CN101857528B - Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation - Google Patents
Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation Download PDFInfo
- Publication number
- CN101857528B CN101857528B CN2010102138573A CN201010213857A CN101857528B CN 101857528 B CN101857528 B CN 101857528B CN 2010102138573 A CN2010102138573 A CN 2010102138573A CN 201010213857 A CN201010213857 A CN 201010213857A CN 101857528 B CN101857528 B CN 101857528B
- Authority
- CN
- China
- Prior art keywords
- phenol
- hydroxylation
- pyrocatechol
- hydroquinone
- mmc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 25
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title abstract description 15
- 238000007146 photocatalysis Methods 0.000 title description 6
- 230000001699 photocatalysis Effects 0.000 title description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 21
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 5
- 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 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000009466 transformation Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 210000005252 bulbus oculi Anatomy 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- 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
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- WRCHFMBCVFFYEQ-UHFFFAOYSA-N clofedanol Chemical compound C=1C=CC=C(Cl)C=1C(O)(CCN(C)C)C1=CC=CC=C1 WRCHFMBCVFFYEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ZRBGFWOXAQPDTH-UHFFFAOYSA-N umbellatine Natural products C1=C2C3=CC4=CC=C(OC)C(OC)=C4C(O)N3CCC2=CC2=C1OCO2 ZRBGFWOXAQPDTH-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing pyrocatechol and hydroquinone by adopting photochemical catalysis and hydroxylation, comprising the following steps of irradiating water as a solvent, acetonitrile as a cosolvent, H2O2 as a hydroxylation reagent and Fe-Al/MMC as a photochemical catalyst by using ultraviolet light and then directly hydroxylating and transforming phenol to the pyrocatechol and the hydroquinone. Since the phenol is directly transformed to the pyrocatechol and the hydroquinone in a one-step method, the hydroxylation reaction can be generated at normal temperature without high-temperature energy consumption; exciting light may be sunlight and is clean and low-cost reaction driving power so that energy sources are saved; since the H2O2 can be fully utilized and the solvent can be recovered, the method has less three-waste discharge; and the method has the advantages of higher transformation rate of hydroxylation reaction, selectivity and yield and easier enforcement of a photochemical catalysis operation process.
Description
Technical field
The invention belongs to the preparation method of aromatic ring class hydroxyl substitution compound, proposed the method that a kind of photochemical catalysis hydroxylation prepares pyrocatechol and Resorcinol especially.
Background technology
Pyrocatechol and Resorcinol are important fine chemical products, have wide application field.Pyrocatechol has another name called pyrocatechol, is used for industries such as medicine, agricultural chemicals, spices, photograph, resin and coating.It is the raw material of producing spices such as vanillin food grade,1000.000000ine mesh, piperonylaldehyde; Or the midbody of amino methyl class agricultural chemicals such as furans pellet, Propoxur 97, the mould prestige of second; Be the precursor of stopper and oxidation inhibitor, also can be used to make antitussin, oxymethoxyallylbenzene, Umbellatine and Racemic isoproterenol etc.Resorcinol has another name called quinhydrones; Be important source material, auxiliary agent and the midbody of rubber, medicine, dyestuff, agricultural chemicals and fine chemistry industry, be mainly used in the system filmstrip the black-and-white development agent, produce anthraquinone dye and azoic dyestuff, synthetic gas desulfurization technology catalyzer, make stablizer and inhibitor, the anticoagulant etc. of anti-aging agent, monomer stopper, food and the coating varnish of rubber and plastics.
Traditional Process of Hydroquinone Production technology has aniline oxidation style, p-Diisopropylbenzene oxidation style etc.Pyrocatechol mainly obtains through hydrolysis such as ortho chloro phenol or hydroxyanisoles.But these traditional working methods exist, and reactions step is many, complex process, discharge of wastewater is many, production efficiency is low and problem such as seriously corroded.
