CN103464214B - 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 PDF

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CN103464214B
CN103464214B CN201310367381.2A CN201310367381A CN103464214B CN 103464214 B CN103464214 B CN 103464214B CN 201310367381 A CN201310367381 A CN 201310367381A CN 103464214 B CN103464214 B CN 103464214B
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tio
mass fraction
modified nano
aqueous solution
water
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CN103464214A (en
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王晓辉
堵锡华
董黎明
蔡可迎
史小琴
唐磊
袁仙琴
陆苏潇
汤楠
王化建
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XUZHOU JIANPING CHEMICAL CO Ltd
Xuzhou University of Technology
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XUZHOU JIANPING CHEMICAL CO Ltd
Xuzhou University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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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

The modified Nano TiO of degradable benzene homologues 2photochemical catalyst and its preparation method and application
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, ink, leather, high-grade paint, plastics, dyestuff and household chemicals, be prevalent in water body, soil, air with different concentration, being entered in people's carcass with directly contacting by breathing, food, causing " 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 H be induced under solar radiation condition 2o molecular ionization goes out hydroxyl free radical (OH), the organic pollution that decomposable asymmetric choice net is nearly all, generates CO 2and H 2o is one of environmental protection catalyst having DEVELOPMENT PROSPECT most.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 the imbalance of Ti-O key makes its polarity very strong, very easily mutually reunites, affects its practical effect; Research is had to confirm, compared with suspended particulate substance in water (SPM), the TiO of nanomorphic 2particle easily moves in water body, not free settling, has and significantly increases enrichment As(III in carp body), As(V) and the risk of Cd etc.; In addition, nano-TiO 2particle also has the risk causing genetic damage.
Prior art as Chinese patent CN102205253 disclose one possess under visible light highly active can load type photocatalytic material and preparation method thereof: first prepare PVA-TiO by sol-gel process 2composite membrane, combines with chemical bond between polymer with inorganic matter, forms the network structure be cross-linked with each other, then is carried on various inorganic carrier.This composite has developed TiO 2band gap, widened photoresponse scope, improve the utilization ratio of sunshine, and preparation technology is simple, fast and easy, filming performance is good, save cost, but still it is more weak to there is load forces, recycles in process cannot avoid TiO for a long time 2the deficiency that nano particle runs off; Chinese patent CN102527439 discloses a kind of polymer/TiO with photocatalytic activity 2the preparation method of hybridized film, achieves TiO 2the chemical load of nano particle in thin polymer film, not only effectively improve the reunion of nano particle, and after photocatalysis terminates, described hybridized film can directly be taken out from organic pollutant solution, nano particle is recycled, solve conventional load method insoluble in Long-Time Service process TiO 2the losing issue of nano particle, ensures photocatalytic activity higher in Long-Time Service, and technique is simple, but the base membrane fibers diameter of its hybridized film is increased to 100 ~ 300nm from 2 ~ 50nm of primary particle diameter, limits the raising of photocatalytic activity.In sum, the deficiency how overcoming prior art existence has 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 the modified Nano TiO proposing 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 benzo pollutants degradation rate, can reusing strong, be widely used in the process of benzo pollutants.
