CN104128208A - Modified nanometer titanium dioxide photocatalyst, and preparation method and application thereof - Google Patents
Modified nanometer titanium dioxide photocatalyst, and preparation method and application thereof Download PDFInfo
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- CN104128208A CN104128208A CN201410356921.1A CN201410356921A CN104128208A CN 104128208 A CN104128208 A CN 104128208A CN 201410356921 A CN201410356921 A CN 201410356921A CN 104128208 A CN104128208 A CN 104128208A
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Abstract
The invention provides a modified nanometer titanium dioxide photocatalyst and a preparation method and application thereof. The preparation method comprises the following steps: 1) adding nanometer TiO2 powder in a reactor filled with CCl4, adding a CCl4 solution of PCl3 at 80 DEG C, carrying out a reaction at 90 DEG C for 2 to 4 h and removing CCl4 to obtain powder I; 2) preparing 4-sodium sulfonate-phenylalkyl sodium sulfonate; 3) preparing 4-sodium sulfonate-phenyl-brominated alkyl sodium sulfonate; and 4) pouring treated metallic magnesium into a reactor filled with anhydrous ether, adding the product obtained in the step 3 until magnesium is fully reacted, adding bis(1,3-dibenzylphosphine)propyl nickel dichloride and the product obtained in the step 1), carrying out reflux for 15 to 20 h and carrying out treatment so as to obtain a finished product. The modified nanometer titanium dioxide photocatalyst is separated and recovered after degradation of high-concentration benzene-series pollutants, and the photocatalyst still has high catalytic activity after usage a plurality of times; after the photocatalyst is used 7 times, the degradation efficiency of the photocatalyst to high-concentration and hardly degradable benzene series reaches 100% in 8.0 h.
Description
Technical field
The invention belongs to catalytic oxidant and preparing technical field thereof, particularly a kind of modified nano-titanium dioxide photochemical catalyst and its preparation method and application.
Background technology
The high-concentration waste water of modern chemistry industry has following characteristics: colourity is high, has peculiar smell, easily gives out pungent stench, exerts a gradual, corrupting influence on environment; Organic matter supersaturation, concentration (in COD) is higher than 2000mg/L, have even up to hundreds thousand of mg/L, and contain dissimilar surfactant and organic solvent etc., self-emulsifying, certainly disperse and trapping ability strong, pollutant becomes suspended state and droplet-like; Complicated component, with aromatic compound and heterocyclic compound (BOD in the majority
5/ COD value ﹤ 0.3), also contain sulfide, nitride, heavy metal and other toxic organic compound, biodegradability extreme difference, long processing period; Often contain numerous acid, alkali, salt, and concentration is high, the salt content of part waste water is even up to mg/L up to ten thousand.Its pollution problem is in engineering of water treatment, to need a difficult problem of capturing badly always.
The character of high concentration benzene homologues waste water is different with source, improvement technology is various, have solvent extraction, film separation, absorption, ultrasonic degradation, burning, Fenton oxidation, ozone oxidation, electrochemical oxidation and bioanalysis etc., these methods mainly exist construction costs expensive, can not move for a long time, can not qualified discharge and the more high deficiency of operating cost of the effective unit water yield.This is because water treatment effect is not only relevant with the external environment condition such as water quality, the water yield, treatment cycle, temperature and pH value, also have substantial connection with the chemical composition and structure of high-concentration waste water and microbial population etc., this has also increased difficulty for the too high problem of workout cost.
Detitanium-ore-type TiO
2be that a kind of catalytic activity is higher, the semiconductor catalyst of stable chemical nature, safe, cheap, environment protecting and power-saving, under day illumination condition, can induce H
2o molecular ionization goes out hydroxyl free radical (OH), can decompose nearly all organic pollution, generates CO
2, H
2o.By TiO
2the ultra-fine nanomorphic that changes into can also improve its photocatalytic activity greatly, but nano-titania particle specific area is large, coordination wretched insufficiency, and also the imbalance of Ti-O key makes its polarity very strong, very easily mutually reunites, and affects its practical effect; Studies confirm that, compared with suspended particulate substance in water (SPM), the TiO of nanomorphic
2particle easily migration, free settling not in water body, have the risk of enrichment As (III), As (V) and Cd etc. in remarkable increase carp body; In addition, nano-TiO
2particle also has the risk of the genetic damage of causing.
Prior art has been announced a kind of synthetic method of visible photocatalyst by modifying titanium dioxide by using ammonium fluoride as Chinese patent CN102266792: take mesoporous MCF as carrier, at its duct internal burden TiO
2, then in conjunction with cryogenic vacuum activation method, utilize NH by hydro-thermal method
4f modification TiO
2visible light catalyst synthetic method.This catalyst is by the superior adsorption capacity of mesoporous material, the visible light photocatalytic degradation performance of enhancing to the organic pollution of high concentration, and have advantages of simple to operate, with low cost, raw material is easy to get and UV, visible light photolytic activity is higher, but a little less than existing load active force, in recycling process for a long time, cannot avoid TiO
2the problem that nano particle runs off, and the degradation experiment of pollutant proves that it processes that waste strength is lower, adsorbance is limited, has larger distance with photocatalysis feature and the mechanism process of actual high-concentration waste water; Chinese patent CN102527439 has announced a kind of polymer/TiO with photocatalytic activity
2the preparation method of hybridized film, has realized TiO
2the chemical load of nano particle in thin polymer film, not only effectively improved the reunion of nano particle, and after photocatalysis finishes, described hybridized film can directly be taken out from organic pollution solution, nano particle is recycled, solved conventional load method insoluble in long-term use procedure TiO
2the losing issue of nano particle, guarantee higher photocatalytic activity in long-term use, and technique is simple, but similar to traditional hydrophobically modified agent, this hybridized film itself is easy under illumination by TiO
2degraded, greatly reduces stability, and the basement membrane fibre diameter of hybridized film is increased to 100～300nm from 2～50nm of primary particle diameter, has limited the raising of photocatalytic activity.In sum, how to overcome the deficiency that prior art exists and become catalytic oxidant field technical barrier urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and propose a kind of modified nano-titanium dioxide photochemical catalyst and its preparation method and application, the present invention has good decentralized photo capacitive in water-based system, applicable 2000 to hundreds thousand of mg/L high concentration, difficult degradation benzo pollutants are processed, degraded is fast, efficiency is high, can be recycled, and nano-TiO
2particle is not easy to run off, and acid and alkali resistance, salt stable performance, be widely used in the processing of high concentration benzo pollutants.
