CN102167437B - Photochemical method for removing organic phenolic pollutants and hexavalent chromium in water body and preparation method of catalytic agent - Google Patents
Photochemical method for removing organic phenolic pollutants and hexavalent chromium in water body and preparation method of catalytic agent Download PDFInfo
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Abstract
The invention relates to a photochemical method for removing organic phenolic pollutants and hexavalent chromium in water body and a preparation method of a catalytic agent. The method comprises the steps of: arousing a mesoporous Bi203/TiO2 composite nano-visible light catalytic agent with visible light response to generate charge separation under the irradiation of visible light; reducing the hexavalent chromium which is high in toxicity in the wastewater into trivalent chromium which is low in toxicity and small in solubility by a conduction electron of Bi2O3; and removing the organic phenolic pollutants in the wastewater by a valence band hole oxidation method of TiO2 to achieve the aim of effectively purifying the composite polluted wastewater. The method can be performed under a normal temperature, the method is wide in application range, the wastewater does not need to be subsequently treated, the catalytic agent can be circularly used during reacting, and the use ratio of the visible light in the sunlight can be greatly improved, so that the method is wide in application prospect.
Description
Technical field:
The invention belongs to technical field of sewage, particularly a kind of preparation method who utilizes the excited by visible light photocatalyst to remove highly toxic organic phenolic comp ' ds pollution and chromic sewage disposal technology and used photocatalysis agent in the waste water simultaneously.
Background technology:
Phenolic cpd is one type of protoplasma poisonous substance, to all toxic effect of nearly all biology.Especially bigger to nerve system of human body harm, can make protein coagulating, the phenol in the aqueous solution can be caused poisoning by skin absorption, phenolic wastewater can make the biological death in the water.Because phenolic cpd has very big potential hazard to human health and ecotope, thereby it is extremely important with detection that it is carried out the comprehensive regulation.129 preferential detections in the things of U.S. EPA promulgation have 11 to be phenolic cpd, also have 6 to be phenolic cpd in 68 in China's priority pollutants Black List.Simultaneously, in phenols wastewater, usually be attended by the existence of heavy metal ion such as chromium, mercury, lead.Pollution of chromium mainly is Cr (VI) and Cr (III) in the water body, and Cr (III) mainly is adsorbed on solid matter surface and is present in the settling, and how soluble in water Cr (VI) is, and be stable, can be converted into Cr (III) through reduction.Wherein water miscible Cr (VI) has very strong toxicity, mainly with Cr
2O
7 2-And CrO
4 2-Form exists, and oxidisability is very strong, and the generation harm such as skin, breathing and Digestive tract to the people can produce teratogenesis, mutagenesis and carcinogenesis when serious.It is complicated more that the water body combined pollution that phenols organic pollutant and Cr (VI) cause jointly not only makes its behavior in environment transform; More increased the difficulty of governance of contaminate environment, removed significant when therefore studying the organic and inorganic combined pollutant for the comprehensive regulation of environment.
The sunshine that the optically catalytic TiO 2 technology can make full use of cheapness and " green " to remove effectively the pollutent in the environment; Comprising photochemical catalytic oxidation pollutent and photoreduction heavy metal ion, is an important channel that solves present global environmental degradation and energy dilemma.But research in the past is to the removal of certain single pollutent and unfolded mostly, like the article " TiO of the 2365th page of " environmental science and technology " magazine calendar year 2001s 35 volume
2The research of dihydroxyphenyl propane in the photocatalyst for degrading water body " (Ohko, Y.; Ando, I.; Niwa, C.; Et al. Degradation of bisphenol A in water by TiO
2Photocatalyst.
Environ. Sci. Technol. 2001, 35,2365-2368) rolled up the 1880th page article " TiO at 2005 39 with this magazine
2Arsenious research in the photochemical catalytic oxidation water: the influence of reaction kinetics and absorption " (Ferguson, M.A.; Hoffmann, M.R.; Hering, J.G., TiO
2-photocatalyzed As (III) oxidation in aqueous suspensions:Reaction kinetics and effects of adsorption.
