed 3h.After finishing dealing with, naturally cool to room temperature.Gained is suspended to slurries and carries out isolated by filtration, and gained filter cake is repeatedly washed with distilled water, until filtrate is colourless.Then gained sediment is placed in to drying box and is dried at 100 DEG C, dry be ground to powder after completely, obtain light yellow PY154/TiO
2catalyst, this catalyst can be used for following photochemical catalyst hydroxylating.For simplicity, this catalyst is designated as to PYT-B.
Embodiment 3
Material proportion is:
TiO
2: C.I. pigment yellow 154=1:0.1(mass ratio);
TiO
2: dimethyl sulfoxide (DMSO)=1:20(mass ratio);
TiO
2: Tween-80=1:0.15(mass ratio);
In beaker, add 1g C.I. pigment yellow 154, then add 200g dimethyl sulfoxide (DMSO), stir, make its dissolving.Add wherein again 10g TiO
2(trade names P25), and add 1.5g Tween-80, stir until form yellow and be suspended uniformly slurries.This is suspended to slurries system and forwards in stainless steel autoclave, at 180 DEG C, constant temperature is processed 2h.After finishing dealing with, naturally cool to room temperature.Gained is suspended to slurries and carries out isolated by filtration, and gained filter cake is repeatedly washed with distilled water, until filtrate is colourless.Then gained sediment is placed in to drying box and is dried at 100 DEG C, dry be ground to powder after completely, obtain light yellow PY154/TiO
2catalyst, this catalyst can be used for following photochemical catalyst hydroxylating.For simplicity, this catalyst is designated as to PYT-C.
It is below photocatalysis hydroxylating example.
Embodiment 4
The proportioning of material is:
Phenol: H
2o
2=1:2(mass ratio, content 30%);
Phenol: acetonitrile=1:8(mass ratio);
Phenol: catalyst (PYT-A prepared by embodiment 1)=1:0.2(mass ratio);
Phenol: H
2o=1:30 (mass ratio);
The catalyst P YT-A, 3g phenol, 90g deionized water and the 24g acetonitrile that take 0.6g, add in Photoreactor.Under stirring, splash into 6g H
2o
2(content 30%), continues to stir 20min and keeps adsorption equilibrium, then under 250W high-pressure sodium lamp, irradiates 3h, and wavelength is 365nm.Timing sampling, centrifugation, gets supernatant liquor and carries out liquid-phase chromatographic analysis, calculates thus phenol conversion 63.0%, CAL yield 28.7%, HQE yield 27.6% and selectivity of product 89.3%.
Embodiment 5
The proportioning of material is:
Phenol: H
2o
2=1:1.1(mass ratio, content 30%);
Phenol: acetonitrile=1:10(mass ratio);
Phenol: catalyst (PYT-B prepared by embodiment 2)=1:0.3(mass ratio);
Phenol: H
2o=1:45 (mass ratio);
The catalyst P YT-B, 3g phenol, 135g deionized water and the 30g acetonitrile that take 0.9g, add in Photoreactor.Under stirring, splash into 3.3g H
2o
2(content 30%), continues to stir 20min and keeps adsorption equilibrium, then under 300W xenon lamp, irradiates 2h, and ultraviolet wavelength is 365nm.Timing sampling, centrifugation, gets supernatant liquor and carries out liquid-phase chromatographic analysis, calculates thus phenol conversion 62.0%, CAL yield 26.7%, HQE yield 26.6% and selectivity of product 86.0%.
Embodiment 6
The proportioning of material is:
Phenol: H
2o
2=1:2.5(mass ratio, content 30%);
Phenol: acetonitrile=1:5(mass ratio);
Phenol: catalyst (PYT-C prepared by embodiment 3)=1:0.07(mass ratio);
Phenol: H
2o=1:20 (mass ratio);
The catalyst P YT-C, 3g phenol, 60g deionized water and the 15g acetonitrile that take 0.21g, add in Photoreactor.Under stirring, splash into 7.5g H
2o
2(content 30%), continues to stir 20min and keeps adsorption equilibrium, then under 150W high-pressure sodium lamp, irradiates 4h, and ultraviolet wavelength is 365nm.Timing sampling, centrifugation, gets supernatant liquor and carries out liquid-phase chromatographic analysis, calculates thus phenol conversion 63.7%, CAL yield 28.9%, HQE yield 26.6% and selectivity of product 87.1%.