Technical scheme of the present invention:
Modified nano-titanium dioxide photochemical catalyst, by following steps, prepare and obtain:
1) by nano-TiO
2powder adds CCl
4in, after stirring, be warming up to 80 ℃, obtain mixture A; By PCl
3be dissolved in CCl
4in, mix, by PCl
3cCl
4solution drops in mixture A, after be warming up to 90 ℃, reaction 2-4h, reclaims the CCl in reactant liquor
4, obtain powder I, wherein: CCl
4, nano-TiO
2powder, PCl
3, PCl
3cCl
4the mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10);
2) benzene is added in alpha-olefin sulfonic acid, stir and be warming up to 130 ℃, treat alpha-olefin sulfonic acid content constant, obtain phenylalkyl sulfonic acid; Be cooled to 10 ℃-20 ℃, continue to stir, drip oleum, dropwise, stirring reaction 2-3h at 25 ℃, drips 0.2molL
-1watery hydrochloric acid, after to add mass fraction be 20% the NaOH aqueous solution, to solution, be neutral, except desolventizing, obtain paste II, paste II is dissolved in absolute ethyl alcohol, filter, get filtrate, except desolventizing, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-sodium alkyl sulfonate, wherein: the mass ratio of alpha-olefin sulfonic acid, benzene, oleum, watery hydrochloric acid, absolute ethyl alcohol is 1:(1/2-1): (3-5): (1-3): (2-4);
3) by step 2) gained 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4and Br
2add successively reactor, be heated to reflux, reaction 12-20h, the NaHCO that is 9% with mass fraction successively
3the aqueous solution, distilled water, saturated common salt water washing, dry, obtain 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, wherein: 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4, Br
2, NaHCO
3the mass ratio of the aqueous solution, distilled water, saturated aqueous common salt is 1:(20-40): (2-5): (50-200): (100-300): (100-200);
4) use the oxide of salt acid treatment metallic magnesium surface, with absolute ethyl alcohol and absolute ether, clean successively, after magnesium metal is poured in the reactor that fills absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, be stirred to magnesium total overall reaction, add successively two (1,3-diphenylphosphine) propyl group Nickel Chloride and steps 1) gained powder I, backflow 15-20h, pours reactant liquor into the 2molL of 5 ℃-10 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photochemical catalyst finished product, wherein: the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, two (1,3-diphenylphosphine) propyl group Nickel Chloride, step 1) mass ratio of products therefrom, aqueous hydrochloric acid solution and water is (1/10-1/3): (2-5): 1:(1/1500-1/2000): (1/3-1/4): (15-30): (50-70).
The preparation method of modified nano-titanium dioxide photochemical catalyst, comprises the following steps:
1) by nano-TiO
2powder adds CCl
4in, after stirring, be warming up to 80 ℃, obtain mixture A; By PCl
3be dissolved in CCl
4in, mix, by PCl
3cCl
4solution drops in mixture A, after be warming up to 90 ℃, reaction 2-4h, reclaims the CCl in reactant liquor
4, obtain powder I, wherein: CCl
4, nano-TiO
2powder, PCl
3, PCl
3cCl
4the mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10);
2) benzene is added in alpha-olefin sulfonic acid, stir and be warming up to 130 ℃, treat alpha-olefin sulfonic acid content constant, obtain phenylalkyl sulfonic acid; Be cooled to 10 ℃-20 ℃, continue to stir, drip oleum, dropwise, stirring reaction 2-3h at 25 ℃, drips 0.2molL
-1watery hydrochloric acid, after to add mass fraction be 20% the NaOH aqueous solution, to solution, be neutral, except desolventizing, obtain paste II, paste II is dissolved in absolute ethyl alcohol, filter, get filtrate, except desolventizing, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-sodium alkyl sulfonate, wherein: the mass ratio of alpha-olefin sulfonic acid, benzene, oleum, watery hydrochloric acid, absolute ethyl alcohol is 1:(1/2-1): (3-5): (1-3): (2-4);
3) by step 2) gained 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4and Br
2add successively reactor, be heated to reflux, reaction 12-20h, the NaHCO that is 9% with mass fraction successively
3the aqueous solution, distilled water, saturated common salt water washing, dry, obtain 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, wherein: 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4, Br
2, NaHCO
3the mass ratio of the aqueous solution, distilled water, saturated aqueous common salt is 1:(20-40): (2-5): (50-200): (100-300): (100-200);
4) use the oxide of salt acid treatment metallic magnesium surface, with absolute ethyl alcohol and absolute ether, clean successively, after magnesium metal is poured in the reactor that fills absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, be stirred to magnesium total overall reaction, add successively two (1,3-diphenylphosphine) propyl group Nickel Chloride and steps 1) gained powder I, backflow 15-20h, pours reactant liquor into the 2molL of 5 ℃-10 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photochemical catalyst finished product, wherein: the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, two (1,3-diphenylphosphine) propyl group Nickel Chloride, step 1) mass ratio of products therefrom, aqueous hydrochloric acid solution and water is (1/10-1/3): (2-5): 1:(1/1500-1/2000): (1/3-1/4): (15-30): (50-70).