Environ. Sci. Technol. 2005, 39,1880-1886).Also have calendar year 2001 " water body research " magazine 35 article of rolling up the 135th page " utilize chromic research in the optically catalytic TiO 2 reductive water system under the UV-irradiation " (Ku, Y. in addition; Jung, I. L., Photocatalytic reduction of Cr (VI) in aqueous solution by UV irradiation with the presence of titanium dioxide.
Water Research,
2001, 35,135-142), the article that " applied catalysis B: environment " magazine 2007 77 volume is the 157th page " preparation of neodymium doped titanium dioxide photocatalyst, characterize and under UV-irradiation to the reduction of chromium (VI) " (Rengaraj, S.; Venkataraj, S.; Yeon, J. W.; Et al. Preparation, characterization and application of Nd-TiO
2Photocatalyst for the reduction of Cr (VI) under UV light illumination.
Appl. Catal. B:Environ. 2007, 77,157-165).But about TiO
2It is also rare that photocatalysis technology is handled the report of colourless organic phenolic comp ' ds pollution and reduction of hexavalent chromium simultaneously, and these correlative studys all are TiO
2Under the irradiation of UV-light, carry out, the article of rolling up the 913rd page like " environmental science and technology " magazine in 2008 42 " utilizes nano-TiO
2While degradation of phenol compounds and reducing heavy metal ionic dynamics research " (Vinu. R.; Madras. G. Kinetics of simultaneous photocatalytic degradation of phenolic compounds and reduction of metal ions with nano-TiO
2.
Environ. Sci. Technol. 2008, 42,913-919).On the other hand; Because titanium oxide greater band gap (3.2 eV); Can only be by the ultraviolet excitation of wavelength less than 385nm; And UV-light only occupies 3 ~ 5% ratio in solar spectrum, as uses the electric energy that artificial ultraviolet source can labor, therefore attempts using low price, visible light with low cost or sunshine synchronous processing phenols organic pollutant and reduction of hexavalent chromium that environmental protection and energy-conservation all is extremely important.Visible light-responded for titanium oxide is produced, the investigator has made many outstanding work both at home and abroad, comprises mainly that semi-conductor is compound, nonmetal doping, dye sensitization etc.
Summary of the invention:
In sum; In order to overcome the deficiency of prior art problem; The invention provides a kind of preparation method who removes organic phenolic comp ' ds pollution and chromic photochemical method and catalyst system therefor in the water body, it is under visible light radiation, excites to have visible light-responded mesoporous Bi
2O
3/ TiO
2Composite photo-catalyst produces chargeseparated, utilizes Bi
2O
3Conduction band electron be the trivalent chromium that toxicity is low, solubleness is little with highly toxic hexavalent chrome reduction in the sewage, utilize TiO simultaneously
2Valence band hole oxidation removal sewage in organic phenolic comp ' ds pollution, reach the purpose of high purification combined pollution waste water.
For solving the problems of the technologies described above, technical scheme of the present invention is achieved in that
Organic phenolic comp ' ds pollution and chromic photochemical method in a kind of removal water body, wherein: in reactor drum, add and contain phenolic comp ' ds pollution and chromic combined pollution waste water, then with mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst joins in the above-mentioned waste water, and using inorganic acid for adjusting pH is 1.0～5.5, the mesoporous Bi of dispersed with stirring
2O
3/ TiO
2The composite Nano visible light catalyst is opened the visible light source irradiation, makes mesoporous Bi
2O
3/ TiO
2The composite Nano visible-light photocatalyst is produced chargeseparated by excited by visible light, utilizes Bi
2O
3Conduction band electron also in the raw waste water highly toxic sexavalent chrome be the low trivalent chromium of toxicity, TiO simultaneously
2The hydroxyl radical free radical photoxidation of valence band hole or generation remove the phenolic comp ' ds pollution in the water body.
