CN107008253B - A kind of method of high-selectivity oxidation benzene synthesizing phenol - Google Patents
A kind of method of high-selectivity oxidation benzene synthesizing phenol Download PDFInfo
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- CN107008253B CN107008253B CN201710300718.6A CN201710300718A CN107008253B CN 107008253 B CN107008253 B CN 107008253B CN 201710300718 A CN201710300718 A CN 201710300718A CN 107008253 B CN107008253 B CN 107008253B
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 114
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 47
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 32
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000005286 illumination Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 150000001621 bismuth Chemical class 0.000 claims abstract description 3
- 150000001661 cadmium Chemical class 0.000 claims abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 238000010189 synthetic method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- 230000000694 effects Effects 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229910001882 dioxygen Inorganic materials 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 208000019155 Radiation injury Diseases 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 nitrogenous compound Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004875 x-ray luminescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/58—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 molecular oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method for high-selectivity oxidation benzene synthesizing phenol, this method has the advantages that selectivity is high, energy consumption is small and free of contamination.It is as follows that the present invention prepares the step of high efficiency photocatalyst: taking cadmium salt, tungstates to be dissolved in amine solution, stirs evenly after adjusting pH, hydrothermal treatment is centrifuged, is filtered, washed, the obtained cadmium tungstate of drying and other steps；It takes bismuth salt, tungstates to be dissolved in alcoholic solution, stirs evenly mixing, add cadmium tungstate obtained, cadmium tungstate-bismuth tungstate composite photocatalyst is made through crystallization, cooling, filtering, separation, drying and other steps after；It takes cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in solvent and reaction solution, is passed through oxygen, illumination is to get phenol.The present invention can improve the conversion ratio of benzene by the molar ratio of bismuth and cadmium in control catalyst, and obtained phenol selectivity is greater than 99%.
Description
[technical field]
The present invention relates to photochemical catalytic oxidation fields, and in particular to a kind of method of high-selectivity oxidation benzene synthesizing phenol.
[background technique]
Phenol is usually used in producing resin, fungicide, preservative, surface-active as a kind of important Organic Chemicals
Agent, plastics and drug (such as aspirin).Industrially often using benzene as raw material, sulfonation is carried out with sulfuric acid and generates benzene sulfonic acid, with Asia
Sulfuric acid neutralizes, then carries out alkali fusion with caustic soda, sulfonated to prepare phenol with vacuum distillation.Other preparation method packets of phenol
Include cumene method, Hydrolysis of Chlorobenzene method, Raschig process etc..All there is production procedure length, complex technical process, production in the above synthetic method
The disadvantages of at high cost, equipment seriously corroded.Therefore, it is concerned by the method for benzene direct oxidation green syt phenol.
One step phenol of benzene direct oxidation, mainly from selection efficient oxidation agent and exploration effective catalyst system etc.
It conducts a research, oxidant mainly includes hydrogen peroxide, nitric acid, nitrous oxide, oxygen etc..Nitrous oxide, nitric acid, hydrogen peroxide are made
For a kind of efficient oxygen carrier reagent, have many advantages, such as that process is simple, phenol yield is high as oxidant using them.But due to
Its production and transportation is at high cost, and the nitrogenous compound for reacting generation can cause certain pollution to environment.Therefore, with oxidation
Sub- nitrogen, nitric acid, hydrogen peroxide as oxidant catalysis oxidation Benzene to phenol receive restriction.In recent years, using molecular oxygen as oxidation
Agent, by photochemical catalytic oxidation Benzene to phenol by favor, this method has reaction temperature using solar energy as energy source
The advantages such as low, less energy intensive, equipment is simple；But phenol yield is lower, needs to research and develop effective catalyst.
Cadmium tungstate is important scintillator or X-ray luminescence body, has the high and low radiation injury of refractive index, luminous intensity big
The advantages that with excellent scintillation properties, plays an important role in the photoelectric materials such as fluorescence and laser.Bismuth tungstate (Bi2WO6) it is typical
N-type direct band-gap semicondictor material, have piezoelectricity, ferroelectricity and catalysis etc. physical and chemical performances, be to have in Bi base oxide
There is one of the semiconductor catalyst of best visible light catalysis activity, is applied to photocatalysis organic matter degradation, photocatalytic water and organic
The fields such as synthesis.In conjunction with the advantages of bismuth tungstate and cadmium tungstate photochemical catalyst, it can develop while there is visible light-responded, mild oxygen
Change ability, compared with high visible light catalytic activity the advantages that catalysis material.
