CN103464214A - Modified nano TiO2 photocatalyst capable of degrading benzene series, and preparation method and application of same - Google Patents
Modified nano TiO2 photocatalyst capable of degrading benzene series, and preparation method and application of same Download PDFInfo
- Publication number
- CN103464214A CN103464214A CN2013103673812A CN201310367381A CN103464214A CN 103464214 A CN103464214 A CN 103464214A CN 2013103673812 A CN2013103673812 A CN 2013103673812A CN 201310367381 A CN201310367381 A CN 201310367381A CN 103464214 A CN103464214 A CN 103464214A
- Authority
- CN
- China
- Prior art keywords
- tio
- modified nano
- mass fraction
- aqueous solution
- benzene homologues
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The invention provided a modified nano TiO2 photocatalyst capable of degrading benzene series, and a preparation method and application of the modified nano TiO2 photocatalyst. The modified nano TiO2 photocatalyst is prepared by the following steps: step 1, adding an organic solvent, nanometer TiO2 powder and hexadecyl trimethyl ammonium bromide into a reactor, stirring the mixture to be uniform, heating to increase the temperature up to 90-130 DEG C, dripping epoxide, continuously reacting for 2.5-8.0 hours, cooling liquid reactant after finishing the reaction, dripping a KOH aqueous solution under the condition of stirring, adding water for dissolving generated salt, performing suction filtration, washing filter cakes with distilled water, and drying; step 2, sequentially adding a product obtain in the step 1, a methyl sulfoxide aqueous solution, methylene chloride and a perchloric acid aqueous solution, stirring for 36 hours at room temperature, diluting liquid reactant by ethyl acetate, performing water washing and drying to obtain a finished product. The photocatalyst provided by the invention has relatively high activity, and is high in degradation rate of pollutants of the benzene series, high in reutilization, and widely used in treatment of the pollutants of the benzene series.
Description
Technical field
The invention belongs to catalytic oxidant and preparing technical field thereof, particularly a kind of modified Nano TiO of degradable benzene homologues
2photochemical catalyst and its preparation method and application.
Background technology
Benzene homologues belongs to the toxic organic pollutant of difficult degradation, be widely used in the industries such as medicine, agricultural chemicals, papermaking, washing agent, printing ink, leather, high-grade paint, plastics, dyestuff and household chemicals, with different concentration, be prevalent in water body, soil, air, by breathing, food with directly contact and enter in people's carcass, cause " three cause " disease.
The environmental treatment method of benzene homologues has absorption method, activated sludge process, electrochemistry and catalytic oxidation.Detitanium-ore-type TiO
2have that catalytic activity is higher, stable chemical nature, safety, the advantage such as cheap, can induce H under the solar radiation condition
2the O molecular ionization goes out hydroxyl free radical (OH), can decompose nearly all organic pollution, generates CO
2and H
2o is one of environmental protection catalyst had most DEVELOPMENT PROSPECT.By TiO
2the ultra-fine nanomorphic that changes into can also improve its photocatalytic activity greatly, but the nano-titania particle specific area is large, the 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 enrichment As(III in remarkable increase carp body), the As(V) and the risk of Cd etc.; In addition, nano-TiO
2particle also has the risk of the genetic damage of causing.
Possesses highly active load type photocatalytic material and preparation method thereof but prior art is as a kind of in Chinese patent CN102205253 has announced under visible ray: first by sol-gel process, prepare PVA-TiO
2composite membrane, combine with chemical bond between polymer and inorganic matter, forms the network structure be cross-linked with each other, then be carried on various inorganic carriers.This composite has developed TiO
2band gap, widened the photoresponse scope, improved the utilization ratio of sunshine, and preparation technology is simple, fast and easy, filming performance is good, save cost, but still, a little less than existing the load active force, in recycling process for a long time, can't avoids TiO
2the deficiency that nano particle runs off; Chinese patent CN102527439 has announced a kind of polymer/TiO with photocatalytic activity
2the preparation method of hybridized film, 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 the conventional load method insoluble in long-term use procedure TiO
2the losing issue of nano particle, guarantee higher photocatalytic activity in long-term the use, and technique is simple, but the basement membrane fibre diameter of its 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 modified Nano TiO that the objective of the invention is to overcome the deficiencies in the prior art and propose a kind of degradable benzene homologues
2photochemical catalyst and its preparation method and application, the present invention has good decentralized photo capacitive in water-based system, high to the benzo pollutants degradation rate, but reusing is strong, is widely used in the processing of benzo pollutants.