Technical scheme of the present invention can also be achieved in that organic phenolic comp ' ds pollution concentration in the described combined pollution sewage less than 600 mg/litre, and hexavalent chromium concentration is less than 500 mg/litre, and phenolic comp ' ds pollution and chromic concentration ratio are 1:12 ~ 10:1.
Technical scheme of the present invention can also be achieved in that described mesoporous Bi
2O
3/ TiO
2The consumption of nano composite photo-catalyst is 0.2 ~ 5.0 grams per liter compound sewage.
Technical scheme of the present invention can also be achieved in that the time of described unlatching visible light source irradiation is 90 ~ 240 minutes.
Technical scheme of the present invention can also be achieved in that described visible light source is halogen tungsten lamp, xenon lamp or sunshine.
Technical scheme of the present invention can also be achieved in that described stirring is a magnetic agitation.
Technical scheme of the present invention can also be achieved in that Bismuth trinitrate is dissolved in the certain density nitric acid; Dropwise drip the mixing solutions of titanium isopropylate and Virahol under the room temperature while stirring, the mol ratio of Bismuth trinitrate and titanic acid ester is 0:100 ~ 5:100, dropwises the continued stirring at room 1.5 ~ 2.5 hours; Hydrothermal treatment consists is 4 ~ 6 hours then; Be cooled to room temperature and remove supernatant liquid, infrared drying 2 ~ 3 hours obtains flaxen mesoporous Bi after the grinding
2O
3/ TiO
2The composite Nano visible-light photocatalyst.
Beneficial effect of the present invention is:
1, the present invention is under visible light radiation, excites to have visible light-responded mesoporous Bi
2O
3/ TiO
2Composite photo-catalyst produces chargeseparated, utilizes Bi
2O
3Conduction band electron be the trivalent chromium that toxicity is low, solubleness is little with highly toxic hexavalent chrome reduction in the sewage, utilize TiO simultaneously
2Valence band hole oxidation removal sewage in organic phenolic comp ' ds pollution, reach the purpose of high purification combined pollution waste water.
2, can carry out under the method normal temperature of the present invention, applied widely, sewage need not aftertreatment, and catalyzer can be recycled in reaction process, has greatly improved the utilization ratio to visible light part in the sunshine, has broad application prospects.
3, catalyzer of the present invention also has meso-hole structure and bigger specific surface area, can significantly strengthen in the water body pollutent in its surperficial absorption and degraded, thereby further improve phenolic comp ' ds pollution and chromic removal efficient in the sewage.
Description of drawings:
Fig. 1 is Trichlorophenol 98 (TCP, pH=3) the degraded dynamic curve synoptic diagram under different experimental conditions;
Curve a:TCP 60 mg/L, Cr (VI) 45 mg/L, Bi
2O
3/ TiO
2Photocatalyst 1.0g/L, radiation of visible light;
Curve b:TCP 60 mg/L, Bi
2O
3/ TiO
2Photocatalyst 1.0g/L, radiation of visible light;
Curve c:TCP 60 mg/L, Cr (VI) 45 mg/L do not add photocatalyst, radiation of visible light;
Curve d:TCP 60 mg/L do not add photocatalyst, radiation of visible light;
Curve e:TCP 60 mg/L, Cr (VI) 45 mg/L, Bi
2O
3/ TiO
2Photocatalyst 1.0g/L, unglazed photograph;
Fig. 2 is the photo catalytic reduction dynamic curve synoptic diagram of sexavalent chrome (pH=3) under different experimental conditions;
Curve a:TCP 60 mg/L, Cr (VI) 45 mg/L, Bi
2O
3/ TiO
2Photocatalyst 1.0g/L, radiation of visible light;
Curve b:Cr (VI) 45 mg/L, Bi
2O
3/ TiO
2Photocatalyst 1.0g/L, radiation of visible light;