[summary of the invention]
The present invention provides a kind of method for high-selectivity oxidation benzene synthesizing phenol, this method have selectivity it is high,
Energy consumption is small and free of contamination advantage.Its preparation step is as follows:
Take cadmium salt, tungstates to be dissolved in amine solution, be mixed uniformly and adjust pH to neutrality, by hydro-thermal process,
It is centrifuged, is filtered, washed, drying obtained cadmium tungstate；
Take bismuth salt, tungstates to be dissolved in alcoholic solution, stir evenly, add cadmium tungstate obtained, subsequent crystallization, cooling,
Filtering, separation, dry obtained cadmium tungstate-bismuth tungstate composite photocatalyst；
It takes cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in solvent and reaction solution, is passed through oxygen, illumination is to get benzene
Phenol.
Preferably, the amine solution is ethylenediamine or triethylamine solution.
Preferably, the alcoholic solution is ethyl alcohol, ethylene glycol or glycerin solution.
Preferably, the crystallization temperature is 100~200 DEG C, and crystallization time is 12~48h.
Preferably, the alcoholic solution volume is 1~80mL.
Preferably, the solvent is acetonitrile, and volume is 1~10mL.
Preferably, the speed for being passed through oxygen is calculated as 20~400mL/min/g by the quality of catalyst.
Preferably, the illumination is visible light greater than 400 nanometers, light irradiation time is 1~for 24 hours.
Preferably, in the cadmium tungstate-bismuth tungstate composite photocatalyst molar ratio of bismuth tungstate and cadmium tungstate be 1:[1~
10]。
The present invention can synthesize CdWO by changing cadmium tungstate-bismuth tungstate preparation condition4-Bi2WO6Composite photocatalyst
Agent, and be used in catalysis oxidation benzene synthesizing phenol.This method has selectivity height, energy consumption small, low to equipment corrosion, right
The features such as environmental nonpollution, and the conversion ratio of benzene is greater than the selectivity of 5%, phenol greater than 99%.
[specific embodiment]
Below with reference to the embodiment of the present invention, the present invention will be further described；In the following example, cadmium tungstate, bismuth tungstate are equal
For now-making-now-using, commercially available cadmium tungstate is directlyed adopt, bismuth tungstate has the effect of being equal with following embodiments, and not to the present invention
Technical solution bring substantial effect.
Embodiment 1
The present invention prepares light to change the molar ratio of cadmium tungstate in cadmium tungstate-bismuth tungstate composite photocatalyst, bismuth tungstate and urges
Agent:
The preparation of cadmium tungstate nanometer rods: 1.234g cadmium nitrate, 0.240g ethylenediamine solution is taken to be dissolved in 20mL deionization respectively
In water, solution A is mixed to form after being vigorously stirred 10min；It is molten that the aqueous solution B of 20mL sodium tungstate containing 1.316g is added dropwise to A
Liquid stirs and evenly mixs, and with nitre acid for adjusting pH to 7, continues to stir 20min, obtains solution C.Then by resulting solution C in 160 DEG C of crystalline substances
Change 20 hours.Cooling centrifuge separation, is washed with deionized three times, can obtain cadmium tungstate within dry 4 hours in 80 DEG C；
The preparation of composite material: it takes 0.015g sodium tungstate, 0.040g bismuth nitrate to be dissolved in 30mL ethylene glycol solution respectively, stirs
Solution D is mixed to form after mixing uniformly；Then 1mmol cadmium tungstate is added in solution D and forms solution E, resulting solution E is existed
Crystallization 24 hours at 160 DEG C.It is cooled to be separated by filtration, composite photo-catalyst can be obtained within dry 4 hours at 80 DEG C.
Under visible light, molecular oxygen prepares the phenol light prepared as model reaction investigation as oxidizing benzene and urges
The catalytic activity of agent:
Composite photocatalyst material prepared by 50mg is taken, then addition 0.5mmol benzene, 100 μ L deionized waters, 5mL acetonitrile,
Control oxygen gas flow rate is 60mL/min/g, first carries out 30min dark processing, and then opening light source, (optical filter is added in 300W xenon lamp
Filter light of the wavelength less than 400 nanometers) illumination 3h, opening condensation water management reacting liquid temperature is room temperature.After illumination, sampling
It is centrifugated out catalyst, instrument is finally used in conjunction using gas chromatography-mass spectrum, qualitative analysis is carried out to product, using gas chromatograph
(GC2010, hydrogen flameionization device detector, Shimadzu Corporation produce) carries out quantitative analysis to product, and the positive last of the ten Heavenly stems is used when quantitative analysis
For alkane as internal standard compound, the product that catalysis oxidation benzene obtains is phenol, and benzene conversion ratio is 5.8%, and the selectivity of phenol is greater than 99%.