Above-mentioned steps 1) PCl described in
3cCl
4the rate of addition of solution is 0.13333-0.26667g/min, step 2) described in oleum and 0.2molL
-1the rate of addition of watery hydrochloric acid is 0.16667-0.33333g/min.
Described nano-TiO
2the particle diameter < 20nm of powder.
The carbon number range of described alpha-olefin sulfonic acid is C12-C20.
Modified Nano TiO
2the application of photochemical catalyst in the wastewater treatment of high concentration benzene homologues.
Described modified Nano TiO
2the application of photochemical catalyst in the wastewater treatment of high concentration benzene homologues, wherein said benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
The present invention's nano-TiO
2particle is as matrix, by benzene sulfonic acid sodium salt alkyl sulfonic acids sodium, be grafted to particle surface, improve its dispersion in water and to the emulsification of benzene homologues, trapping effect, degraded is made into benzene homologues (analyzing pure) has the oversaturated simulation industrial wastewater of high concentration.Prepare respectively at a certain temperature a stand oil (Gu) emulsification or the dispersion soln of water ratio, under certain rotating speed, constant temperature stirs certain hour, with mechanical agitation, carry out degradation reaction, institute's simulated wastewater is degraded and removed benzo pollutants, then utilize zeta current potential nano particle size instrument to carry out dynamic light scattering test to emulsification or the dispersion liquid of preparation, measure particle diameter and distribute; Get treatment fluid on centrifuge, under certain rotating speed, carry out centrifugal after, get its supernatant liquor, with cuvette, by UV-6 type ultraviolet-visible spectrophotometer, measure the absorbance for the treatment of fluid, take and test saturated solution as benchmark, calculate the relative concentration of pollutant.Change each factor that affects degradation reaction effect, by investigating concentration and degradation efficiency, finally draw the optimum reaction condition of processing waste water.Simulated wastewater is degraded and removed after benzo pollutants, and photocatalyst powder is separated, recycling.
The present invention compared with prior art its remarkable advantage is:
(1) the present invention effectively utilizes sunshine, with a kind of clean, environmental protection and energy-conservation mode, solve environmental pollution, applicable 2000 to hundreds thousand of mg/L high concentration, difficult degradation benzo pollutants are processed, widely applicable, especially the high-concentration waste water of complicated component is had to good effect, can realize qualified discharge;
(2) the present invention is directed to the oversaturated feature of most of high-concentration waste water pollutants, benzene sulfonic acid sodium salt alkyl sulfonic acids sodium is grafted to nano-TiO
2particle surface, the surface-active of photochemical catalyst and the dispersiveness in water-based system, compatibility have greatly been improved, pass through self-emulsifying, certainly disperse and trapping effect, be enriched in the contaminant particles surface of suspended state and droplet-like, the pollutant not only dissolving in degradable high-concentration waste water, also can directly the degrade particle of pollutant of emulsification, dispersion, accelerated degradation process, in the process of degrading high concentration benzene homologues, during 1.0h, can reach the degradable of high concentration benzene homologues, after 8.0h, can make difficult degradation benzene homologues reach degradable;
(3) after the modified nano-titanium dioxide photocatalyst for degrading high concentration benzo pollutants that prepared by this method, through separated, recovery, can be recycled, after being repeatedly used, still there is higher catalytic activity, after reusing 7 times, after 8.0h, to the degradation efficiency of high concentration, difficult degradation benzene homologues, still can reach 100%, and nano-TiO
2particle is not easy to run off;
(4) this photochemical catalyst acid and alkali resistance, salt stable performance, process when pH value is relied on to larger benzene homologues, and effect is remarkable, has avoided load TiO
2the degraded of the polymer film of nano particle, prevents that particle from reuniting again, has effectively avoided the reduction of photocatalytic activity.
Accompanying drawing explanation
Fig. 1 is nano-TiO before and after modification
2phenol concentration curve map over time while disposing waste liquid middle phenol;
Fig. 2 is nano-TiO before and after modification
2parachlorophenol concentration curve map over time while disposing waste liquid middle parachlorophenol;
Fig. 3 is nano-TiO before and after modification
2paracide concentration curve map over time while disposing waste liquid middle paracide;
Fig. 4 is for using unmodified nano-TiO
2with the nano-TiO after the alpha-olefin sulfonic acid modified of different carbon number range
2in disposing waste liquid 1,2, during 4-trichloro-benzenes 1,2,4-trichloro-benzenes concentration is curve map over time;
Fig. 5 is in waste liquid 1,2, and 4-trichloro-benzenes is at the absorbance curve map of different degradation times;
Fig. 6 is in waste liquid 1,2, and 4-trichloro-benzenes is at the emulsion droplet grading curve figure of different degradation times;
Fig. 7 is during finished product of the present invention disposes waste liquid 1,2, and during 4-trichloro-benzenes, emulsion droplet particle diameter is with the change curve of solution temperature;
Fig. 8 is during finished product of the present invention disposes waste liquid 1,2, and during 4-trichloro-benzenes, emulsion droplet particle diameter is with the change curve of pH.