Curve c:TCP 60 mg/L, Cr (VI) 45 mg/L do not add photocatalyst, radiation of visible light;
Curve d:Cr (VI) 45 mg/L do not add photocatalyst, radiation of visible light;
Curve e:TCP 60 mg/L, Cr (VI) 45 mg/L, Bi
2O
3/ TiO
2Photocatalyst 1.0g/L, unglazed photograph;
Fig. 3 for a change catalyst levels to the synoptic diagram that influences of TCP degradation rate;
Fig. 4 for a change catalyst levels to the synoptic diagram that influences of hexavalent chrome reduction rate;
Fig. 5 is the mesoporous Bi that different initial bismuths and titanium mol ratio are prepared
2O
3/ TiO
2Composite photo-catalyst is to the synoptic diagram that influences of oxidative degradation phenolic comp ' ds pollution and collaborative reduction of hexavalent chromium;
Fig. 6 is mesoporous Bi
2O
3/ TiO
2The different pH values of composite Nano visible light catalyst system are to the synoptic diagram that influences of TCP degradation rate;
Fig. 7 is mesoporous Bi
2O
3/ TiO
2The different pH values of composite Nano visible light catalyst system are to the synoptic diagram that influences of hexavalent chrome reduction rate.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed description.
Embodiment one:
Prepare mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst:
Bismuth trinitrate is dissolved in the certain density nitric acid; Dropwise drip the mixing solutions of titanium isopropylate and Virahol under the room temperature while stirring, the mol ratio of Bismuth trinitrate and titanic acid ester is 3.0%, dropwises continued and stirs 2 hours; Hydrothermal treatment consists is 5 hours then; Be cooled to room temperature and remove supernatant liquid, infrared drying 2 hours obtains flaxen mesoporous Bi
2O
3/ TiO
2The composite Nano visible-light photocatalyst.
One glass reactor contains 50 milliliters of 60 mg/L TCP and the chromic analog composite pollutant effluents of 45 mg/L, mesoporous Bi
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 90 minutes, and made mesoporous Bi
2O
3/ TiO
2Composite visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can be hypotoxic trivalent chromium with the hexavalent chrome reduction of coexistence, reaction result is seen the curve a among the curve a and Fig. 2 among Fig. 1.The result shows 90 minutes, and the degradation rate of TCP can reach 98.5 %, and hexavalent chrome reduction becomes chromic reduction ratio can reach 90.6% simultaneously.
Embodiment two:
Contain 50 milliliters of analog composite pollutant effluents in three glass reactors respectively, wherein contain the sexavalent chrome of 45 mg/L and the TCP that concentration is respectively 60,200,600 mg/L, add mesoporous Bi respectively
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 90 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can with the coexistence hexavalent chrome reduction be hypotoxic trivalent chromium, reaction result is seen table 1, shows that the photocatalytic degradation rate of TCP is relevant with its initial concentration.
Embodiment three:
Contain 50 milliliters of analog composite pollutant effluents in three glass reactors respectively, wherein contain the TCP of 60 mg/L and the sexavalent chrome that concentration is respectively 20,150,500 mg/L, add mesoporous Bi respectively
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 90 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can with the coexistence hexavalent chrome reduction be hypotoxic trivalent chromium; Reaction result is seen table 1; Show that chromic photo catalytic reduction rate is also relevant with its initial concentration, under lower concentration, hexavalent chrome reduction becomes chromic reduction ratio can reach 100 % in the short period of time.