Embodiment 2~5
Cadmium tungstate, bismuth tungstate composite photocatalyst to different mol ratio, operating procedure is similar with embodiment 1, only changes
The amount that sodium tungstate and bismuth nitrate are added in change composite material, remaining condition is constant, and sample number into spectrum be BCW-1, BCW-2,
BCW-3,BCW-4,BCW-5.Composite catalyst condition and reaction result prepared by embodiment 2~5 is shown in Table 1.
The bismuth tungstate of 1. different mol ratio of table-cadmium tungstate composite photo-catalyst reaction result
As shown in Table 1, different cadmium tungstates, bismuth tungstate molar ratio under obtain different benzene conversion ratios, wherein bismuth tungstate-
It is 5.8% that the conversion ratio of benzene is catalyzed when cadmium tungstate ratio is 4:10, and the selectivity of phenol is greater than 99%, and photocatalysis effect is fine.
Embodiment 6~10
The step of according to effect optimal embodiment 1, remaining condition it is constant (bismuth tungstate, cadmium tungstate molar ratio be 4:
10), only change crystallization temperature when composite photo-catalyst preparation, become 100 DEG C, 120 DEG C, 140 DEG C, 180 DEG C, 200 DEG C respectively,
And by its sample number into spectrum be A1, A2, A3, A4, A5.Composite catalyst condition and reaction result prepared by embodiment 6~10 is shown in Table
2。
Bismuth tungstate-cadmium tungstate composite photo-catalyst reaction result obtained by 2. different temperatures crystallization of table
It can be obtained by table 2, the benzene conversion ratio obtained under different crystallization temperatures compares with embodiment 1, and crystallization temperature is
The conversion ratio highest of benzene under the conditions of 160 DEG C has optimal photocatalysis effect.
Embodiment 11~13
The step of according to embodiment 1, remaining condition it is constant (bismuth tungstate, cadmium tungstate molar ratio be 4:10), change it is compound
Crystallization time when prepared by photochemical catalyst, difference crystallization 12h, 36h, 48h, and be B1, B 2, B3 its sample number into spectrum.Embodiment
11~13 composite photo-catalyst preparation conditions and reaction result are shown in Table 3.
Bismuth tungstate-cadmium tungstate composite photo-catalyst reaction result of 3. crystallization different time of table
It can be obtained by table 3, the conversion ratio of benzene under different crystallization times compares with embodiment 1, and crystallization time is item for 24 hours
The conversion ratio highest of benzene under part has optimal photocatalysis effect.
Embodiment 14~16
The step of according to embodiment 1, remaining condition it is constant (bismuth tungstate, cadmium tungstate molar ratio be 4:10), probe into its second
Influence of the change of glycol dosage to its photochemical catalytic oxidation.It is 20mL, 40mL, 80mL that ethylene glycol dosage, which is respectively adopted, and number is
C1,C2,C3.Embodiment 14~16 obtains corresponding reaction result and is shown in Table 4.
4. ethylene glycol dosage of table is to the influence of bismuth tungstate-cadmium tungstate composite photo-catalyst performance
It can be obtained by table 4, different benzene conversion ratios is obtained under different ethylene glycol volumetric usages, is compared with embodiment 1,
It was found that the benzene conversion ratio 5.8% under conditions of ethylene glycol volumetric usage is 60mL, has optimal photocatalysis effect.
Embodiment 17~19
It is 4:10 composite material according to the optimal molar ratio of bismuth tungstate, cadmium tungstate effect in reaction mixture is catalysis
Agent, remaining reaction condition is same as Example 1, probes into influence of the change to its photochemical catalytic oxidation of its reaction condition acetonitrile.
By taking the different volumes for controlling solvent acetonitrile as an example, the acetonitrile that solvent is 1mL, 3mL, 7mL is respectively adopted, corresponding number is denoted as
D1, D2, D3, embodiment 17~19 obtain corresponding reaction result and are shown in Table 5.