Technical scheme of the present invention:
The modified Nano TiO of degradable benzene homologues 2photochemical catalyst, is characterized in that being prepared by following steps and obtaining:
(1) in the reactor that organic solvent is housed, nano-TiO is added successively 2powder, softex kw, after ultrasonic disperse stirs, stir and be warming up to 90-130 DEG C, drip epoxides, dropwise and continue reaction 2.5-8.0h, after having reacted, reactant liquor is cooled to room temperature, drips the KOH aqueous solution that mass fraction is 50% while stirring, be dissolved in water the salt generated, suction filtration, filter cake distilled water washs, dry, wherein: organic solvent, nano-TiO 2powder, softex kw, epoxides, mass fraction are the KOH aqueous solution of 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 step (1) products obtained therefrom in the reactor successively, mass fraction be 70% the methyl-sulfoxide aqueous solution, carrene, mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, by reactant liquor diluted ethyl acetate, washing, dry White crystal powder, is the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product, wherein: the mass ratio of the high chloro acid solution that the methyl-sulfoxide aqueous solution that step (1) products obtained therefrom added, mass fraction are 70%, carrene, mass fraction are 80%, ethyl acetate and water 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 the reactor that organic solvent is housed, nano-TiO is added successively 2powder, softex kw, after ultrasonic disperse stirs, stirring is warming up to 90-130 DEG C, drip epoxides, dropwise and continue reaction 2.5-8.0h, after having reacted, reactant liquor is cooled to room temperature, drip the KOH aqueous solution that mass fraction is 50% while stirring, be dissolved in water the salt generated, suction filtration, filter cake distilled water washs, dry, wherein: organic solvent, TiO_2 nanoparticles, softex kw, epoxides, mass fraction is the KOH aqueous solution of 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 step (1) products obtained therefrom in the reactor successively, mass fraction be 70% the methyl-sulfoxide aqueous solution, carrene, mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, by reactant liquor diluted ethyl acetate, washing, dry, obtain White crystal powder, be the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product, wherein: the mass ratio of the high chloro acid solution that the methyl-sulfoxide aqueous solution that step (1) products obtained therefrom added, mass fraction are 70%, carrene, mass fraction are 80%, ethyl acetate and water 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 2the particle diameter < 20nm of powder.
Described epoxides is epoxychloropropane, methyl epichlorohydrin or 1,2-epoxy chlorobutane.
Modified Nano TiO 2the application of photochemical catalyst in degrading waste water in benzene homologues.
Described modified Nano TiO 2the application of photochemical catalyst in degrading waste water in benzene homologues, 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, and improve its dispersion in water, what degraded benzene homologues (analyzing pure) was made into has certain density simulation industrial wastewater.Under certain condition, static placement or in addition mechanical agitation carry out degradation reaction, degraded is carried out to institute's simulated wastewater and removes benzo pollutants, then treatment fluid is got on centrifuge, carry out under certain rotating speed centrifugal after, get its supernatant liquor, measured the absorbance for the treatment of fluid with cuvette by UV-6 type ultraviolet-visible spectrophotometer, calculate contaminant degradation rate.Changing each factor affecting degradation reaction effect, by investigating degradation rate, finally drawing the optimum reaction condition of process waste water.After carrying out degraded removal benzo pollutants to simulated wastewater, photocatalyst powder is separated, recycling.
The present invention compared with prior art its remarkable advantage is:
(1) epoxides is grafted to nano-TiO by the present invention 2particle surface, improve the dispersiveness of photochemical catalyst in water-based system and compatibility, substantially increase activity, in the process of degrading benzene thing, 10min can make difficult degradation benzene homologues degradable after can reaching 98.21%, 110min to the degradation rate of benzene homologues;
(2) modified light catalyst of the present invention have stronger can reusing, after repeatedly using, still have higher catalytic activity, after reusing 7 times, 60min still can reach 98.86% to the degradation rate of benzene homologues;
(3) preparation method's reaction condition of the present invention is gentle, and preparation process is simple, easy to operate, can be widely used in the process of benzo pollutants.
(4) the modified Nano TiO for preparing of this method 2after particle degrading benzene pollutant, through being separated, reclaiming, recycle, also can continue through chemical solid support method evenly distributed and be distributed in filter membrane surface, improve that load forces is more weak, nano-TiO 2the problem that particle easily runs off, what improve membrane material can reusing.
Accompanying drawing explanation
Fig. 1 is nano-TiO 2before modified afterwards to Phenol in Aqueous Solution degradation rate curve over time;
Fig. 2 is nano-TiO 2before modified afterwards to parachlorophenol degradation rate curve over time in solution;
Fig. 3 is nano-TiO 2before modified afterwards to paracide degradation rate curve over time in solution;
Fig. 4 is unmodified nano-TiO 2with with the nano-TiO after different rings oxide modifying 2to 1,2,4-trichloro-benzenes degradation rate curve over time in solution;
Fig. 5 be in solution 1,2,4-trichloro-benzenes at the absorbance curve of different degradation time;
Fig. 6 is that finished product of the present invention is to the change curve of the degradation rate of 1,2,4-trichloro-benzenes in solution with solution temperature.
Detailed description of the invention
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.
Set forth the present invention further below in conjunction with embodiment, but the present invention is not only confined to following embodiment.