Table
1TCP and chromic starting point concentration are to the influence of its photochemical catalysis clearance
(pH 3.0, radiation of visible light 90 minutes, Bi
2O
3/ TiO
2Photocatalyst 1.0 g/L)
Embodiment four:
Contain 50 milliliters of analog composite pollutant effluents in three glass reactors respectively, wherein contain 60 mg/L TCP and 45 mg/L sexavalent chromes, in three glass reactors, add mesoporous Bi respectively
2O
3/ TiO
2The composite Nano visible light catalyst; Consumption is respectively 0.2 grams per liter compound wastewater, 1.0 grams per liter compound wastewaters, 5.0 grams per liter compound wastewaters; Using sulfuric acid to regulate waste water ph is 2.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 90 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can be hypotoxic trivalent chromium with the hexavalent chrome reduction of coexistence, reaction result is seen Fig. 3, Fig. 4, showing increases the carrying out that catalyst consumption can be quickened light-catalyzed reaction.
Embodiment five:
One glass reactor contains 50 milliliters of 90 mg/L TCP and the chromic analog composite pollutant effluents of 68 mg/L, mesoporous Bi
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using hydrochloric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 120 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can be trivalent chromium with the hexavalent chrome reduction of coexistence, the result shows 120 minutes, the degradation rate of TCP can reach 94.8 %, simultaneously chromic reduction ratio can reach 90.2 %.
Embodiment six:
One glass reactor contains 50 milliliters of 90 mg/L TCP and the chromic analog composite pollutant effluents of 45 mg/L, mesoporous Bi
2O
3/ TiO
2150 milligrams of composite Nano visible light catalysts (consumption 3.0 grams per liter combined pollution waste waters), using hydrochloric acid to regulate waste water ph is 2.0, the magnetic agitation dispersed catalyst directly utilized solar light irradiation 150 minutes, made Bi
2O
3/ TiO
2Composite visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation trichlorophenol that produces of valence band hole or oxidizing water, utilize Bi simultaneously
2O
3The conduction band electron reduction of hexavalent chromium, the result shows 150 minutes, the degradation rate of TCP can reach 93.7%, simultaneously hexavalent chrome reduction becomes chromic reduction ratio can reach 89.5 %.
Embodiment seven
:
Contain 50 milliliters of the chromic analog composite pollutant effluents of 60 mg/L TCP and 45 mg/L in a plurality of glass reactors respectively, add a plurality of mesoporous Bi that different initial bismuths, titanium mol ratio are prepared respectively
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using nitric acid to regulate simulated wastewater pH value is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 90 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can be trivalent chromium with the hexavalent chrome reduction of coexistence, reaction result is seen Fig. 5, best for bismuth, titanium mol ratio be the 3.0% mesoporous Bi for preparing
2O
3/ TiO
2The composite Nano visible-light photocatalyst.
Embodiment eight:
Contain 50 milliliters of the chromic analog composite pollutant effluents of 60 mg/L TCP and 45 mg/L in a plurality of glass reactors respectively, add mesoporous Bi
2O
3/ TiO
225 milligrams of composite Nano visible light catalysts (consumption is 0.5 grams per liter combined pollution waste water); Use hydrochloric acid to regulate that simulated wastewater pH value is 1.0,2.0,3.0,4.0,5.5 in each reactor drum respectively; The artificial light that uses is the 300W xenon lamp; Dispose the cut-off type spectral filter of 420 nm, opened the light source radiation of visible light 150 minutes, make mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3Conduction band electron can with the coexistence hexavalent chrome reduction be trivalent chromium, reaction result is seen Fig. 6, Fig. 7, waste water solution pH is 3.0 o'clock, TCP and chromic photochemical catalysis clearance reach the highest.
Embodiment nine:
One glass reactor contains 50 milliliters of 120 mg/L dihydroxyphenyl propanes and the chromic analog composite pollutant effluents of 75 mg/L, mesoporous Bi
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using sulfuric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 120 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation dihydroxyphenyl propane that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3The reducible sexavalent chrome of conduction band electron be trivalent chromium, the result shows 120 minutes, the degradation rate of dihydroxyphenyl propane can reach 93.6%, simultaneously hexavalent chrome reduction becomes chromic reduction ratio can reach 91.0 %.