5. acetonitrile content of table is to the influence of bismuth tungstate-cadmium tungstate photocatalysis performance
Benzene conversion ratio under the different volumes of acetonitrile obtained by table 5, compares with embodiment 1, finds in acetonitrile volume
Under the conditions of 5mL, there is optimal photocatalysis effect.
Embodiment 20~23
It is 4:10 composite material according to the optimal molar ratio of bismuth tungstate, cadmium tungstate effect in reaction mixture is catalysis
Influence of the change to its photochemical catalytic oxidation of its light application time is probed into agent.It is 1h, 5h, 7h, 9h that light application time, which is respectively adopted, is divided
It Bian Hao not be E1, E2, E3, E4.Remaining reaction conditioned response condition is same as Example 1, and embodiment 20~23 obtains accordingly
Reaction result is shown in Table 6.
6. light application time of table is to the influence of bismuth tungstate-cadmium tungstate photocatalysis performance
By table 6 can under different light application times benzene generating rate, compare discovery with embodiment 1, in light application time
For 3h, there is optimal phenol generating rate.
Embodiment 24~28
It is 4:10 composite material according to the optimal molar ratio of bismuth tungstate, cadmium tungstate effect in reaction mixture is catalysis
Influence of the change to its photochemical catalytic oxidation of its reaction condition is probed into agent.For controlling the different flow velocity of oxygen, according to urging
Agent quality meter, is respectively adopted 20mL/min/g, 120mL/min/g, 240mL/min/g, 360mL/min/g and 400mL/min/
The oxygen gas flow rate of g is denoted as F1, F2, F3, F4, F5 accordingly, and remaining reaction conditioned response condition is same as Example 1, obtains phase
The reaction result answered is shown in Table 7.
7. oxygen gas flow rate of table is to the influence of bismuth tungstate-cadmium tungstate photocatalysis performance
Different benzene conversion ratios is obtained under different oxygen gas flow rates by the discovery of table 7, comparing with embodiment 1 can obtain, should
Catalyst is best in the reaction effect that flow velocity is 60mL/min/g.
Comparative example 1
The preparation method of cadmium tungstate: 1.234g cadmium nitrate, 0.240g ethylenediamine solution is taken to be dissolved in 20mL deionized water respectively
In, solution A is mixed to form after being vigorously stirred 10min；Solution A is added dropwise in the solution B of 20mL sodium tungstate containing 1.316g to mix
Stirring is continued to stir 20min, is obtained solution C with nitric acid tune pH to 7.Then resulting solution C is small in 160 DEG C of crystallization 24
When.Crystallization liquid is centrifugated through cooling, is washed with deionized three times, can obtain cadmium tungstate within dry 4 hours in 80 DEG C.
Using under visible light, molecular oxygen as oxidizer catalytic Oxybenzene prepare phenol as model reaction investigate prepared by urge
The photocatalytic activity of agent: then 0.5mmol benzene, 100 μ L deionizations are added in composite photocatalyst material prepared by taking 50 milligrams
Water, 5mL acetonitrile, control oxygen gas flow rate be 60mL/min/g, first carry out 30min dark processing, afterwards open light source (300W xenon lamp,
Optical filter is added and filters light of the wavelength less than 400 nanometers) illumination 3h, opening condensation water management reacting liquid temperature is room temperature.Illumination
After, sampling is centrifugated out catalyst, and instrument finally is used in conjunction using gas chromatography-mass spectrum and carries out qualitative analysis to product, adopts
Quantitative analysis is carried out to product with gas chromatograph (GC2010, hydrogen flameionization device detector, Shimadzu Corporation produce), it is quantitative to divide
Using n-decane as internal standard compound when analysis.The product that benzene catalysis oxidation obtains is phenol, and phenol generation is not detected.
Comparative example 2
The preparation method of bismuth tungstate: taking 0.060g sodium tungstate, 0.160g bismuth nitrate to be dissolved in 30ml ethylene glycol solution respectively,
It is mixed to form solution A after mixing evenly；Then 1mmol cadmium tungstate is added in solution A and forms solution B, by resulting solution B
Crystallization 24 hours at 160 DEG C.Crystallization liquid is separated through cold filtration, be washed with deionized three times, dehydrated alcohol washed once,
Composite photo-catalyst can be obtained within dry 4 hours at 80 DEG C.