Embodiment 1
(1) in the reactor that 15g toluene is housed, 5.00g nano-TiO is added successively 2powder, 0.05g softex kw, after ultrasonic disperse stirs, stirring is warming up to 90 DEG C, drips 0.25g epoxychloropropane in 60min, dropwises and continues reaction 2.5h, after having reacted, reactant liquor is cooled to room temperature, drip the KOH aqueous solution that 5g mass fraction is 50% while stirring, add the water-soluble salt separating generation of 10g, suction filtration, filter cake 150g distilled water washing, in 300Pa and 120 DEG C of dry 5.0h;
(2) add 1.00g step (1) products obtained therefrom in the reactor successively, 100g mass fraction be 70% the methyl-sulfoxide aqueous solution, 100g carrene, 0.1g mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, reactant liquor is used 100g diluted ethyl acetate, wash with 100g water, dry 5.0h at 300Pa and 120 DEG C, obtain White crystal powder, be the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product.
Embodiment 2
(1) in the reactor that 50g toluene is housed, 5.00g nano-TiO is added successively 2powder, 0.20g softex kw, after ultrasonic disperse stirs, stirring is warming up to 110 DEG C, drips 2.50g methyl epichlorohydrin in 60min, dropwises and continues reaction 4.0h, after having reacted, reactant liquor is cooled to room temperature, drip the KOH aqueous solution that 100g mass fraction is 50% while stirring, add the water-soluble salt separating generation of 50g, suction filtration, filter cake 500g distilled water washing, in 300Pa and 120 DEG C of dry 5.0h;
(2) add 1.00g step (1) products obtained therefrom in the reactor successively, 30g mass fraction be 70% the methyl-sulfoxide aqueous solution, 20g carrene, 0.033g mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, reactant liquor is used 50g diluted ethyl acetate, wash with 40g water, dry 5.0h at 300Pa and 120 DEG C, obtain White crystal powder, be the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product.
Embodiment 3
(1) in the reactor that 30g paraxylene is housed, 5.00g nano-TiO is added successively 2powder, 0.10g softex kw, after ultrasonic disperse stirs, stir and be warming up to 130 DEG C, in 60min, drip 0.50g1,2-epoxy chlorobutane, dropwise and continue reaction 8.0h, after having reacted, reactant liquor is cooled to room temperature, drip the KOH aqueous solution that 50g mass fraction is 50% while stirring, add the water-soluble salt separating generation of 30g, suction filtration, filter cake 300g distilled water washing, in 300Pa and 120 DEG C of dry 6.0h;
(2) add 1.00g step (1) products obtained therefrom in the reactor successively, 40g mass fraction be 70% the methyl-sulfoxide aqueous solution, 30g carrene, 0.05g mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, reactant liquor is used 60g diluted ethyl acetate, wash with 60g water, dry 6.0h at 300Pa and 120 DEG C, obtain White crystal powder, be the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product.
Application examples 1
At 30 DEG C, by unmodified for 0.12g nano-TiO 2it is in the phenol solution of 10.00mg/L that powder and 0.12g embodiment 1 gained finished product add two groups of 50mL concentration respectively, under light illumination, 3.0h is stirred with the rotating speed of 180r/min, sample time is set as 10min/ time, and treatment fluid is carried out centrifugation under 600r/min rotating speed, 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, unmodified nano-TiO is used 2after powder handling, the degradation rate after 30min reaches 98.56%, and with modified nano-TiO 2after powder handling, the degradation rate after 10min can reach 99.20%.
Application examples 2
At 30 DEG C, by unmodified for 0.12g nano-TiO 2it is in the parachlorophenol solution of 10.00mg/L that powder and 0.12g embodiment 1 gained finished product add two groups of 50mL concentration respectively, under light illumination, 3.0h is stirred with the rotating speed of 180r/min, sample time is set as 10min/ time, and treatment fluid is carried out centrifugation under 600r/min rotating speed, 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, unmodified nano-TiO is used 2after powder handling, the degradation rate after 180min reaches 99.98%, and with modified nano-TiO 2after powder handling, the degradation rate after 60min can reach 99.20%.