For overcoming the shortcoming of above-mentioned old technology, there is the direct hydroxylation of a lot of thermocatalysis phenol to prepare the method for dihydroxy-benzene at present, this method mainly obtains pyrocatechol and Resorcinol.Representational work has: Chaudhari etc. have reported Sn
2The phenol hydroxylation catalytic activity of MCM-41 is when n (phenol): n (H
2O
2)=3: 1, water are solvent, and behind the reaction 24h, phenol conversion is 22.8%, products distribution be pyrocatechol 57.8%, Resorcinol 18.4% (Journal ofCatalysis, 1999,183:281-291).Rives etc. have prepared CoNiAl ternary hydrotalcite class catalyst applications in phenol hydroxylation reaction, at n (phenol): n (H
2O
2Under)=2: 1 and the 65 ℃ of conditions, phenol conversion 14.2%, adjacent (to) the dihydroxy-benzene ratio can reach 3.8 (Journal ofCatalysis, 2003,220 (1): 161-171).Villa has reported the catalytic performance of the hydroxylating of Fe-Cu-ZSM-5 molecular sieve; With water is solvent, under 80 ℃ of temperature of reaction, behind the reaction 4h; The transformation efficiency of phenol reaches about 32%; N (neighbour): n (to)=1.5 (Journal ofMolecular Catalysis A:Chemistry, 2005,228:233-240).What good luck etc. are catalyzer with the full-silicon beta zeolite, and behind reaction 6h under 80 ℃, the transformation efficiency of phenol is 34.6%, and the selectivity of pyrocatechol is 69.8%, and the selectivity of Resorcinol is 27% (applied chemistry, 2007,24 (7): 290-295).Shi Fengwei etc. are catalyzer with the CuMgAl houghite, phenol and H
2O
2Mol ratio is 1: 2, and temperature is 60 ℃, and phenol conversion is up to 42.8% (catalysis journal, 2009,3 (30): 201-206); Zhu Yanjing etc. are with Fe (OH)
3Be catalyzer, H
2O
2With the mol ratio of phenol be 1.5,60~70 ℃ of temperature, phenol conversion is 64%, the selectivity of dihydroxy-benzene is 67.5% (petrochemical complex, 2009,7 (38): 739-744).
Though thermocatalysis can prepare pyrocatechol and Resorcinol by phenol one one-step hydroxylation reaction, reactions step is few, problem such as have temperature of reaction height, power consumption, phenol conversion is low, the diphenol yield is low, by product is many, the diphenol selectivity is low.So the directly synthetic diphenol novel process of research and development high conversion, highly selective phenol single stage method hydroxylation becomes people's research focus.And the photochemical catalysis hydroxylating carries out at normal temperature, normal pressure, and transformation efficiency is high, yield is high, and atom utilization is high, is a kind of eco-friendly phenols green synthesis process.
Summary of the invention
The deficiency for preparing pyrocatechol and Resorcinol technology to traditional method; And the problem that phenol conversion is low, the diphenol productive rate is low, by product is many, the diphenol selectivity is low, temperature of reaction is high of the direct hydroxylation existence of thermocatalysis, the present invention has proposed a kind of method through the synthetic dihydroxy-benzene of the direct hydroxylation of phenol photochemical catalysis especially.(MMC representes the Sodium base montmorillonite as photocatalyst to use Fe-Al/MMC; Fe-Al/MMC is the Sodium base montmorillonite that load has iron, aluminium); Under UV-irradiation, successfully synthesized pyrocatechol and Resorcinol by direct hydroxylation of one step of phenol, transformation efficiency and selectivity are all higher.Overcome former traditional technology and polluted shortcomings such as big, long flow path, complex process, by product are many.The photochemical catalysis hydroxylating carries out at normal temperature, normal pressure, and transformation efficiency is high, yield is high, and atom utilization is high, is a kind of eco-friendly phenols green synthesis process.By the synthetic dihydroxy-benzene of the direct hydroxylation of phenol photochemical catalysis is one of research focus in the green catalysis synthetic technology.
It is photocatalyst that the present invention adopts Fe-Al/MMC, is the hydroxylation substrate with phenol, and water is solvent, and acetonitrile is a cosolvent, uses H
2O
2Be hydroxylation reagent, photochemical catalysis hydroxylation single step reaction has synthesized pyrocatechol and Resorcinol.Reaction equation is following:
The primary process of photochemical catalysis hydroxylating is following:
In photo catalysis reactor, add a certain amount of phenol, H
2O
2, solvent, catalyzer.In the room temperature magnetic agitation, simultaneously, use the high voltage mercury lamp radiation of predominant wavelength as 365nm, to take a sample behind the reaction certain hour, it is quantitative that product is done gas chromatographic analysis, calculates feed stock conversion, product yield and reaction preference.Method of calculation are following:
Photochemical catalysis prepares the method for pyrocatechol and Resorcinol, is solvent with water, and acetonitrile is a cosolvent, H
2O
2Be hydroxylation reagent, Fe-Al/MMC is a photocatalyst, through UV-irradiation, the direct hydroxylation of phenol is converted into pyrocatechol and Resorcinol.