Embodiment ten:
One glass reactor contains 48 mg/L 4-chloro-3,50 milliliters of the chromic analog composite pollutant effluents of 5-xylenol and 45 mg/L, mesoporous Bi
2O
3/ TiO
2100 milligrams of composite Nano visible light catalysts (consumption 2.0 grams per liter combined pollution waste waters); Using perchloric acid acid to regulate waste water ph is 2.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Opened the light source radiation of visible light 100 minutes, and made mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is utilized TiO by excited by visible light generation chargeseparated
2The hydroxyl photocatalytic degradation 4-chloro-3 that produces of valence band hole or oxidizing water, 5-xylenol, Bi simultaneously
2O
3The reducible sexavalent chrome of conduction band electron, the result shows 100 minutes, 4-chloro-3, the degradation rate of 5-xylenol can reach 96.2 %, and hexavalent chrome reduction becomes chromic reduction ratio can reach 90.4 % simultaneously.
Embodiment 11:
Contain 50 milliliters of combined pollution waste waters in the one glass surface ware, its pH is 5.0, and containing TCP concentration is 45 mg/L, and hexavalent chromium concentration is 60 mg/L, adds mesoporous Bi
2O
3/ TiO
2100 milligrams of composite Nano visible light catalysts (consumption 2.0 grams per liter combined pollution waste waters), the magnetic agitation dispersed catalyst directly utilizes sun power, reacts 240 minutes, makes mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is excited the generation chargeseparated by sunshine, utilizes TiO
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3The reducible sexavalent chrome of conduction band electron, the result shows 240 minutes, and the degradation rate of TCP can reach 96.8%, and hexavalent chrome reduction becomes chromic reduction ratio can reach 93.2 % simultaneously.
Embodiment 12:
In the reactor drum of 20 liters of wide-mouths, add 15 liters and contain TCP and chromic waste liquid, its pH is 5.0, contains TCP 50 mg/L, and sexavalent chrome 30 mg/L add mesoporous Bi
2O
3/ TiO
2Composite Nano visible light catalyst 50 gram (consumption 3.3 grams per liter combined pollution waste waters), the magnetic agitation dispersed catalyst directly utilizes solar light irradiation, and 9 of time from mornings made mesoporous Bi to totally 8 hours at 5 in afternoon
2O
3/ TiO
2The composite Nano visible light catalyst is excited the generation chargeseparated by sunshine, utilizes TiO
2The hydroxyl photocatalytic degradation TCP that produces of valence band hole or oxidizing water, Bi simultaneously
2O
3The reducible sexavalent chrome of conduction band electron, the result shows that the organic phenolic comp ' ds pollution greater than 96.8 % is removed in the waste water, is reduced into trivalent chromium greater than the sexavalent chrome of 98.5 %, reaches national sewage comprehensive emission standard (GB 8978-1996).
Reference examples one:
One glass reactor contains 50 milliliters of the 60 mg/L TCP aqueous solution, Bi
2O
3/ TiO
250 milligrams of composite photo-catalysts (consumption 1.0 grams per liter phenolic wastewater); Using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Open the light source radiation of visible light, the degradation rate of 90 minutes TCP is 43.1 %.
Reference examples two:
One glass reactor contains 50 milliliters of 45 mg/L hexavalent chromium water solutions, Bi
2O
3/ TiO
250 milligrams of composite photo-catalysts (consumption 1.0 grams per liter chromate waste waters); Using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Open the light source radiation of visible light, the hexavalent chrome reduction of 90 minutes 30.2 % is a trivalent chromium.
Reference examples three:
One glass reactor contains 50 milliliters of 60 mg/L TCP and the chromic analog composite pollutant effluents of 45 mg/L; Do not contain any catalyzer, using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp; Dispose the cut-off type spectral filter of 420 nm; Open the light source radiation of visible light and stop after 90 minutes, the result shows the degradation rate of TCP less than 15.11 %, is trivalent chromium less than the hexavalent chrome reduction of 8.9 %.