The specific embodiment
Benzene homologues of the present invention is benzene, toluene, ortho-xylene, meta-xylene, paraxylene, nitrobenzene, phenol, chlorobenzene, parachlorophenol, o-chlorphenol, m-Chlorophenol, aniline, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), o-chloraniline, m-chloroaniline, parachloroanilinum, o-dichlorohenzene, m-dichlorobenzene, paracide, 2,3-dichloroaniline, 3,4-DCA, 3,5-dichloroaniline, 2,4-chlorophenesic acid, 2,6-chlorophenesic acid, 1,2,4-trichloro-benzenes, 1,3,5-trichloro-benzenes, 1,2,3-trichloro-benzenes, 2,3,4-trichlorophenol, 2,4,6,-T, 2,4,5-trichlorophenol, 2,4,6,-T, 2,4,6-trichlorophenol, 2,4,6,-T, 3,4,5-trichlorophenol, 2,4,6,-T, 3,4,6-trichlorophenol, 2,4,6,-T, 1,2,3,4-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, 2,3,4,5-tetrachlorophenol, 2,3,4,6-tetrachlorophenol, 2,3,5,6-tetrachlorophenol, 1,2,3,4,5-pentachlorobenzene, pentachloroaniline, nitro pentachlorobenzene, pentachlorophenol, hexachloro-benzene, 2-chlorohydroquinone, 4-chloro resorcinol, 4-chlorine catechol, the chloro-Resorcinol of 2-, one or more in Polychlorinated biphenyls.
In the present invention, alpha-olefin sulfonic acid is respectively total carbon number be the alpha-olefin sulfonic acid of C12-C14, the alpha-olefin sulfonic acid of the alpha-olefin sulfonic acid of C14-C16, C16-C18, the alpha-olefin sulfonic acid of C18-C20 by Nanjing Yangzi petrochemical industry Co., Ltd, supply with.
Below in conjunction with embodiment, further set forth the present invention, but the present invention is not only confined to following embodiment.
Embodiment 1
(1) 100g CCl is being housed
4reactor in add 5.00g nano-TiO
2powder, after ultrasonic dispersion stirs, stirs and is warming up to 80 ℃; By 2.50g PCl
3be dissolved in 50g CCl
4in, mix, by PCl
3cCl
4solution adds in reactor, dropwises and is warming up to 90 ℃, and reaction 2h, removes the CCl in reactant liquor
4and reclaim, obtaining yellow transparent powder is powder I;
(2) in reactor, adding successively 80g carbon number is alpha-olefin sulfonic acid, the 80g benzene of C12-C14, stirring is warming up to 130 ℃, every 1h sample analysis sulfonic acid content, treat alpha-olefin sulfonic acid content constant, obtain brown liquid phenyl-(12-14) alkyl sulfonic acid; Be cooled to 10 ℃, continue to stir, drip 400g oleum, dropwise stirring at room reaction 2h, drip 240g0.2molL
-1watery hydrochloric acid, add mass fraction to be that 20% the NaOH aqueous solution to solution is neutral, treatment fluid is revolved to steaming, residue paste is dissolved in 320g absolute ethyl alcohol, filter, get filtrate and again revolve steaming, remove ethanol and obtain white paste and be 4-sodium sulfonate group-phenyl-(12-14) sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-(12-14) sodium alkyl sulfonate;
(3) by products therefrom, 20g CCl in 1.00g step (2)
4and 2.00g Br
2add successively reactor, be heated to reflux, reaction 12h, the NaHCO that is 9% with 50g mass fraction successively
3the aqueous solution, 100g distilled water, the water washing of 100g saturated common salt, dry concentrated that buff solid is 4-sodium sulfonate group-phenyl-(11-13)-bromo-(12-14) sodium alkyl sulfonate;
(4) by 3.33g magnesium metal 2molL
-1hydrochloric acid treatment surface black oxide is to vivid silvery white, with absolute ethyl alcohol and absolute ether, clean successively, magnesium metal is poured in the reactor that fills 50g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(11-13)-bromo-(12-14) sodium alkyl sulfonate solid, be stirred to magnesium total overall reaction complete, add successively 6.67mg two (1,3-diphenylphosphine) propyl group Nickel Chloride and 3.33g step (1) products therefrom, backflow 15h, pours mixed liquor into the 2molL of 300g5 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, 700g distilled water washing for filter cake, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photochemical catalyst finished product.
Embodiment 2
(1) 85g CCl is being housed
4reactor in add 5.00g nano-TiO
2powder, after ultrasonic dispersion stirs, stirs and is warming up to 80 ℃; By 2.20g PCl
3be dissolved in 40g CCl
4in, mix, by PCl
3cCl
4solution adds in reactor, dropwises and is warming up to 90 ℃, and reaction 3h, removes the CCl in reactant liquor
4and reclaim, obtaining yellow transparent powder is powder I;
(2) in reactor, adding successively 80g carbon number is alpha-olefin sulfonic acid, the 68g benzene of C14-C16, stirring is warming up to 130 ℃, every 1h sample analysis sulfonic acid content, treat alpha-olefin sulfonic acid content constant, obtain brown liquid phenyl-(14-16) alkyl sulfonic acid; Be cooled to 20 ℃, continue to stir, drip 325g oleum, dropwise stirring at room reaction 2.5h, drip 190g0.2molL
-1watery hydrochloric acid, add mass fraction to be that 20% the NaOH aqueous solution to solution is neutral, treatment fluid is revolved to steaming, residue paste is dissolved in 260g absolute ethyl alcohol, filter, get filtrate and again revolve steaming, remove ethanol and obtain white paste and be 4-sodium sulfonate group-phenyl-(14-16) sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-(14-16) sodium alkyl sulfonate;
(3) by products therefrom, 25g CCl in 1.00g step (2)
4and 3.00g Br
2add successively reactor, be heated to reflux, reaction 16h, the NaHCO that is 9% with 100g mass fraction successively
3the aqueous solution, 180g distilled water, the water washing of 150g saturated common salt, dry concentrated that buff solid is 4-sodium sulfonate group-phenyl-(13-15)-bromo-(14-16) sodium alkyl sulfonate;
(4) by 2.50g magnesium metal 2molL
-1hydrochloric acid treatment surface black oxide is to vivid silvery white, with absolute ethyl alcohol and absolute ether, clean successively, magnesium metal is poured in the reactor that fills 40g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(13-15)-bromo-(14-16) sodium alkyl sulfonate solid, be stirred to magnesium total overall reaction complete, add successively 6.00mg two (1,3-diphenylphosphine) propyl group Nickel Chloride and 3.00g step (1) products therefrom, backflow 18h, pours mixed liquor into the 2molL of 250g10 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, 650g distilled water washing for filter cake, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photochemical catalyst finished product.