Application examples 3
At 30 DEG C, by unmodified for 0.12g nano-TiO 2it is in the paracide solution of 10.00mg/L that powder and 0.12g embodiment 1 gained finished product add two groups of 50mL concentration respectively, under light illumination, 3.0h is stirred with the rotating speed of 180r/min, sample time is set as 10min/ time, and treatment fluid is carried out centrifugation under 600r/min rotating speed, 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, unmodified nano-TiO is used 2after powder handling, the degradation rate after 60min reaches 100.00%, and with modified nano-TiO 2after powder handling, the degradation rate after 30min can reach 100%.
Application examples 4
Utilize 1,2,4-trichloro-benzenes in gained finished product degrading waste water in embodiment 1-3.
Control group: at 30 DEG C, by unmodified for 0.12g nano-TiO 2powder 50mL concentration is in 1,2, the 4-trichlorobenzene solution of 10.00mg/L, under light illumination, stir 3.0h with the rotating speed of 180r/min, sample time is set as 10min/ time, treatment fluid is carried out centrifugation under 600r/min rotating speed, reclaim photocatalyst powder, get its supernatant liquor, detect residual 1 with UV-6 type ultraviolet-visible spectrophotometer, 2, the absorbance of 4-trichloro-benzenes, calculates its concentration and degradation rate, and draws degradation rate curve over time.As seen from Figure 4, it is 98.63% that the degradation rate after 60min is only the degradation rate after 99.25%, 180min;
At (1) 30 DEG C, 0.12g embodiment 1 gained finished product is added 50mL concentration is 10.00mg/L 1,2, in 4-trichlorobenzene solution, under light illumination, 3.0h is stirred with the rotating speed of 180r/min, sample time is set as 10min/ time, and treatment fluid is carried out centrifugation under 600r/min rotating speed, reclaims photocatalyst powder, get its supernatant liquor, the absorbance of residual 1,2,4-trichloro-benzenes is detected with UV-6 type ultraviolet-visible spectrophotometer, 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%; Detect the absorbance of supernatant respectively when 20min, 40min and 60min and see Fig. 5, as shown in Figure 5, after 60min, the absorption of 210nm no longer occurs, benzene homologues is degraded substantially completely.
At (2) 30 DEG C, it is 1 of 10.00mg/L that 0.12g embodiment 2 gained finished product is added two groups of 50mL concentration respectively, 2, in 4-trichlorobenzene solution, under light illumination, 3.0h is stirred with the rotating speed of 180r/min, sample time is set as 10min/ time, and treatment fluid is carried out centrifugation under 600r/min rotating speed, reclaims photocatalyst powder, get its supernatant liquor, the absorbance of residual 1,2,4-trichloro-benzenes is detected with UV-6 type ultraviolet-visible spectrophotometer, 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%.
At (3) 30 DEG C, it is 1 of 10.00mg/L that 0.12g embodiment 3 gained finished product is added two groups of 50mL concentration respectively, 2, in 4-trichlorobenzene solution, under light illumination, 3.0h is stirred with the rotating speed of 180r/min, sample time is set as 10min/ time, and treatment fluid is carried out centrifugation under 600r/min rotating speed, reclaims photocatalyst powder, get its supernatant liquor, the absorbance of residual 1,2,4-trichloro-benzenes is detected with UV-6 type ultraviolet-visible spectrophotometer, 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, has comparatively ideal degradation rate when 60min to 1,2,4-trichloro-benzenes in solution, and wherein embodiment 1 gained modified catalyst effect is better.
Application examples 5
Investigate solution temperature to the impact of modified light catalyst activity.
It is 1 of 10.00mg/L that 0.12g embodiment 1 gained finished product is added a series of 50mL concentration respectively, 2, in 4-trichlorobenzene solution, temperature control is 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 50 DEG C respectively, under light illumination, 60min is stirred with the rotating speed of 180r/min, treatment fluid is carried out centrifugation under 600r/min rotating speed, reclaim photocatalyst powder, get its supernatant liquor, detect residual 1 with UV-6 type ultraviolet-visible spectrophotometer, 2, the absorbance of 4-trichloro-benzenes, calculates its concentration and degradation rate, and draws 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 DEG C, and the activity of photochemical catalyst is the highest at this moment.