Using under visible light, molecular oxygen as oxidizer catalytic Oxybenzene prepare phenol as model reaction investigate prepared by urge
The photocatalytic activity of agent: then 0.5mmol benzene, 100 μ L deionizations are added in composite photocatalyst material prepared by taking 50 milligrams
Water, 5mL acetonitrile control oxygen gas flow rate 60mL/min/g, first carry out 30min dark processing, and opening light source afterwards, (300W xenon lamp, adds
Enter optical filter and filter light of the wavelength less than 400 nanometers) illumination 3h, opening condensation water management reacting liquid temperature is room temperature.Illumination knot
Shu Hou, sampling are centrifugated out catalyst, and instrument finally is used in conjunction using gas chromatography-mass spectrum and carries out qualitative analysis to product, uses
Gas chromatograph (GC2010, hydrogen flameionization device detector, Shimadzu Corporation produce) carries out quantitative analysis, quantitative analysis to product
Shi Caiyong n-decane is as internal standard compound.The product that benzene catalysis oxidation obtains is phenol, and benzene conversion ratio is 0.8%, the selection of phenol
Property be greater than 99%.
Comparative example 3
It takes commercially available cadmium tungstate 0.036g and 0.523g bismuth tungstate is taken to be dissolved in 30mL ethylene glycol solution respectively, after mixing evenly
It is mixed to form solution；By resulting solution at 160 DEG C crystallization 24 hours.Crystallization liquid is separated through cold filtration, uses deionized water
Washing three times, dehydrated alcohol washed once, composite photo-catalyst can be obtained within dry 4 hours at 80 DEG C.
Composite photocatalyst material prepared by 50mg is taken, then addition 0.5mmol benzene, 100 μ L deionized waters, 5mL acetonitrile,
Control oxygen gas flow rate is 60mL/min/g, first carries out 30min dark processing, and opening light source afterwards, (300 watts of xenon lamp is added and filters
Piece filters light of the wavelength less than 400 nanometers) illumination 3h, opening condensation water management reacting liquid temperature is room temperature.After illumination, take
Sample is centrifugated out catalyst, and instrument finally is used in conjunction using gas chromatography-mass spectrum and carries out qualitative analysis to product, using gas-chromatography
Instrument (GC2010, hydrogen flameionization device detector, Shimadzu Corporation produce) carries out quantitative analysis to product, using just when quantitative analysis
For decane as internal standard compound, the product that benzene catalysis oxidation obtains is phenol, and benzene conversion ratio is 2.8%, and the selectivity of phenol is greater than
99%.
It can be seen that the method for the present invention from above-described embodiment and comparative example and CdWO be made4-Bi2WO6Composite photo-catalyst light
Catalysis oxidation benzene synthesizing phenol, using molecular oxygen as oxidant, under room temperature visible light can highly selective obtained phenol, compare
There is preferably activity in commercially available catalyst.
Claims (7)
1. a kind of method of high-selectivity oxidation benzene synthesizing phenol comprising the steps of:
It takes cadmium salt, tungstates to be dissolved in amine solution, stirs evenly after adjusting pH, hydrothermal treatment is centrifuged, is filtered, washed, doing
It is dry, cadmium tungstate is made；
Take bismuth salt, tungstates to be dissolved in alcoholic solution, stir evenly mixing, add cadmium tungstate obtained, subsequent crystallization, cooling,
Filtering, separation, dry, obtained cadmium tungstate-bismuth tungstate composite photocatalyst；
It takes cadmium tungstate-bismuth tungstate composite photocatalyst to be dispersed in solvent and reaction solution, is passed through oxygen, illumination is to get phenol；
Wherein, the amine solution is ethylenediamine or triethylamine solution；
Wherein, the alcoholic solution is ethyl alcohol, ethylene glycol or glycerin solution.
2. synthetic method according to claim 1, which is characterized in that the crystallization temperature is 100~200 DEG C, when crystallization
Between be 12~48h.
3. synthetic method according to claim 1, which is characterized in that the alcoholic solution volume is 1~80mL.
4. synthetic method according to claim 1, which is characterized in that the solvent is acetonitrile, and volume is 1~7mL.
5. synthetic method according to claim 1, which is characterized in that according to catalyst quality meter, the oxygen that is passed through
Speed is 20~400mL/min/g.
6. synthetic method according to claim 1, which is characterized in that the illumination is the visible light greater than 400 nanometers, light
According to when it is a length of 1~for 24 hours.
7. synthetic method according to claim 1, which is characterized in that in the cadmium tungstate-bismuth tungstate composite photocatalyst
The molar ratio of bismuth tungstate and cadmium tungstate is 1:[1~10].
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