Embodiment 3
(1) 65g CCl is being housed
4reactor in add 5.00g nano-TiO
2powder, after ultrasonic dispersion stirs, stirs and is warming up to 80 ℃; By 2.00g PCl
3be dissolved in 35g CCl
4in, mix, by PCl
3cCl
4solution adds in reactor, dropwises and is warming up to 90 ℃, and reaction 4h, removes the CCl in reactant liquor
4and reclaim, obtaining yellow transparent powder is powder I;
(2) in reactor, adding successively 80g carbon number is alpha-olefin sulfonic acid, the 56g benzene of C16-C18, stirring is warming up to 130 ℃, every 1h sample analysis sulfonic acid content, treat alpha-olefin sulfonic acid content constant, obtain brown liquid phenyl-(16-18) alkyl sulfonic acid; Be cooled to 10 ℃, continue to stir, drip 296g oleum, dropwise stirring at room reaction 3h, drip 156g0.2molL
-1watery hydrochloric acid, add mass fraction to be that 20% the NaOH aqueous solution to solution is neutral, treatment fluid is revolved to steaming, residue paste is dissolved in 208g absolute ethyl alcohol, filter, get filtrate and again revolve steaming, remove ethanol and obtain white paste and be 4-sodium sulfonate group-phenyl-(16-18) sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-(16-18) sodium alkyl sulfonate;
(3) by products therefrom, 35g CCl in 1.00g step (2)
4and 4.00g Br
2add successively reactor, be heated to reflux, reaction 20h, the NaHCO that is 9% with 150g mass fraction successively
3the aqueous solution, 250g distilled water, the water washing of 190g saturated common salt, dry concentrated that buff solid is 4-sodium sulfonate group-phenyl-(15-17)-bromo-(16-18) sodium alkyl sulfonate;
(4) by 1.50g magnesium metal 2molL
-1hydrochloric acid treatment surface black oxide is to vivid silvery white, with absolute ethyl alcohol and absolute ether, clean successively, magnesium metal is poured in the reactor that fills 30g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(15-17)-bromo-(16-18) sodium alkyl sulfonate solid, be stirred to magnesium total overall reaction complete, add successively 5.50mg two (1,3-diphenylphosphine) propyl group Nickel Chloride and 2.80g step (1) products therefrom, backflow 20h, pours mixed liquor into the 2molL of 200g5 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, 580g distilled water washing for filter cake, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photochemical catalyst finished product.
Embodiment 4
(1) 50g CCl is being housed
4reactor in add 5.00g nano-TiO
2powder, after ultrasonic dispersion stirs, stirs and is warming up to 80 ℃; By 1.67g PCl
3be dissolved in 25g CCl
4in, mix, by PCl
3cCl
4solution adds in reactor, dropwises and is warming up to 90 ℃, and reaction 3h, removes the CCl in reactant liquor
4and reclaim, obtaining yellow transparent powder is powder I;
(2) in reactor, adding successively 80g carbon number is alpha-olefin sulfonic acid (), the 40g benzene of C18-C20, stirring is warming up to 130 ℃, every 1h sample analysis sulfonic acid content, treat alpha-olefin sulfonic acid content constant, obtain brown liquid phenyl-(18-20) alkyl sulfonic acid; Be cooled to 20 ℃, continue to stir, drip 240g oleum, dropwise stirring at room reaction 2.5h, drip 80g0.2molL
-1watery hydrochloric acid, add mass fraction to be that 20% the NaOH aqueous solution to solution is neutral, treatment fluid is revolved to steaming, residue paste is dissolved in 160g absolute ethyl alcohol, filter, get filtrate and again revolve steaming, remove ethanol and obtain white paste and be 4-sodium sulfonate group-phenyl-(18-20) sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-(18-20) sodium alkyl sulfonate;
(3) by products therefrom, 40g CCl in 1.00g step (2)
4and 5.00g Br
2add successively reactor, be heated to reflux, reaction 16h, the NaHCO that is 9% with 200g mass fraction successively
3the aqueous solution, 300g distilled water, the water washing of 200g saturated common salt, dry concentrated that buff solid is 4-sodium sulfonate group-phenyl-(17-19)-bromo-(18-20) sodium alkyl sulfonate;
(4) by 1.00g magnesium metal 2molL
-1hydrochloric acid treatment surface black oxide is to vivid silvery white, with absolute ethyl alcohol and absolute ether, clean successively, magnesium metal is poured in the reactor that fills 20g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(17-19)-bromo-(18-20) sodium alkyl sulfonate solid, be stirred to magnesium total overall reaction complete, add successively 5.00mg two (1,3-diphenylphosphine) propyl group Nickel Chloride and 2.50g step (1) products therefrom, backflow 18h, pours mixed liquor into the 2molL of 150g10 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, 500g distilled water washing for filter cake, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photochemical catalyst finished product.