During the photochemical catalysis hydroxylating, the proportioning of reaction mass is:
Phenol: H
2O
2=1: 0.3~1.2 (mol ratio is by pure H
2O
2Calculate);
Phenol: acetonitrile=1: 6~10 (ratio of quality and the number of copies);
Phenol: catalyzer=1: 0.1~0.2 (ratio of quality and the number of copies);
Phenol: H
2O=1: 4~16 (ratios of quality and the number of copies);
The photochemical catalysis hydroxylating rayed time: 3~6h;
Photochemical catalysis hydroxylating temperature: temperature of reaction is little to the hydroxylating influence, usually operation at normal temperatures.
The present invention is a kind of new photochemical catalysis hydroxylated synthetic o dihydroxy-benzene and Resorcinol technology, and employing water is solvent, and acetonitrile is a cosolvent, with H
2O
2Be hydroxylation reagent, under the Fe-Al/MMC photocatalysis, the direct single stage method of phenol be converted into pyrocatechol and Resorcinol.Hydroxylating can take place in normal temperature, does not need the high temperature power consumption; Exciting light possibly be sunshine, is cleaning 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; Hydroxylating transformation efficiency, selectivity, yield are than higher; The photochemical catalysis operating procedure is prone to implement.
Embodiment
The preparation of catalyst Fe-Al/MMC:
Preparation of catalysts method reference literature J.Agric.Food Chem., 2007, the 55:4877-4882 preparation.Take by weighing AlCl respectively
30.168g, FeCl
31.06g, it is dissolved in the 100mL deionized water, the dissolving back adds the 2.15g polynite fully.After stirring, slowly splash into the NaOH solution 50mL of concentration 0.2mol/L, behind the restir 60min, leave standstill 24h with tap funnel.Filter, 60 ℃ of oven dry down.It is last to pulverize, and puts into retort furnace, rises to 500 ℃ with the heat-up rate of 3 ℃/min, at 500 ℃ of roasting 3h.
Embodiment 1
In photo catalysis reactor, add 0.5g phenol (0.005mol), 0.05g Fe-Al/MMC catalyzer, 3.0g second eyeball, 8g H
2O and 0.0015mol H
2O
2The room temperature magnetic agitation; Use the 100W high voltage mercury lamp radiation 4h of predominant wavelength simultaneously as 365nm; It is centrifugal to take a sample then, gets supernatant liquid and carries out gas chromatographic analysis, calculates: phenol conversion is 63%, the pyrocatechol yield is 29.8%, the Resorcinol yield is 28.3%, selectivity 92.2%.
Embodiment 2
In photo catalysis reactor, add 0.5g phenol (0.005mol), 0.08g Fe-Al/MMC catalyzer, 4g second eyeball, 4g H
2O and 0.003mol H
2O
2The room temperature magnetic agitation; Use the 100W high voltage mercury lamp radiation 3h of predominant wavelength simultaneously as 365nm; It is centrifugal to take a sample then, gets supernatant liquid and carries out gas chromatographic analysis, calculates: phenol conversion is 38.2%, the pyrocatechol yield is 23.7%, the Resorcinol yield is 10.8%, selectivity is 90.3%.
Embodiment 3
In photo catalysis reactor, add 0.5g phenol (0.005mol), 0.1g Fe-Al/MMC catalyzer, 5g second eyeball, 2g H
2O and 0.006mol H
2O
2The room temperature magnetic agitation; Use the 100W high voltage mercury lamp radiation 6h of predominant wavelength simultaneously as 365nm; It is centrifugal to take a sample then, gets supernatant liquid and carries out gas chromatographic analysis, calculates: phenol conversion is 47.9%, the pyrocatechol yield is 28.6%, the Resorcinol yield is 11.8%, selectivity is 84.3%.
The present invention is not limited to the technology described in the embodiment, and its description is illustrative, and nonrestrictive.Authority of the present invention is limited claim, based on present technique field personnel according to the present invention can change, the technology relevant that method such as reorganization obtains with the present invention, all within protection scope of the present invention.
Claims (2)
1. photochemical catalysis hydroxylation prepares the method for pyrocatechol and Resorcinol, it is characterized in that with water being solvent, and acetonitrile is a cosolvent, H
2O
2Be hydroxylation reagent, Fe-Al/MMC is a photocatalyst; Through UV-irradiation,
The direct hydroxylation of phenol is converted into pyrocatechol and Resorcinol;
The proportioning of reaction mass is:
Phenol: H
2O
2Mol ratio=1: 0.3~1.2;
Phenol: acetonitrile ratio of quality and the number of copies=1: 6~10;
Phenol: photocatalyst ratio of quality and the number of copies=1: 0.1~0.2;
Phenol: H
2O ratio of quality and the number of copies=1: 4~16;
Among the described Fe-Al/MMC, MMC representes the Sodium base montmorillonite, and Fe-Al/MMC representes that load has the Sodium base montmorillonite of iron, aluminium.