Reference examples four:
One glass reactor contains 50 milliliters of the 60 mg/L TCP aqueous solution, does not contain any catalyzer, and using nitric acid to regulate waste water ph is 3.0; The artificial light that uses is the 300W xenon lamp; Dispose the cut-off type spectral filter of 420 nm, open the light source radiation of visible light, the degradation rate of 90 minutes TCP is less than 2.9 %.
Reference examples five:
One glass reactor contains 50 milliliters of 45 mg/L hexavalent chromium water solutions; Do not contain any catalyzer; Using nitric acid to regulate waste water ph is 3.0, and the artificial light that uses is the 300W xenon lamp, disposes the cut-off type spectral filter of 420 nm; Open the light source radiation of visible light, 90 minutes hexavalent chrome reductions less than 3.0 % are trivalent chromium.
Reference examples six:
One glass reactor contains 50 milliliters of 60 mg/L TCP and the chromic analog composite pollutant effluents of 45 mg/L, mesoporous Bi
2O
3/ TiO
250 milligrams of composite Nano visible light catalysts (consumption 1.0 grams per liter combined pollution waste waters); Using nitric acid to regulate waste water ph is 3.0; Be heated to 80 ℃ under the condition of unglazed photograph; React and stop after 90 minutes, the result shows the degradation rate of TCP less than 3.1%, and the hexavalent chrome reduction less than 3.0% is a trivalent chromium.
Embodiment one contrasts and can know, visible light-mesoporous Bi with reference examples one and reference examples two
2O
3/ TiO
2The composite nano-catalyst system has been quickened phenolic comp ' ds pollution and the collaborative speed of removing of chromic photochemical catalysis in the waste water greatly.
Embodiment one contrasts and can know with reference examples three, reference examples four and reference examples five, and catalyzer phenolic comp ' ds pollution in removing waste water plays a part to improve removal efficient and removal effect with chromic process.
Embodiment one can know that with the contrast of reference examples six phase illumination condition is to mesoporous Bi
2O
3/ TiO
2The importance of composite Nano visible light catalyst.
Be noted that; The above embodiment is to the explanation of technical scheme of the present invention and unrestricted; Other modification that is equal to replacement or makes of affiliated technical field those of ordinary skill according to prior art; As long as do not exceed the thinking and the scope of technical scheme of the present invention, all should be included within the interest field of the presently claimed invention.
Claims (6)
1. remove organic phenolic comp ' ds pollution and chromic photochemical method in the water body for one kind, it is characterized in that: in reactor drum, add and contain organic phenolic comp ' ds pollution and chromic combined pollution waste water, then with mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst joins in the above-mentioned waste water, and using inorganic acid for adjusting pH is 1.0～5.5, the mesoporous Bi of dispersed with stirring
2O
3/ TiO
2The composite Nano visible light catalyst is opened the visible light source irradiation, makes mesoporous Bi
2O
3/ TiO
2The composite Nano visible light catalyst is produced chargeseparated by excited by visible light, utilizes Bi
2O
3Conduction band electron also in the raw waste water highly toxic sexavalent chrome be the low trivalent chromium of toxicity, TiO simultaneously
2The hydroxyl radical free radical photoxidation of valence band hole or generation remove the organic phenolic comp ' ds pollution in the water body; Organic phenolic comp ' ds pollution concentration≤600 mg/litre in the described combined pollution waste water; Hexavalent chromium concentration≤500 mg/litre, organic phenolic comp ' ds pollution and chromic concentration ratio are 1:12 ~ 10:1.
2. organic phenolic comp ' ds pollution and chromic photochemical method in the removal water body according to claim 1 is characterized in that: described mesoporous Bi
2O
3/ TiO
2The consumption of composite Nano visible light catalyst is 0.2 ~ 5.0 grams per liter combined pollution waste water.
3. organic phenolic comp ' ds pollution and chromic photochemical method in the removal water body according to claim 1 is characterized in that: the time of described unlatching visible light source irradiation is 90 ~ 240 minutes.