Technical scheme of the present invention:
The modified Nano TiO of degradable benzene homologues
2photochemical catalyst is characterized in that being obtained by the following steps preparation:
(1) in being housed, the reactor of organic solvent adds successively nano-TiO
2powder, softex kw, after ultrasonic dispersion stirs, stir and be warming up to 90-130 ℃, drip epoxides, dropwise and continue reaction 2.5-8.0h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring mass fraction be 50%, the salt that is dissolved in water and generates, suction filtration, filter cake washs with distilled water, drying, wherein: organic solvent, nano-TiO
2the mass ratio of the KOH aqueous solution, dissolved water and distilled water that powder, softex kw, epoxides, mass fraction are 50% is (3-10): 1:(1/100-1/25): (1/20-1/2): (1-20): (2-10): (30-100).
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, carrene, mass fraction that step (1) products obtained therefrom, mass fraction are 70% are 80% in reactor, stirring at room 36h, reactant liquor is diluted with ethyl acetate, washing, dry white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product, wherein: the mass ratio of high chloro acid solution, ethyl acetate and water that the methyl-sulfoxide aqueous solution, carrene, the mass fraction that the step added (1) products obtained therefrom, mass fraction are 70% is 80% is 1:(30-100): (20-100): (1/30-1/10): (50-100): (40-100).
The modified Nano TiO of degradable benzene homologues
2the preparation method of photochemical catalyst comprises the following steps:
(1) in being housed, the reactor of organic solvent adds successively nano-TiO
2powder, softex kw, after ultrasonic dispersion stirs, stirring is warming up to 90-130 ℃, drip epoxides, dropwise and continue reaction 2.5-8.0h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring mass fraction be 50%, the salt that is dissolved in water and generates, suction filtration, filter cake washs with distilled water, dry, wherein: organic solvent, the nano TiO 2 powder, softex kw, epoxides, the KOH aqueous solution that mass fraction is 50%, the mass ratio of dissolved water and distilled water is (3-10): 1:(1/100-1/25): (1/20-1/2): (1-20): (2-10): (30-100).
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, carrene, mass fraction that step (1) products obtained therefrom, mass fraction are 70% are 80% in reactor, stirring at room 36h, reactant liquor is diluted with ethyl acetate, washing, dry, obtain white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product, wherein: the mass ratio of high chloro acid solution, ethyl acetate and water that the methyl-sulfoxide aqueous solution, carrene, the mass fraction that the step added (1) products obtained therefrom, mass fraction are 70% is 80% is 1:(30-100): (20-100): (1/30-1/10): (50-100): (40-100).
Described in step (1), organic solvent is toluene or paraxylene.
Described in step (1), the rate of addition of epoxides is 0.00417-0.04167g/min.
Described nano-TiO
2particle diameter<the 20nm of powder.
Described epoxides is epoxychloropropane, methyl epichlorohydrin or 1,2-epoxy chlorobutane.
Modified Nano TiO
2photochemical catalyst is the application in benzene homologues in degrading waste water.
Described modified Nano TiO
2photochemical catalyst is the application in benzene homologues in degrading waste water, and described benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
The present invention's nano-TiO
2particle, as matrix, is grafted to particle surface by epoxides, improves its dispersion in water, the certain density simulation industrial wastewater that has of degrading and being made into benzene homologues (analyzing pure).Under certain condition, static placement or in addition mechanical agitation carry out degradation reaction, institute's simulated wastewater is degraded and removed benzo pollutants, then get treatment fluid on centrifuge, under certain rotating speed, carry out centrifugal after, get its supernatant liquor, measure the absorbance for the treatment of fluid with cuvette by UV-6 type ultraviolet-visible spectrophotometer, calculate the contaminant degradation rate.Change each factor that affects the degradation reaction effect, by investigating degradation rate, finally draw the optimum reaction condition of processing waste water.After simulated wastewater is degraded and removed benzo pollutants, photocatalyst powder is separated, recycling.