2. the method for claim 1 is characterized in that the described photochemical catalysis hydroxylating rayed time is 3-6h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010102138573A CN101857528B (en) | 2010-06-30 | 2010-06-30 | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010102138573A CN101857528B (en) | 2010-06-30 | 2010-06-30 | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101857528A CN101857528A (en) | 2010-10-13 |
CN101857528B true CN101857528B (en) | 2012-07-04 |
Family
ID=42943722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010102138573A Expired - Fee Related CN101857528B (en) | 2010-06-30 | 2010-06-30 | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101857528B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103240129B (en) * | 2013-05-14 | 2014-08-20 | 天津大学 | Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol |
CN107324975B (en) * | 2016-04-28 | 2020-11-24 | 中国科学院理化技术研究所 | Direct hydroxylation or amination method of photocatalytic benzene and derivatives thereof |
CN109794282B (en) * | 2019-03-21 | 2021-07-13 | 陕西延长石油(集团)有限责任公司 | Photocatalyst for preparing phenol by benzene oxidation and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1361094A (en) * | 2000-12-29 | 2002-07-31 | 北京燕山石油化工公司研究院 | Integrated phenol hydroxylating process of preparing dihydroxylbenzene |
-
2010
- 2010-06-30 CN CN2010102138573A patent/CN101857528B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1361094A (en) * | 2000-12-29 | 2002-07-31 | 北京燕山石油化工公司研究院 | Integrated phenol hydroxylating process of preparing dihydroxylbenzene |
Non-Patent Citations (1)
Title |
---|
周春晖等.《介孔铁铝/蒙脱土复合材料: 解离柱撑制备、结构及催化羟基化性能》.《无机化学学报》.2006,第22卷(第4期),617-624. * |
Also Published As
Publication number | Publication date |
---|---|
CN101857528A (en) | 2010-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1847206A (en) | Synthesis process of cyclohexanone and cyclohexanol | |
CN101857528B (en) | Method for preparing pyrocatechol and hydroquinone by adopting photocatalysis and hydroxylation | |
EP3042719B1 (en) | Use of a catalyst for fixed bed aniline rectification residue recycling | |
CN107890867A (en) | Gray Pd/TiO2Nanowire photocatalyst and preparation method and application thereof | |
CN103709061B (en) | Photochemistry method for synthesizing imine or oxime by using alcohol and amine in one pot | |
CN110385138A (en) | A kind of preparation of the perforated tubular carbon nitride photocatalyst of rhodium load and its hydrogenation-dechlorination of parachlorphenol are catalyzed reaction | |
CN107827709B (en) | Method for synthesizing crotyl alcohol by photocatalytic ethanol conversion | |
CN103304380A (en) | Production process for continuously hydrolyzing and producing hydroquinone through multi-kettles in series | |
CN101961661B (en) | Organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and preparation method and application thereof | |
CN107398290B (en) | Catalyst for synthesizing thymol | |
CN104230635A (en) | Preparation method of ethylbenzene from acetophenone hydrogenation | |
CN108484366B (en) | Method for preparing hydroquinone by hydroxylation of phenol under visible light catalysis | |
CN101747156A (en) | New method for preparing 2,4-ditert-pentyl-phenol | |
CN101723808B (en) | Method for preparing 1-naphthol by using pigment green B catalysis | |
CN102351656B (en) | Synthesis method of hydroquinone | |
CN101921178B (en) | Method for preparing methylphenol from methylbenzene by one-step hydroxylation | |
CN103240129B (en) | Photocatalyst for synthesizing o-(p-)benzenediol, and synthetic method for o-(p-)benzenediol | |
CN114181047A (en) | Method for preparing biphenol from cresol | |
CN105013534B (en) | Effective photocatalysis system for selective oxidation of hydrocarbon by N2O | |
CN107185564A (en) | A kind of spherical nucleocapsid BiOCl/SnO2Visible light catalyst and its preparation method and application | |
CN1204105C (en) | Method for preparing dihydroxy-benzene | |
CN104959155A (en) | Nanometer copper/cuprous halide composite material and its preparation method and use | |
CN106242977B (en) | A kind of method for being catalyzed hydrogenation of chloronitrobenzene and preparing aniline | |
CN100457702C (en) | Environment-friendly preparation method for 2-tertiary butyl hydroquinone | |
CN102627530A (en) | Method for preparing phenol and dihydroxybenzene by catalytic hydroxylation of benzene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 |