In the present invention, part material and the structural formula that respectively walks product see the following form 1:
Part material and respectively walk the structural formula of product in table 1 the present invention
1, use respectively unmodified nano-TiO
2high concentration benzene homologues in the modified nano-titanium dioxide photocatalyst treatment waste water that powder and the present invention make
(1), process the phenol in waste water
At 30 ℃, by the unmodified nano-TiO of 0.12g
2powder and 0.12g embodiment 1 gained finished product add respectively in the phenol solution that two groups of 50mL concentration are 100000mg/L, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, under illumination, rotating speed with 180r/min stirs 24.0h, be 0.25h/ sample time, treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect the absorbance of residual phenol, calculate its relative concentration (relative value of actual concentrations and saturated concentration, with %, represent), and draw relative concentration curve over time.As seen from Figure 1, use unmodified nano-TiO
2after powder handling, the relative concentration after 2.75h reaches 10.0%, and with the nano-TiO after modification
2after powder handling, 1.0h can be degradable.
(2), process the parachlorophenol in waste water
At 30 ℃, by the unmodified nano-TiO of 0.12g
2powder and 0.12g embodiment 1 gained finished product add respectively in the parachlorophenol solution that two groups of 50mL concentration are 100000mg/L, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, under illumination, rotating speed with 180r/min stirs 24.0h, be 2.0h/ sample time, treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect the absorbance of residual parachlorophenol, calculate its relative concentration, and draw relative concentration curve over time.As seen from Figure 2, use unmodified nano-TiO
2after powder handling, the relative concentration after 10.0h reaches 85.2%, and with the nano-TiO after modification
2after powder handling, it is degradable that 8.0h can reach.
(3), process the paracide in waste water
At 30 ℃, by the unmodified nano-TiO of 0.12g
2powder and 0.12g embodiment 1 gained finished product add respectively in the paracide solution that two groups of 50mL concentration are 100000mg/L, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, under illumination, rotating speed with 180r/min stirs 24.0h, be 1.0h/ sample time, treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect the absorbance of residual paracide, calculate its relative concentration, and draw relative concentration curve over time.As seen from Figure 3, use unmodified nano-TiO
2after powder handling, the relative concentration after 7.0h reaches 93.5%, and with the nano-TiO after modification
2after powder handling, 4.0h can be degradable.
2, utilize 1,2 in gained finished product degrading high concentration waste water in embodiment 1-4,4-trichloro-benzenes
(1), control group
At 30 ℃, by the unmodified nano-TiO of 0.12g
2it is 1 of 100000mg/L that powder adds 50mL concentration, 2, in 4-trichloro-benzenes solution, without under optical condition with 180r/min rotating speed under constant temperature stir 10min, under illumination, rotating speed with 180r/min stirs 24.0h, be 2.0h/ sample time, treatment fluid carried out under 600r/min rotating speed to centrifugation, reclaims photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect residual 1,2, the absorbance of 4-trichloro-benzenes, calculate its relative concentration, and draw relative concentration curve over time.As seen from Figure 4, the relative concentration after 22.0h reach 33.6%, 24.0h can be degradable;
(2), utilize 1,2 in embodiment 1 gained finished product degrading high concentration waste water, 4-trichloro-benzenes
At 30 ℃, it is 1 of 100000mg/L that 0.12g embodiment 1 gained finished product is added to 50mL concentration, 2, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, under illumination, with the rotating speed stirring 24.0h of 180r/min, be 2.0h/ sample time, treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect residual 1,2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration, and draws relative concentration curve over time.As seen from Figure 4, the relative concentration after 8.0h reach 5.8%, 10.0h can be degradable.
(3), utilize 1,2 in embodiment 2 gained finished product degrading high concentration waste water, 4-trichloro-benzenes
At 30 ℃, it is 1 of 100000mg/L that 0.12g embodiment 2 gained finished products are added to 50mL concentration, 2, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, under illumination, with the rotating speed stirring 24.0h of 180r/min, be 2.0h/ sample time, treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect residual 1,2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration, and draws relative concentration curve over time.As seen from Figure 4, the relative concentration after 8.0h reach 4.3%, 10.0h can be degradable.
(4), utilize 1,2 in embodiment 3 gained finished product degrading high concentration waste water, 4-trichloro-benzenes
At 30 ℃, it is 1,2 of 100000mg/L that 0.12g embodiment 3 gained finished products are added to 50mL concentration, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, utilize zeta current potential nano particle size instrument to measure the particle diameter distribution of the emulsion of preparation; Under illumination, rotating speed with 180r/min stirs 24.0h, be 2.0h/ sample time, treatment fluid carried out under 600r/min rotating speed to centrifugation, reclaims photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect residual 1,2, the absorbance of 4-trichloro-benzenes, calculate its relative concentration, and draw relative concentration curve over time.As seen from Figure 4, the relative concentration after 6.0h reach 13.3%, 8.0h can be degradable; Detect the supernatant absorbance when 2.0h, 4.0h, 6.0h, 7.0h and 8.0h respectively, see Fig. 5, as shown in Figure 5, because solution is supersaturated solution, therefore curve initial, 2h, 4h overlaps, after 8h, the absorption of 200-210nm no longer occurs, benzene homologues degraded completely; When initial, 2.0h and 4.0h, the particle diameter of emulsion distributes and sees Fig. 6, as shown in Figure 6, emulsion droplet particle size range is between 3-30 μ m, and average grain diameter is respectively 22 μ m, 14 μ m and 5 μ m, after 6.0h, particle diameter distribution map no longer occurs, high concentration emulsion droplet diminishes gradually to disappearance.
(5), utilize 1,2 in embodiment 4 gained finished product degrading high concentration waste water, 4-trichloro-benzenes
At 30 ℃, it is 1 of 100000mg/L that 0.12g embodiment 4 gained finished products are added to 50mL concentration, 2, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, under illumination, with the rotating speed stirring 24.0h of 180r/min, be 2.0h/ sample time, treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect residual 1,2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration, and draws relative concentration curve over time.As seen from Figure 4, the relative concentration after 8.0h reach 3.1%, 10.0h can be degradable.