The present invention compared with prior art its remarkable advantage is:
(1) the present invention is grafted to nano-TiO by epoxides
2particle surface, improved dispersiveness and the compatibility of photochemical catalyst in water-based system, greatly improved activity, and in the process of degrading benzene thing, 10min can make the difficult degradation benzene homologues degradable after can reaching 98.21%, 110min to the degradation rate of benzene homologues;
(2) but modified light catalyst of the present invention has stronger reusing, still there is higher catalytic activity after being repeatedly used, after reusing 7 times, 60min still can reach 98.86% to the degradation rate of benzene homologues;
(3) preparation method's reaction condition gentleness of the present invention, preparation process is simple, easy to operate, can be widely used in the processing of benzo pollutants.
(4) the modified Nano TiO that prepared by this method
2after particle degrading benzene pollutant, through separating, reclaiming, recycle, also can continue evenly distributed by chemical solid support method and be distributed in filter membrane surface, improved that the load active force is weak, nano-TiO
2particle is the problem of loss easily, but has improved the reusing of membrane material.
The accompanying drawing explanation
Fig. 1 is nano-TiO
2before and after modification to Phenol in Aqueous Solution degradation rate curve over time;
Fig. 2 is nano-TiO
2before and after modification to the curve over time of parachlorophenol degradation rate in solution;
Fig. 3 is nano-TiO
2before and after modification to the curve over time of paracide degradation rate in solution;
Fig. 4 is unmodified nano-TiO
2with the nano-TiO with after the different rings oxide modifying
2to in solution 1,2,4-trichloro-benzenes degradation rate is curve over time;
Fig. 5 is in solution 1,2, and the 4-trichloro-benzenes is at the absorbance curve of different degradation times;
Fig. 6 is finished product of the present invention in solution 1,2, and the degradation rate of 4-trichloro-benzenes is with the change curve of solution temperature.
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, the nitro pentachlorobenzene, pentachlorophenol, hexachloro-benzene, the 2-chlorohydroquinone, the 4-chloro resorcinol, 4-chlorine catechol, the chloro-Resorcinol of 2-, one or more in Polychlorinated biphenyls.
Further set forth the present invention below in conjunction with embodiment, but the present invention not only is confined to following embodiment.
Embodiment 1
(1) add successively the 5.00g nano-TiO in the reactor that 15g toluene is housed
2powder, 0.05g softex kw, after ultrasonic dispersion stirs, stirring is warming up to 90 ℃, drips the 0.25g epoxychloropropane in 60min, dropwises and continues reaction 2.5h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring the 5g mass fraction be 50%, add the salt that the water-soluble solution of 10g generates, suction filtration, 150g distilled water washing for filter cake, in 300Pa and 120 ℃ of dry 5.0h;
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, 100g carrene, 0.1g mass fraction that 1.00g step (1) products obtained therefrom, 100g mass fraction are 70% are 80% in reactor, stirring at room 36h, by 100g ethyl acetate dilution for reactant liquor, with 100g water, wash, dry 5.0h under 300Pa and 120 ℃, obtain white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product.
Embodiment 2
(1) add successively the 5.00g nano-TiO in the reactor that 50g toluene is housed
2powder, 0.20g softex kw, after ultrasonic dispersion stirs, stirring is warming up to 110 ℃, drips the 2.50g methyl epichlorohydrin in 60min, dropwises and continues reaction 4.0h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring the 100g mass fraction be 50%, add the salt that the water-soluble solution of 50g generates, suction filtration, 500g distilled water washing for filter cake, in 300Pa and 120 ℃ of dry 5.0h;
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, 20g carrene, 0.033g mass fraction that 1.00g step (1) products obtained therefrom, 30g mass fraction are 70% are 80% in reactor, stirring at room 36h, by 50g ethyl acetate dilution for reactant liquor, with 40g water, wash, dry 5.0h under 300Pa and 120 ℃, obtain white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product.