4. according to organic phenolic comp ' ds pollution and chromic photochemical method in claim 1 or the 3 described removal water bodys, it is characterized in that: described visible light source is halogen tungsten lamp, xenon lamp or sunshine.
5. organic phenolic comp ' ds pollution and chromic photochemical method in the removal water body according to claim 1 is characterized in that: described stirring is a magnetic agitation.
6. employed Preparation of catalysts method in organic phenolic comp ' ds pollution and the chromic photochemical method in the removal water body according to claim 1; It is characterized in that: Bismuth trinitrate is dissolved in the certain density nitric acid; Dropwise drip the mixing solutions of titanium isopropylate and Virahol under the room temperature while stirring, the mol ratio of Bismuth trinitrate and titanium isopropylate is 3:100 ~ 5:100, dropwises the continued stirring at room 1.5 ~ 2.5 hours; Hydrothermal treatment consists is 4 ~ 6 hours then; Be cooled to room temperature and remove supernatant liquid, infrared drying 2 ~ 3 hours obtains flaxen mesoporous Bi after the grinding
2O
3/ TiO
2The composite Nano visible light catalyst.
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| CN102380366B (en) * | 2011-09-16 | 2014-01-08 | 河南理工大学 | Bismuth and silicon doped nano titanium dioxide photocatalyst, preparation and application thereof |
| CN102500354B (en) * | 2011-11-18 | 2014-04-02 | 东华大学 | Beta-bismuth oxide/magnesium aluminum metal oxide photo-catalyst and preparation as well as application thereof |
| WO2013187028A1 (en) | 2012-06-14 | 2013-12-19 | パナソニック株式会社 | Method for treating arsenic-containing aqueous solution |
| JP5512060B1 (en) * | 2012-06-14 | 2014-06-04 | パナソニック株式会社 | Method for treating an aqueous solution containing hexavalent chromium |
| CN103816912B (en) * | 2014-03-05 | 2016-04-06 | 阜阳师范学院 | Bi 2o 3/ Co 3o 4the preparation method of composite photo-catalyst and application |
| CN104707560A (en) * | 2015-03-09 | 2015-06-17 | 云南大学 | Preparation method of modified mesopore TiO2 capable of effectively removing phosphorus in wastewater |
| CN104984756B (en) * | 2015-07-10 | 2018-07-31 | 浙江工商大学 | A kind of NF-Bi2O3- SBA visible light responsive photocatalysts and its preparation method and application |
| CN109201100A (en) * | 2018-07-27 | 2019-01-15 | 南京邮电大学 | A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof |
| CN111320253B (en) * | 2018-11-28 | 2022-08-30 | 香港科技大学 | Photocatalytic process using ultraviolet, visible, near infrared radiation to activate monovalent chlorine to produce active oxidizing species |
| CN109956519B (en) * | 2019-04-21 | 2021-11-12 | 贵州大学 | Method for removing hexavalent chromium and organic phenol pollutants in water through photochemical synergy |
| CN110292923B (en) * | 2019-07-04 | 2020-02-14 | 宁波航天米瑞科技有限公司 | Bismuth molybdate/titanium dioxide composite photocatalyst and preparation method thereof |
| CN111330648A (en) * | 2020-04-03 | 2020-06-26 | 中南大学 | MIL-101(Fe)/g-C3N4Composite visible light photocatalyst and preparation method and application thereof |
| CN111559775B (en) * | 2020-05-14 | 2023-04-21 | 东南大学 | Method for degrading nitrate nitrogen in water body by utilizing glucose photocatalysis |
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| 杨娟等.Bi2O3/TiO2复合纳米颗粒的可见光光催化性能.《无机化学学报》.2011,第27卷(第3期),第547-555页. * |
| 谈俊.二氧化钛纳米材料及有机污染物光催化降解研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2010,第26-33页. * |
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