Embodiment 7
Contrast experiment.Experiment condition is with embodiment 4, but do not add catalyst, and phenol conversion 30.7%, does not detect that HQE generates, selectivity of product 10.4% at CAL yield 3.2%.
Embodiment 8
Contrast test.Experiment condition is with embodiment 4, but without UV-irradiation, phenol conversion only has 7.4%, does not detect that CAL and HQE generate.
Can clearly find out by above-described embodiment: photochemical catalyst of the present invention is easily prepared; Easy to implement for the synthetic CAL of photocatalysis hydroxylating and HQE technology; Can there is hydroxylating in normal temperature; Reaction speed is fast; Phenol conversion (more than 62%), selectivity of product (more than 86%), CAL and HQE total recovery (more than 53%) are higher.A kind of than prior art better new synthetic CAL and HQE technology.
The present invention is not limited to the technology described in embodiment, and its description is illustrative, and nonrestrictive.Authority of the present invention is limited by claim, based on the art personnel according to the technology related to the present invention that the present invention can change, the method such as restructuring obtains, all within protection scope of the present invention.
Claims (5)
1. a photochemical catalyst for synthesizing o-dihydroxybenzene and hydroquinones, is characterized in that C.I. pigment yellow 154 to be dissolved in solvent dimethyl sulfoxide (DMSO), then adds wherein TiO
2powder, then add surfactant Tween-80, stir and form the yellow slurries that are suspended; This is suspended to slurries system and transfers in closed container, at 180～210 DEG C, process 2～4h; Naturally cool to room temperature; Gained suspension is carried out to isolated by filtration, after filtration cakes torrefaction is complete, obtain light yellow PY154/TiO
2complex catalyst;
The material mass ratio of raw material is:
TiO
2: C.I. pigment yellow 154=1:0.05～0.1;
TiO
2: dimethyl sulfoxide (DMSO)=1:13～20;
TiO
2: Tween-80=1:0.05～0.15.
2. adopt the catalyst synthesizing o-dihydroxybenzene of claim 1 and the method for hydroquinones, it is characterized in that by light-catalyzed reaction, taking phenol as hydroxylating substrate, water and acetonitrile mixture are solvent, use H
2o
2for hydroxylating reagent, photocatalysis hydroxylating single step reaction has synthesized catechol and hydroquinones.
3. method as claimed in claim 2, is characterized in that the quality proportioning of reaction mass is:
Phenol: H
2o
2=1:1.1～2.5;
Phenol: acetonitrile=1:5～10;
Phenol: catalyst=1:0.07～0.3;
Phenol: H
2o=1:20～45.
4. method as claimed in claim 2, is characterized in that the synthetic reaction time of photocatalysis hydroxylating single step reaction is 2～4h.
5. method as claimed in claim 2, is characterized in that the UV-irradiation that photocatalysis hydroxylating single step reaction is 365nm with wavelength when synthetic always.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705677A (en) * | 1995-11-28 | 1998-01-06 | Ube Industries, Ltd. | Diphenyl oxalate-phenol adduct, process for producing the adduct and method of producing diphenyl oxalate from the adduct |
| CN101723808A (en) * | 2009-12-08 | 2010-06-09 | 天津大学 | Method for preparing 1-naphthol by using pigment green B catalysis |
| CN101857528A (en) * | 2010-06-30 | 2010-10-13 | 天津大学 | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation |
| CN102199072A (en) * | 2011-04-08 | 2011-09-28 | 天津大学 | Method for preparing 2,5-dimethyl phenol through direct catalytic hydroxylation of p-xylene |
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2013
- 2013-05-14 CN CN201310177192.9A patent/CN103240129B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705677A (en) * | 1995-11-28 | 1998-01-06 | Ube Industries, Ltd. | Diphenyl oxalate-phenol adduct, process for producing the adduct and method of producing diphenyl oxalate from the adduct |
| CN101723808A (en) * | 2009-12-08 | 2010-06-09 | 天津大学 | Method for preparing 1-naphthol by using pigment green B catalysis |
| CN101857528A (en) * | 2010-06-30 | 2010-10-13 | 天津大学 | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation |
| CN102199072A (en) * | 2011-04-08 | 2011-09-28 | 天津大学 | Method for preparing 2,5-dimethyl phenol through direct catalytic hydroxylation of p-xylene |
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