Embodiment 3
(1) add successively the 5.00g nano-TiO in the reactor that the 30g paraxylene is housed
2powder, 0.10g softex kw, after ultrasonic dispersion stirs, stir and be warming up to 130 ℃, drip 0.50g1 in 60min, 2-epoxy chlorobutane, dropwise and continue reaction 8.0h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring the 50g mass fraction be 50%, add the salt that the water-soluble solution of 30g generates, suction filtration, 300g distilled water washing for filter cake, in 300Pa and 120 ℃ of dry 6.0h;
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, 30g carrene, 0.05g mass fraction that 1.00g step (1) products obtained therefrom, 40g mass fraction are 70% are 80% in reactor, stirring at room 36h, by 60g ethyl acetate dilution for reactant liquor, with 60g water, wash, dry 6.0h under 300Pa and 120 ℃, obtain white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product.
Application examples 1
Under 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 10.00mg/L, under illumination, rotating speed with 180r/min stirs 3.0h, be set as 10min/ sample time, treatment fluid carried out under the 600r/min rotating speed to centrifugation, reclaims photocatalyst powder, get its supernatant liquor, detect the absorbance of residual phenol with UV-6 type ultraviolet-visible spectrophotometer, calculate its concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 1, use unmodified nano-TiO
2after powder handling, the degradation rate after 30min reaches 98.56%, and with the nano-TiO after modification
2after powder handling, the degradation rate after 10min can reach 99.20%.
Application examples 2
Under 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 10.00mg/L, under illumination, rotating speed with 180r/min stirs 3.0h, be set as 10min/ sample time, treatment fluid carried out under the 600r/min rotating speed to centrifugation, reclaims photocatalyst powder, get its supernatant liquor, detect the absorbance of residual parachlorophenol with UV-6 type ultraviolet-visible spectrophotometer, calculate its concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 2, use unmodified nano-TiO
2after powder handling, the degradation rate after 180min reaches 99.98%, and with the nano-TiO after modification
2after powder handling, the degradation rate after 60min can reach 99.20%.
Application examples 3
Under 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 10.00mg/L, under illumination, rotating speed with 180r/min stirs 3.0h, be set as 10min/ sample time, treatment fluid carried out under the 600r/min rotating speed to centrifugation, reclaims photocatalyst powder, get its supernatant liquor, detect the absorbance of residual paracide with UV-6 type ultraviolet-visible spectrophotometer, calculate its concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 3, use unmodified nano-TiO
2after powder handling, the degradation rate after 60min reaches 100.00%, and with the nano-TiO after modification
2after powder handling, the degradation rate after 30min can reach 100%.
Application examples 4
Utilize 1,2 in gained finished product degrading waste water in embodiment 1-3, the 4-trichloro-benzenes.
Control group: under 30 ℃, by the unmodified nano-TiO of 0.12g
2powder 50mL concentration is 10.00mg/L 1,2, in 4-trichloro-benzenes solution, under illumination, with the rotating speed stirring 3.0h of 180r/min, be set as 10min/ sample time, treatment fluid is carried out under the 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, calculate its concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 4, the degradation rate after 60min is only that the degradation rate after 99.25%, 180min is 98.63%;
Under (1) 30 ℃, it is 1 of 10.00mg/L that 0.12g embodiment 1 gained finished product is added to 50mL concentration, 2, in 4-trichloro-benzenes solution, under illumination, rotating speed with 180r/min stirs 3.0h, be set as 10min/ sample time, treatment fluid carried out under the 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 concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 4, the degradation rate after 60min reaches 99.25%; Fig. 5 is shown in by the detection supernatant absorbance when 20min, 40min and 60min respectively, and as shown in Figure 5, after 60min, the absorption of 210nm no longer occurs, benzene homologues is degraded substantially fully.
Under (2) 30 ℃, by 0.12g embodiment 2 gained finished products, to add respectively two groups of 50mL concentration be 10.00mg/L 1,2, in 4-trichloro-benzenes solution, under illumination, rotating speed with 180r/min stirs 3.0h, be set as 10min/ sample time, treatment fluid carried out under the 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 concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 4, the degradation rate after 60min reaches 94.09%.
Under (3) 30 ℃, by 0.12g embodiment 3 gained finished products, to add respectively two groups of 50mL concentration be 10.00mg/L 1,2, in 4-trichloro-benzenes solution, under illumination, rotating speed with 180r/min stirs 3.0h, be set as 10min/ sample time, treatment fluid carried out under the 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 concentration and degradation rate, and draw degradation rate curve over time.As seen from Figure 4, the degradation rate after 60min reaches 96.83%.