As seen from Figure 4, with unmodified nano-TiO
2powder is compared, and embodiment 1-4 gained modified light catalyst all has higher catalytic activity, and when 6.0-8.0h, to 1,2 in solution, 4-trichloro-benzenes has comparatively ideal degradation efficiency, and wherein embodiment 3 gained modified catalyst effects are better.
3, investigate the impact of solution temperature on modified light catalyst activity
By 0.12g embodiment 3 gained finished products, to add a series of 50mL concentration be 100000mg/L 1,2, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, utilize zeta current potential nano particle size instrument to measure the particle diameter distribution of the emulsion of preparation; Temperature control is 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃ respectively, and under illumination, with the rotating speed stirring 4.0h of 180r/min, the particle diameter that sampling detects emulsion distributes, and draws emulsion droplet average grain diameter variation with temperature curve.As seen from Figure 7, modified light catalyst optimum temperature when degraded 1,2,4-trichloro-benzenes is 35 ℃, and emulsion droplet particle diameter is minimum at this moment, and the activity of photochemical catalyst is the highest at this moment.
4, investigate the impact of pH on modified light catalyst activity
By 0.12g embodiment 3 gained finished products, to add a series of 50mL concentration be 100000mg/L 1,2, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, utilize zeta current potential nano particle size instrument to measure the particle diameter distribution of the emulsion of preparation; In pH value, be 3,5,7,9,11 respectively, under illumination, with the rotating speed stirring 4.0h of 180r/min, the particle diameter that sampling detects emulsion distributes, and draws emulsion droplet average grain diameter with the change curve of pH value.As seen from Figure 8, modified light catalyst optimum pH value when degraded 1,2,4-trichloro-benzenes is 5, and emulsion droplet particle diameter is at this moment less, and the activity of photochemical catalyst is the highest at this moment.
5, the reusability of modified light catalyst of the present invention
At 30 ℃, by the unmodified nano-TiO of 0.12g
2it is 100000mg/L 1 that powder and 0.12g embodiment 3 gained finished products add respectively two groups of 50mL concentration, 2, in 4-trichloro-benzenes solution, without stirring 10min with 180r/min rotating speed constant temperature under optical condition, the former is 8.0h, 24.0h sample time, under illumination, with the rotating speed stirring reaction of 180r/min, be 8.0h sample time, after treatment fluid is carried out under 600r/min rotating speed to centrifugation, reclaim after photocatalyst powder, get its supernatant liquor, with UV-6 type ultraviolet-visible spectrophotometer, detect residual 1,2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration.Catalyst muffin is after 300Pa and 120 ℃ are dry, and again it to be added respectively to two groups of 50mL concentration be 100000mg/L 1,2, in 4-trichloro-benzenes solution, the like, the reusability of photochemical catalyst is investigated, the results are shown in Table 2.
Table 2 modified light catalyst reusability of the present invention data
From table 2, unmodified nano-TiO
2powder is when 8.0h, and in solution 1,2, the concentration of 4-trichloro-benzenes is about 100.00%, is saturated concentration, even if just can reach degradable to 1,2,4-trichloro-benzenes when 24.0h, and gained modified Nano TiO of the present invention
2when 8.0h, in solution 1,2, the relative concentration of 4-trichloro-benzenes is 0.00%, reaches degradable, and along with reusing the increase of number of times, its activity remains unchanged substantially, illustrate that product of the present invention has good catalytic activity and stability, to processing the industrial wastewater of the benzo pollutants of high concentration, difficult degradation, complicated component, have good effect, can realize efficient, qualified discharge.
Claims (7)
1. modified nano-titanium dioxide photochemical catalyst, is characterized in that being prepared and being obtained by following steps:
1) by nano-TiO
2powder adds CCl
4in, after stirring, be warming up to 80 ℃, obtain mixture A; By PCl
3be dissolved in CCl
4in, mix, by PCl
3cCl
4solution drops in mixture A, after be warming up to 90 ℃, reaction 2-4 h, reclaims the CCl in reactant liquor
4, obtain powder I, wherein: CCl
4, nano-TiO
2powder, PCl
3, PCl
3cCl
4the mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10);
2) benzene is added in alpha-olefin sulfonic acid, stir and be warming up to 130 ℃, treat alpha-olefin sulfonic acid content constant, obtain phenylalkyl sulfonic acid; Be cooled to 10 ℃-20 ℃, continue to stir, drip oleum, dropwise, stirring reaction 2-3 h at 25 ℃, drips 0.2 molL
-1watery hydrochloric acid, after to add mass fraction be 20% the NaOH aqueous solution, to solution, be neutral, except desolventizing, obtain paste II, paste II is dissolved in absolute ethyl alcohol, filter, get filtrate, except desolventizing, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-sodium alkyl sulfonate, wherein: the mass ratio of alpha-olefin sulfonic acid, benzene, oleum, watery hydrochloric acid, absolute ethyl alcohol is 1:(1/2-1): (3-5): (1-3): (2-4);
3) by step 2) gained 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4and Br
2add successively reactor, be heated to reflux, reaction 12-20h, the NaHCO that is 9% with mass fraction successively
3the aqueous solution, distilled water, saturated common salt water washing, dry, obtain 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, wherein: 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4, Br
2, NaHCO
3the mass ratio of the aqueous solution, distilled water, saturated aqueous common salt is 1: (20-40): (2-5): (50-200): (100-300): (100-200);
4) use the oxide of salt acid treatment metallic magnesium surface, with absolute ethyl alcohol and absolute ether, clean successively, after magnesium metal is poured in the reactor that fills absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, be stirred to magnesium total overall reaction, add successively two (1,3-diphenylphosphine) propyl group Nickel Chlorides and step 1) gained powder I, backflow 15-20 h, pours reactant liquor into 2 molL of 5 ℃-10 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photochemical catalyst finished product, wherein: the mass ratio of the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, two (1,3-diphenylphosphine) propyl group Nickel Chloride, step 1) products therefrom, aqueous hydrochloric acid solution and water is (1/10-1/3): (2-5): 1: (1/1500-1/2000): (1/3-1/4): (15-30): (50-70).