Application examples 6
At 30 DEG C, by unmodified for 0.12g nano-TiO 2it is in 1,2, the 4-trichlorobenzene solution of 10.00mg/L that powder and 0.12g embodiment 1 gained finished product add two groups of 50mL concentration respectively, and under light illumination, stir with the rotating speed of 180r/min, react, the former is respectively 60min, 180min sample time, and the latter is 60min.Then treatment fluid is carried out centrifugation under 600r/min rotating speed, after reclaiming photocatalyst powder, get its supernatant liquor, detect the absorbance of residual 1,2,4-trichloro-benzenes with UV-6 type ultraviolet-visible spectrophotometer, calculate its concentration and degradation rate.Catalyst muffin is after 300Pa and 120 DEG C drying, and again it being added respectively two groups of 50mL concentration is in 1,2, the 4-trichlorobenzene solution of 10.00mg/L, 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 at the degradation rate of 60min to 1,2,4-trichloro-benzenes, even if it just can reach 98.64% to the degradation rate of 1,2,4-trichloro-benzenes when 180min, and after using 7 times, its activity decreases, and gained modified Nano TiO of the present invention 2at 60min to 1,2,4-trichloro-benzenes degradation rate can reach 99%, 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, for continue through chemistry immobilized in filter membrane surface carry out industrialization use laid good basis.

Claims (7)

1. the modified Nano TiO of degradable benzene homologues 2photochemical catalyst, is characterized in that being prepared by following steps and obtaining:
(1) in the reactor that organic solvent is housed, nano-TiO is added successively 2powder, softex kw, after ultrasonic disperse stirs, stir and be warming up to 90-130 DEG C, drip epoxides, dropwise and continue reaction 2.5-8.0h, after having reacted, reactant liquor is cooled to room temperature, drips the KOH aqueous solution that mass fraction is 50% while stirring, be dissolved in water the salt generated, suction filtration, filter cake distilled water washs, dry, wherein: organic solvent, nano-TiO 2powder, softex kw, epoxides, mass fraction are the KOH aqueous solution of 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), described epoxides is epoxychloropropane, methyl epichlorohydrin or 1,2-epoxy chlorobutane;
(2) add step (1) products obtained therefrom in the reactor successively, mass fraction be 70% the methyl-sulfoxide aqueous solution, carrene, mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, by reactant liquor diluted ethyl acetate, washing, dry White crystal powder, is the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product, wherein: the mass ratio of the high chloro acid solution that the methyl-sulfoxide aqueous solution that step (1) products obtained therefrom added, mass fraction are 70%, carrene, mass fraction are 80%, ethyl acetate and water 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 the reactor that organic solvent is housed, nano-TiO is added successively 2powder, softex kw, after ultrasonic disperse stirs, stir and be warming up to 90-130 DEG C, drip epoxides, dropwise and continue reaction 2.5-8.0h, after having reacted, reactant liquor is cooled to room temperature, drips the KOH aqueous solution that mass fraction is 50% while stirring, be dissolved in water the salt generated, suction filtration, filter cake distilled water washs, dry, wherein: organic solvent, nano-TiO 2powder, softex kw, epoxides, mass fraction are the KOH aqueous solution of 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), described epoxides is epoxychloropropane, methyl epichlorohydrin or 1,2-epoxy chlorobutane;
(2) add step (1) products obtained therefrom in the reactor successively, mass fraction be 70% the methyl-sulfoxide aqueous solution, carrene, mass fraction be the high chloro acid solution of 80%, stirring at room temperature 36h, by reactant liquor diluted ethyl acetate, washing, dry, obtain White crystal powder, be the modified Nano TiO of degradable benzene homologues 2photochemical catalyst finished product, wherein: the mass ratio of the high chloro acid solution that the methyl-sulfoxide aqueous solution that step (1) products obtained therefrom added, mass fraction are 70%, carrene, mass fraction are 80%, ethyl acetate and water 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, is characterized in that the rate of addition of epoxides described in step (1) is 0.00417-0.04167g/min.
5. the modified Nano TiO of degradable benzene homologues according to claim 2 2the preparation method of photochemical catalyst, is characterized in that described nano-TiO 2the particle diameter < 20nm of powder.
6. modified Nano TiO according to claim 1 2the application of photochemical catalyst in degrading waste water in benzene homologues.
7. modified Nano TiO according to claim 6 2the application of photochemical catalyst in degrading waste water in benzene homologues, is characterized in that described benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
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