As seen from Figure 4, with unmodified nano-TiO
2powder is compared, and embodiment 1-3 gained modified light catalyst all has higher catalytic activity, and when 60min, to 1,2 in solution, the 4-trichloro-benzenes has comparatively ideal degradation rate, and wherein embodiment 1 gained modified catalyst effect is better.
Application examples 5
Investigate the impact of solution temperature on the modified light catalyst activity.
By 0.12g embodiment 1 gained finished product, to add respectively a series of 50mL concentration be 10.00mg/L 1,2, in 4-trichloro-benzenes solution, temperature control is 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃ respectively, under illumination, rotating speed with 180r/min stirs 60min, treatment fluid is carried out under the 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, calculate its concentration and degradation rate, and draw degradation rate variation with temperature curve.As seen from Figure 6, modified light catalyst optimum temperature when degraded 1,2,4-trichloro-benzenes is 30-35 ℃, and the activity of photochemical catalyst is the highest at this moment.
Application examples 6
Under 30 ℃, by the unmodified nano-TiO of 0.12g
2it is 10.00mg/L 1,2 that powder and 0.12g embodiment 1 gained finished product add respectively two groups of 50mL concentration, in 4-trichloro-benzenes solution, under illumination, with the rotating speed of 180r/min stir, reaction, the former is respectively 60min, 180min sample time, the latter is 60min.Then treatment fluid is carried out under the 600r/min rotating speed to centrifugation, after reclaiming photocatalyst powder, get its supernatant liquor, detect residually 1,2 with UV-6 type ultraviolet-visible spectrophotometer, the absorbance of 4-trichloro-benzenes, calculate its concentration and degradation rate.The catalyst muffin is after 300Pa and 120 ℃ of dryings, and again it to be added respectively to two groups of 50mL concentration be 10.00mg/L 1,2, in 4-trichloro-benzenes solution, the like, the reusability of photochemical catalyst is investigated, the results are shown in Table 1.
Table 1 modified light catalyst reusability of the present invention data
From table 1, unmodified nano-TiO
2powder is lower to the degradation rate of 1,2,4-trichloro-benzenes at 60min, even its degradation rate to 1,2,4-trichloro-benzenes just can reach 98.64% when 180min, and after using 7 times, its activity decreases, and gained modified Nano TiO of the present invention
2at 60min to 1,2, the 4-trichloro-benzenes degradation rate can reach 99%, and along with the increase of reusing number of times, its activity remains unchanged substantially, illustrate that product of the present invention has good catalytic activity and stability, for continuing to carry out industrialization in filter membrane surface and use and laid good basis by chemistry is immobilized.
Claims (8)
1. the modified Nano TiO of degradable benzene homologues
2photochemical catalyst is characterized in that being obtained by the following steps preparation:
(1) in being housed, the reactor of organic solvent adds successively nano-TiO
2powder, softex kw, after ultrasonic dispersion stirs, stir and be warming up to 90-130 ℃, drip epoxides, dropwise and continue reaction 2.5-8.0 h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring mass fraction be 50%, the salt that is dissolved in water and generates, suction filtration, filter cake washs with distilled water, drying, wherein: organic solvent, nano-TiO
2the mass ratio of the KOH aqueous solution, dissolved water and distilled water that powder, softex kw, epoxides, mass fraction are 50% is (3-10): 1:(1/100-1/25): (1/20-1/2): (1-20): (2-10): (30-100);
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, carrene, mass fraction that step (1) products obtained therefrom, mass fraction are 70% are 80% in reactor, stirring at room 36h, reactant liquor is diluted with ethyl acetate, washing, dry white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product, wherein: the mass ratio of high chloro acid solution, ethyl acetate and water that the methyl-sulfoxide aqueous solution, carrene, the mass fraction that the step added (1) products obtained therefrom, mass fraction are 70% is 80% is 1:(30-100): (20-100): (1/30-1/10): (50-100): (40-100).