2. the preparation method of modified nano-titanium dioxide photochemical catalyst, is characterized in that comprising the following steps:
1) by nano-TiO
2powder adds CCl
4in, after stirring, be warming up to 80 ℃, obtain mixture A; By PCl
3be dissolved in CCl
4in, mix, by PCl
3cCl
4solution drops in mixture A, after be warming up to 90 ℃, reaction 2-4 h, reclaims the CCl in reactant liquor
4, obtain powder I, wherein: CCl
4, nano-TiO
2powder, PCl
3, PCl
3cCl
4the mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10);
2) benzene is added in alpha-olefin sulfonic acid, stir and be warming up to 130 ℃, treat alpha-olefin sulfonic acid content constant, obtain phenylalkyl sulfonic acid; Be cooled to 10 ℃-20 ℃, continue to stir, drip oleum, dropwise, stirring reaction 2-3 h at 25 ℃, drips 0.2 molL
-1watery hydrochloric acid, after to add mass fraction be 20% the NaOH aqueous solution, to solution, be neutral, except desolventizing, obtain paste II, paste II is dissolved in absolute ethyl alcohol, filter, get filtrate, except desolventizing, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, must refine 4-sodium sulfonate group-phenyl-sodium alkyl sulfonate, wherein: the mass ratio of alpha-olefin sulfonic acid, benzene, oleum, watery hydrochloric acid, absolute ethyl alcohol is 1:(1/2-1): (3-5): (1-3): (2-4);
3) by step 2) gained 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4and Br
2add successively reactor, be heated to reflux, reaction 12-20h, the NaHCO that is 9% with mass fraction successively
3the aqueous solution, distilled water, saturated common salt water washing, dry, obtain 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, wherein: 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl
4, Br
2, NaHCO
3the mass ratio of the aqueous solution, distilled water, saturated aqueous common salt is 1: (20-40): (2-5): (50-200): (100-300): (100-200);
4) use the oxide of salt acid treatment metallic magnesium surface, with absolute ethyl alcohol and absolute ether, clean successively, after magnesium metal is poured in the reactor that fills absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, be stirred to magnesium total overall reaction, add successively two (1,3-diphenylphosphine) propyl group Nickel Chlorides and step 1) gained powder I, backflow 15-20 h, pours reactant liquor into 2 molL of 5 ℃-10 ℃
– 1aqueous hydrochloric acid solution in, suction filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photochemical catalyst finished product, wherein: the mass ratio of the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, two (1,3-diphenylphosphine) propyl group Nickel Chloride, step 1) products therefrom, aqueous hydrochloric acid solution and water is (1/10-1/3): (2-5): 1: (1/1500-1/2000): (1/3-1/4): (15-30): (50-70).
3. the preparation method of modified nano-titanium dioxide photochemical catalyst as claimed in claim 2, is characterized in that PCl described in step 1)
3cCl
4the rate of addition of solution is 0.13333-0.26667g/min, step 2) described in oleum and 0.2 molL
-1the rate of addition of watery hydrochloric acid is 0.16667-0.33333 g/min.
4. the preparation method of modified nano-titanium dioxide photochemical catalyst as claimed in claim 2, is characterized in that described nano-TiO
2the particle diameter < 20nm of powder.
5. the preparation method of modified nano-titanium dioxide photochemical catalyst as claimed in claim 2, the carbon number range that it is characterized in that described alpha-olefin sulfonic acid is C12-C20.
6. the application of modified nano-titanium dioxide photochemical catalyst claimed in claim 1 in the wastewater treatment of high concentration benzene homologues.
7. the application of modified nano-titanium dioxide photochemical catalyst as claimed in claim 6 in the wastewater treatment of high concentration benzene homologues, is characterized in that described benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106049179A (en) * | 2016-07-28 | 2016-10-26 | 福建中烟工业有限责任公司 | Method for reducing pentachlorophenol or its salts in paper material |
| CN109225188A (en) * | 2018-09-14 | 2019-01-18 | 湘潭大学 | A kind of efficient Three-element composite photocatalyst and preparation method thereof for sun optical drive |
| CN110882719A (en) * | 2019-12-13 | 2020-03-17 | 谢绵锐 | Photocatalyst for treating phenol wastewater and preparation method and treatment method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4214913A (en) * | 1979-03-05 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Process for producing rutile TiO2 |
| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| CN101985363A (en) * | 2010-10-25 | 2011-03-16 | 江苏考普乐新材料股份有限公司 | Nano titania and preparation method thereof |
-
2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4214913A (en) * | 1979-03-05 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Process for producing rutile TiO2 |
| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| CN101985363A (en) * | 2010-10-25 | 2011-03-16 | 江苏考普乐新材料股份有限公司 | Nano titania and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106049179A (en) * | 2016-07-28 | 2016-10-26 | 福建中烟工业有限责任公司 | Method for reducing pentachlorophenol or its salts in paper material |
| CN109225188A (en) * | 2018-09-14 | 2019-01-18 | 湘潭大学 | A kind of efficient Three-element composite photocatalyst and preparation method thereof for sun optical drive |
| CN110882719A (en) * | 2019-12-13 | 2020-03-17 | 谢绵锐 | Photocatalyst for treating phenol wastewater and preparation method and treatment method thereof |
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