2. the modified Nano TiO of degradable benzene homologues
2the preparation method of photochemical catalyst is characterized in that comprising the following steps:
(1) in being housed, the reactor of organic solvent adds successively nano-TiO
2powder, softex kw, after ultrasonic dispersion stirs, stir and be warming up to 90-130 ℃, drip epoxides, dropwise and continue reaction 2.5-8.0 h, after having reacted, reactant liquor is cooled to room temperature, the KOH aqueous solution that to drip while stirring mass fraction be 50%, the salt that is dissolved in water and generates, suction filtration, filter cake washs with distilled water, drying, wherein: organic solvent, nano-TiO
2the mass ratio of the KOH aqueous solution, dissolved water and distilled water that powder, softex kw, epoxides, mass fraction are 50% is (3-10): 1:(1/100-1/25): (1/20-1/2): (1-20): (2-10): (30-100);
(2) add successively the high chloro acid solution that the methyl-sulfoxide aqueous solution, carrene, mass fraction that step (1) products obtained therefrom, mass fraction are 70% are 80% in reactor, stirring at room 36h, reactant liquor is diluted with ethyl acetate, washing, dry, obtain white crystalline powder, be the modified Nano TiO of degradable benzene homologues
2the photochemical catalyst finished product, wherein: the mass ratio of high chloro acid solution, ethyl acetate and water that the methyl-sulfoxide aqueous solution, carrene, the mass fraction that the step added (1) products obtained therefrom, mass fraction are 70% is 80% is 1:(30-100): (20-100): (1/30-1/10): (50-100): (40-100).
3. the modified Nano TiO of degradable benzene homologues according to claim 2
2the preparation method of photochemical catalyst, is characterized in that described in step (1), organic solvent is toluene or paraxylene.
4. the modified Nano TiO of degradable benzene homologues according to claim 2
2the preparation method of photochemical catalyst, the rate of addition that it is characterized in that epoxides described in step (1) is 0.00417-0.04167 g/min.
5. but the modified Nano TiO of efficient degradation benzene homologues according to claim 2
2the preparation method of photochemical catalyst, is characterized in that described nano-TiO
2particle diameter<the 20nm of powder.
6. the modified Nano TiO of degradable benzene homologues according to claim 2
2the preparation method of photochemical catalyst, is characterized in that described epoxides is epoxychloropropane, methyl epichlorohydrin or 1,2-epoxy chlorobutane.
7. modified Nano TiO
2photochemical catalyst is the application in benzene homologues in degrading waste water.
8. modified Nano TiO according to claim 7
2photochemical catalyst is the application in benzene homologues in degrading waste water, it is characterized in that described benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310367381.2A CN103464214B (en) | 2013-08-22 | 2013-08-22 | Modified nano TiO2 photocatalyst capable of degrading benzene series, and preparation method and application of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310367381.2A CN103464214B (en) | 2013-08-22 | 2013-08-22 | Modified nano TiO2 photocatalyst capable of degrading benzene series, and preparation method and application of same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103464214A true CN103464214A (en) | 2013-12-25 |
| CN103464214B CN103464214B (en) | 2015-02-18 |
Family
ID=49789385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310367381.2A Expired - Fee Related CN103464214B (en) | 2013-08-22 | 2013-08-22 | Modified nano TiO2 photocatalyst capable of degrading benzene series, and preparation method and application of same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103464214B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715733A (en) * | 2018-06-28 | 2018-10-30 | 芜湖市棠华建材科技有限公司 | aqueous environment protection paint |
| US10138135B1 (en) | 2018-04-24 | 2018-11-27 | King Saud University | Synthesis of titanium dioxide nanoparticles using Origanum majorana herbal extracts |
| CN109235023A (en) * | 2018-08-31 | 2019-01-18 | 黄勇 | A kind of preparation method of high-affinity Anti-ultraviolet true silk textile finishing agent material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005224727A (en) * | 2004-02-13 | 2005-08-25 | Asahi Kasei Chemicals Corp | Modified photocatalyst |
| CN1810356A (en) * | 2006-03-02 | 2006-08-02 | 复旦大学 | Prepn process of nanometer crystal titania aerogel with high photocatalysis activity |
| CN102350324A (en) * | 2011-09-02 | 2012-02-15 | 湖南大学 | Multifunctional composite adsorbent, and preparation method and application thereof |
-
2013
- 2013-08-22 CN CN201310367381.2A patent/CN103464214B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005224727A (en) * | 2004-02-13 | 2005-08-25 | Asahi Kasei Chemicals Corp | Modified photocatalyst |
| CN1810356A (en) * | 2006-03-02 | 2006-08-02 | 复旦大学 | Prepn process of nanometer crystal titania aerogel with high photocatalysis activity |
| CN102350324A (en) * | 2011-09-02 | 2012-02-15 | 湖南大学 | Multifunctional composite adsorbent, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 田维等: "改性纳米TiO2光催化降解苯酚活性的研究", 《精细石油化工进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10138135B1 (en) | 2018-04-24 | 2018-11-27 | King Saud University | Synthesis of titanium dioxide nanoparticles using Origanum majorana herbal extracts |
| CN108715733A (en) * | 2018-06-28 | 2018-10-30 | 芜湖市棠华建材科技有限公司 | aqueous environment protection paint |
| CN109235023A (en) * | 2018-08-31 | 2019-01-18 | 黄勇 | A kind of preparation method of high-affinity Anti-ultraviolet true silk textile finishing agent material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103464214B (en) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10118151B2 (en) | Composite with synergistic effect of adsorption and visible light catalytic degradation and preparation method and application thereof | |
| Mohd Adnan et al. | Effect on different TiO 2 photocatalyst supports on photodecolorization of synthetic dyes: a review | |
| Balakrishnan et al. | Immobilized TiO2/chitosan beads for photocatalytic degradation of 2, 4-dichlorophenoxyacetic acid | |
| Motamedi et al. | Recent developments in photocatalysis of industrial effluents։ A review and example of phenolic compounds degradation | |
| Ghoreishian et al. | Decolorization and mineralization of an azo reactive dye using loaded nano-photocatalysts on spacer fabric: Kinetic study and operational factors | |
| Liu et al. | Adsorptive removal of 2, 4-DCP from water by fresh or regenerated chitosan/ACF/TiO2 membrane | |
| CN103357424B (en) | Photocatalyst for selective oxidation of toluene and toluene derivatives | |
| CN108273489A (en) | A kind of preparation method and applications of cerium doped titanium dioxide/graphene aerogel | |
| CN103464122B (en) | A kind of preparation method of graphene/chitosan adsorbent resin | |
| CN103464214B (en) | Modified nano TiO2 photocatalyst capable of degrading benzene series, and preparation method and application of same | |
| CN107570214A (en) | Possesses the preparation method of the paper substrate bismuth ferrite composite of multiphase adsoption catalysis function | |
| CN106582626A (en) | Preparation method and application of novel silver ion doped TiO2 composite material | |
| Falletta et al. | Floatable graphitic carbon nitride/alginate beads for the photodegradation of organic pollutants under solar light irradiation | |
| CN103041780B (en) | Silica supported polyamine water treatment agent, application thereof and preparation method | |
| CN104815616A (en) | Preparation method of layered sulfonated graphene/titanium dioxide composite material and application of the material in the field of sewage treatment | |
| CN103611577A (en) | Visible light catalyst for high-efficiently degrading organic dye waste water and preparation method thereof | |
| CN108906090A (en) | A kind of optic catalytic composite material and its preparation method and application with p-n heterojunction | |
| Su et al. | Heterostructured Bi2O2CO3/rGO/PDA photocatalysts with superior activity for organic pollutant degradation: Structural characterization, reaction mechanism and economic assessment | |
| CN102583636A (en) | Nanometer cobalt-doped titanium dioxide/chitosan composite microspheres for photolyzing organophosphorus pesticide wastewater | |
| CN104128208B (en) | Modified nano-titanium dioxide photocatalyst and its preparation method and application | |
| CN105879896B (en) | Cu3B2O6/g‑C3N4The preparation method of heterojunction photocatalyst and its method for degradation of methylene blue waste water from dyestuff | |
| Gulyas | Solar heterogeneous photocatalytic oxidation for water and wastewater treatment: problems and challenges | |
| CN105363495A (en) | Amphiphilic nano TiO2 powder catalyst, preparation method and use method thereof | |
| CN108786892A (en) | A kind of graphite oxide phase single layer C3N4Composite film material and its preparation method and application | |
| CN102380416A (en) | Method for preparing metal-free high molecular polymer photocatalysis material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150218 Termination date: 20170822 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |