CN104128208B - Modified nano-titanium dioxide photocatalyst and its preparation method and application - Google Patents
Modified nano-titanium dioxide photocatalyst and its preparation method and application Download PDFInfo
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Abstract
Modified nano-titanium dioxide photocatalyst and its preparation method and application, preparation method is as follows: 1) equipped with CCl4Reactor in add nano-TiO2Powder body, adds PCl at 80 DEG C3CCl4Solution, 90 DEG C of reaction 2-4 h, remove CCl4Obtain powder body I；2) preparation of 4-sodium sulfonate-phenyl sodium alkyl sulfonate；3) preparation of 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate；4) magnesium metal after process is poured in the reactor filling absolute ether, add step 3) products therefrom, to magnesium total overall reaction, add double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and step 1) products therefrom, reflux 15-20 h, and process gets product.After degrading high concentration benzo pollutants of the present invention, separated recovery, still there is higher catalytic activity after repeatedly using, after reusing 7 times, after 8.0h to high concentration, difficult degradation benzene homologues degradation efficiency up to 100%.
Description
Technical field
The invention belongs to catalytic oxidant and preparing technical field thereof, particularly to a kind of modified nano-titanium dioxide photocatalyst and its preparation method and application.
Background technology
The high-concentration waste water of modern chemical industry has following characteristics: colourity is high, has abnormal flavour, easily gives out pungent stench, exert a gradual, corrupting influence on environment；Organic substance supersaturation, concentration (in COD) higher than 2000mg/L, have even as high as hundreds thousand of mg/L, and containing different types of surfactant and organic solvent etc., self emulsifying, strong from dispersion and trapping ability, pollutant become suspended state and droplet-like；Complicated component, with aromatic compound and heterocyclic compound (BOD in the majority5/ COD value 0.3), possibly together with sulfide, nitride, heavy metal and other toxic organic compound, biodegradability extreme difference, long processing period；Often containing numerous acid, alkali, salt, and concentration is high, the salt content of effluent part is even as high as mg/L up to ten thousand.Its pollution problem is always up in engineering of water treatment to need the difficult problem captured badly.
The character of high concentration benzene homologues waste water is different with source, Treatment process is various, have solvent extraction, membrance separation, absorption, ultrasonic degradation, burning, Fenton oxidation, ozone oxidation, electrochemical oxidation and bioanalysis etc., these methods be primarily present construction costs costliness, can not longtime running, can not the more high deficiency of operating cost of qualified discharge and the effective unit water yield.This is because water treatment effect is not only relevant with external environment conditions such as water quality, the water yield, process cycle, temperature and pH value, also having substantial connection with the chemical composition and structure of high-concentration waste water and microbial population etc., this is also that the problem solving high cost adds difficulty.
Detitanium-ore-type TiO2It is the semiconductor catalyst of a kind of catalysis higher, stable chemical nature of activity, safety and low cost, environment protecting and power-saving, H can be induced under day illumination condition2O molecular ionization goes out hydroxyl free radical (OH), the almost all of organic pollution of decomposable asymmetric choice net, generates CO2、H2O.By TiO2Ultra-fine chemical conversion nanomorphic can also be greatly improved its photocatalytic activity, but nano-titania particle specific surface area is big, 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 nanomorphic2Particle easily migrates in water body, not free settling, has and dramatically increases the risk of enrichment As (III), As (V) and Cd etc. in Cyprinus carpio body；It addition, nano-TiO2Particle also has the risk causing genetic damage.
Prior art such as Chinese patent CN102266792 discloses the synthetic method of a kind of visible photocatalyst by modifying titanium dioxide by using ammonium fluoride: with mesoporous MCF for carrier, load TiO in its duct2, utilize NH again through hydro-thermal method in conjunction with cryogenic vacuum activation method4F modifiies TiO2Visible light catalyst synthetic method.This catalyst passes through the absorbability that mesoporous material is superior, strengthen the visible light photocatalytic degradation performance of the organic pollution to high concentration, and there is advantage simple to operate, with low cost, that raw material is easy to get and UV, visible light photolytic activity is higher, but it is more weak to there is load forces, TiO cannot be avoided in long-term recycling process2The problem that nanoparticle runs off, and the degradation experiment of pollutant proves that it processes that waste strength is relatively low, adsorbance is limited, has relatively large distance with the photocatalysis feature of actual high-concentration waste water and mechanism process；Chinese patent CN102527439 discloses a kind of polymer/TiO with photocatalytic activity2The preparation method of hybridized film, it is achieved that TiO2Nanoparticle chemical load in thin polymer film, not only effectively improve the reunion of nanoparticle, and after photocatalysis terminates, described hybridized film can directly be taken out from organic pollutant solution, nanoparticle is recycled, and solves the insoluble TiO in life-time service process of conventional load method2The losing issue of nanoparticle, it is ensured that photocatalytic activity higher in life-time service, and technique is simple, but similar to traditional hydrophobic modifier, this hybridized film itself is easy under light illumination by TiO2Degraded, greatly reduces stability, and the base membrane fibers diameter of hybridized film increases to 100～300nm from 2～50nm of primary particle diameter, limits the raising of photocatalytic activity.In sum, the deficiency that prior art exists how is overcome to become the technical barrier that catalytic oxidant field is urgently to be resolved hurrily.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art to propose a kind of modified nano-titanium dioxide photocatalyst and its preparation method and application, the present invention has good dispersion phase capacitive in water-based system, it is suitable for 2000 to process to the high concentration of hundreds thousand of mg/L, difficult degradation benzo pollutants, degraded is fast, efficiency is high, can be recycled, and nano-TiO2Particle is not easy to run off, and acid and alkali resistance, salt stable performance are widely used in the process of high concentration benzo pollutants.
Technical scheme:
Modified nano-titanium dioxide photocatalyst, is prepared by following steps and obtains:
1) by nano-TiO2Powder body adds CCl4In, after stirring, it is warming up to 80 DEG C, obtains mixture A；By PCl3It is dissolved in CCl4In, mixing, by PCl3CCl4Solution drops in mixture A, after be warming up to 90 DEG C, react 2-4h, reclaim the CCl in reactant liquor4, obtain powder body I, wherein: CCl4, nano-TiO2Powder body, PCl3、PCl3CCl4The mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10)；
2) being added by benzene in alpha-olefin sulfonic acid, stirring is warming up to 130 DEG C, treats that alpha-olefin sulfonic acid content is constant, obtains phenylalkyl sulfonic acid；It is cooled to 10 DEG C-20 DEG C, continues stirring, drip oleum, dropwise, stirring reaction 2-3h at 25 DEG C, drip 0.2mol L-1Dilute hydrochloric acid, rear addition mass fraction is the NaOH aqueous solution of 20%, to solution in neutrality, remove solvent, obtain paste II, paste II is dissolved in dehydrated alcohol, filter, take filtrate, remove solvent, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, 4-sodium sulfonate group-phenyl-alkyl sodium sulfonate must be refined, wherein: alpha-olefin sulfonic acid, benzene, oleum, dilute hydrochloric acid, dehydrated alcohol mass ratio be 1:(1/2-1): (3-5): (1-3): (2-4)；
3) by step 2) gained 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl4And Br2Being sequentially added into reactor, heating, to backflow, reacts 12-20h, is the NaHCO of 9% with mass fraction successively3Aqueous 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, CCl4、Br2、NaHCO3Aqueous solution, distilled water, saturated aqueous common salt mass ratio be 1:(20-40): (2-5): (50-200): (100-300): (100-200)；
4) with the oxide of HCl treatment metallic magnesium surface, clean with dehydrated alcohol and absolute ether successively, after magnesium metal is poured in the reactor filling absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, stirring, to magnesium total overall reaction, is sequentially added into double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and step 1) gained powder body I, backflow 15-20h, pours the 2mol L of 5 DEG C-10 DEG C into by reactant liquor–1Aqueous hydrochloric acid solution in, sucking filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photocatalyst finished product, wherein: the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, double; 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 photocatalyst, comprises the following steps:
1) by nano-TiO2Powder body adds CCl4In, after stirring, it is warming up to 80 DEG C, obtains mixture A；By PCl3It is dissolved in CCl4In, mixing, by PCl3CCl4Solution drops in mixture A, after be warming up to 90 DEG C, react 2-4h, reclaim the CCl in reactant liquor4, obtain powder body I, wherein: CCl4, nano-TiO2Powder body, PCl3、PCl3CCl4The mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10)；
2) being added by benzene in alpha-olefin sulfonic acid, stirring is warming up to 130 DEG C, treats that alpha-olefin sulfonic acid content is constant, obtains phenylalkyl sulfonic acid；It is cooled to 10 DEG C-20 DEG C, continues stirring, drip oleum, dropwise, stirring reaction 2-3h at 25 DEG C, drip 0.2mol L-1Dilute hydrochloric acid, rear addition mass fraction is the NaOH aqueous solution of 20%, to solution in neutrality, remove solvent, obtain paste II, paste II is dissolved in dehydrated alcohol, filter, take filtrate, remove solvent, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, 4-sodium sulfonate group-phenyl-alkyl sodium sulfonate must be refined, wherein: alpha-olefin sulfonic acid, benzene, oleum, dilute hydrochloric acid, dehydrated alcohol mass ratio be 1:(1/2-1): (3-5): (1-3): (2-4)；
3) by step 2) gained 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl4And Br2Being sequentially added into reactor, heating, to backflow, reacts 12-20h, is the NaHCO of 9% with mass fraction successively3Aqueous 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, CCl4、Br2、NaHCO3Aqueous solution, distilled water, saturated aqueous common salt mass ratio be 1:(20-40): (2-5): (50-200): (100-300): (100-200)；
4) with the oxide of HCl treatment metallic magnesium surface, clean with dehydrated alcohol and absolute ether successively, after magnesium metal is poured in the reactor filling absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, stirring, to magnesium total overall reaction, is sequentially added into double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and step 1) gained powder body I, backflow 15-20h, pours the 2mol L of 5 DEG C-10 DEG C into by reactant liquor–1Aqueous hydrochloric acid solution in, sucking filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photocatalyst finished product, wherein: the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, double; 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) described in PCl3CCl4The rate of addition of solution is 0.13333-0.26667g/min, step 2) described in oleum and 0.2mol L-1The rate of addition of dilute hydrochloric acid is 0.16667-0.33333g/min.
Described nano-TiO2The particle diameter < 20nm of powder body.
The carbon number range of described alpha-olefin sulfonic acid is C12-C20.
Modified Nano TiO2Photocatalyst application in high concentration benzene homologues wastewater treatment.
Described modified Nano TiO2Photocatalyst application in high concentration benzene homologues wastewater treatment, wherein said benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
Present invention nano-TiO2Particle is as matrix, it is grafted to particle surface by benzene sulfonic acid sodium salt alkyl sulfonic acids sodium, improving its dispersion in water and to the emulsifying of benzene homologues, trapping effect, what degraded benzene homologues (analytical pure) was made into has the oversaturated simulation industrial wastewater of high concentration.Prepare respectively at a certain temperature a stand oil (Gu) emulsifying of water ratio or dispersion soln, constant temperature stirring certain time under certain rotating speed, degradation reaction is carried out with mechanical agitation, institute's simulated wastewater is carried out degraded and removes benzo pollutants, then utilize zeta current potential nano particle size instrument that emulsifying or the dispersion liquid of preparation are carried out dynamic light scattering test, measure particle size distribution；Take treatment fluid on centrifuge, after being centrifuged under certain rotating speed, take its supernatant, measured the absorbance for the treatment of fluid with cuvette by UV-6 type ultraviolet-visible spectrophotometer, to test saturated solution for benchmark, calculate the relative concentration of pollutant.Change each factor affecting degradation reaction effect, by investigating concentration and degradation efficiency, finally draw the optimum reaction condition processing waste water.After simulated wastewater carries out degraded removal benzo pollutants, photocatalyst powder separates, recycling.
Compared with prior art it has the remarkable advantages that the present invention:
(1) present invention effectively utilizes sunlight, by a kind of cleaning, environmental protection and energy-conservation in the way of solve environmental pollution, it is suitable for 2000 to process to the high concentration of hundreds thousand of mg/L, difficult degradation benzo pollutants, widely applicable, especially the high-concentration waste water of complicated component there is good effect, it may be achieved qualified discharge；
(2) the present invention is directed to most of oversaturated feature of high-concentration waste water pollutant, benzene sulfonic acid sodium salt alkyl sulfonic acids sodium is grafted to nano-TiO2Particle surface, substantially increase the surface activity of photocatalyst and dispersibility in water-based system, the compatibility, through self emulsifying, from dispersion and trapping effect, it is enriched in the contaminant particles surface of suspended state and droplet-like, the pollutant not only dissolved in degradable high-concentration waste water, also can directly degrade the particle of emulsifying, scattered pollutant, accelerated degradation process, in the process of degrading high concentration benzene homologues, the degradable of high concentration benzene homologues can be reached during 1.0h, difficult degradation benzene homologues can be made to reach after 8.0h degradable；
(3) after the modified nano-titanium dioxide photocatalyst for degrading high concentration benzo pollutants that prepared by this method, separated, recovery, can be recycled, still there is higher catalysis activity after repeatedly using, after reusing 7 times, after 8.0h to high concentration, difficult degradation benzene homologues degradation efficiency still up to 100%, and nano-TiO2Particle is not easy to run off；
(4) this photocatalyst acid and alkali resistance, salt stable performance, process when pH value is relied on bigger benzene homologues, effect is notable, it is to avoid load TiO2The degraded of the polymeric film of nanoparticle, it is prevented that particle is reunited again, effectively prevent the reduction of photocatalytic activity.
Accompanying drawing explanation
Fig. 1 be before modified after nano-TiO2Dispose waste liquid middle phenol time phenol concentration versus time curve figure；
Fig. 2 be before modified after nano-TiO2Dispose waste liquid middle parachlorophenol time parachlorophenol concentration versus time curve figure；
Fig. 3 be before modified after nano-TiO2Dispose waste liquid middle paracide time paracide concentration versus time curve figure；
Fig. 4 is for use unmodified nano-TiO2With the nano-TiO after the alpha-olefin sulfonic acid modified of different carbon number range2Dispose waste liquid middle 1,2,4-trichloro-benzenes time 1,2,4-trichloro-benzenes concentration versus time curve figure；
Fig. 5 be in waste liquid 1,2,4-trichloro-benzenes at the absorbance curve figure of different degradation times；
Fig. 6 be in waste liquid 1,2,4-trichloro-benzenes at the emulsion droplet size scatter chart of different degradation times；
When Fig. 7 is 1,2,4-trichloro-benzenes in product handling system waste liquid of the present invention, emulsion droplet size is with the change curve of solution temperature；
When Fig. 8 is 1,2,4-trichloro-benzenes in product handling system waste liquid of the present invention, emulsion droplet size is with the change curve of pH.
Detailed description of the invention
nullBenzene homologues of the present invention is benzene、Toluene、O-Dimethylbenzene、Meta-xylene、Xylol、Nitrobenzol、Phenol、Chlorobenzene、Parachlorophenol、O-chlorphenol、M-Chlorophenol、Aniline、O-phenylenediamine、M-diaminobenzene.、P-phenylenediamine、O-chloraniline、M-chloroaniline、Parachloroanilinum、O-dichlorohenzene、M-dichlorobenzene、Paracide、2,3-dichloroaniline、3,4-dichloroaniline、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、Perchlorobenzene、2-chlorohydroquinone、4-chloro resorcinol、4-chlorine catechol、2-chloro-1,3-Benzodiazepines、One or more in Polychlorinated biphenyls.
In the present invention, alpha-olefin sulfonic acid respectively total carbon number is the alpha-olefin sulfonic acid of the alpha-olefin sulfonic acid of C12-C14, the alpha-olefin sulfonic acid of C14-C16, the alpha-olefin sulfonic acid of C16-C18, C18-C20, by the supply of Nanjing Yangzi petrochemical industry company limited.
The present invention is expanded on further below in conjunction with embodiment, but the present invention is not limited solely to following embodiment.
Embodiment 1
(1) equipped with 100gCCl4Reactor in add 5.00g nano-TiO2Powder body, after ultrasonic disperse stirs, stirring is warming up to 80 DEG C；By 2.50gPCl3It is dissolved in 50gCCl4In, mixing, by PCl3CCl4Solution adds in reactor, dropwises and is warming up to 90 DEG C, reacts 2h, removes the CCl in reactant liquor4And reclaim, obtain yellow transparent powder body and powder body I；
(2) alpha-olefin sulfonic acid, the 80g benzene that 80g carbon number is C12-C14 it is sequentially added in the reactor, stirring is warming up to 130 DEG C, every 1h sample analysis sulfonic acid content, treat that alpha-olefin sulfonic acid content is constant, obtain brown liquid phenyl-(ten two-ten four) alkyl sulfonic acid；It is cooled to 10 DEG C, continues stirring, drip 400g oleum, dropwise and reaction 2h is stirred at room temperature, drip 240g0.2mol L-1Dilute hydrochloric acid, adding NaOH aqueous solution to the solution that mass fraction is 20% is neutrality, treatment fluid rotation is steamed, residue paste is dissolved in 320g dehydrated alcohol, filtering, take filtrate and again revolve steaming, removing ethanol obtains white paste and is 4-sodium sulfonate group-phenyl-(ten two-ten four) sodium alkyl sulfonate, dry, obtain refining 4-sodium sulfonate group-phenyl-(ten two-ten four) sodium alkyl sulfonate；
(3) by products therefrom, 20gCCl in 1.00g step (2)4And 2.00gBr2Being sequentially added into reactor, heating, to backflow, reacts 12h, is the NaHCO of 9% with 50g mass fraction successively3Aqueous solution, 100g distilled water, 100g saturated common salt water washing, dry concentrate dark yellow solid is 4-sodium sulfonate group-phenyl-(11-13)-bromo-(ten two-ten four) sodium alkyl sulfonate；
(4) by 3.33g magnesium metal 2mol L-1The silvery white that HCl treatment surface black oxide is extremely vivid, clean with dehydrated alcohol and absolute ether successively, magnesium metal is poured in the reactor filling 50g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(11-13)-bromo-(ten two-ten four) sodium alkyl sulfonate solid, stir complete to magnesium total overall reaction, it is sequentially added into 6.67mg double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and 3.33g step (1) products therefrom, backflow 15h, pours the 2mol L of 300g5 DEG C into by mixed liquor–1Aqueous hydrochloric acid solution in, sucking filtration, filter cake 700g distilled water wash, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photocatalyst finished product.
Embodiment 2
(1) equipped with 85gCCl4Reactor in add 5.00g nano-TiO2Powder body, after ultrasonic disperse stirs, stirring is warming up to 80 DEG C；By 2.20gPCl3It is dissolved in 40gCCl4In, mixing, by PCl3CCl4Solution adds in reactor, dropwises and is warming up to 90 DEG C, reacts 3h, removes the CCl in reactant liquor4And reclaim, obtain yellow transparent powder body and powder body I；
(2) alpha-olefin sulfonic acid, the 68g benzene that 80g carbon number is C14-C16 it is sequentially added in the reactor, stirring is warming up to 130 DEG C, every 1h sample analysis sulfonic acid content, treat that alpha-olefin sulfonic acid content is constant, obtain brown liquid phenyl-(ten four-ten six) alkyl sulfonic acid；It is cooled to 20 DEG C, continues stirring, drip 325g oleum, dropwise and reaction 2.5h is stirred at room temperature, drip 190g0.2mol L-1Dilute hydrochloric acid, adding NaOH aqueous solution to the solution that mass fraction is 20% is neutrality, treatment fluid rotation is steamed, residue paste is dissolved in 260g dehydrated alcohol, filtering, take filtrate and again revolve steaming, removing ethanol obtains white paste and is 4-sodium sulfonate group-phenyl-(ten four-ten six) sodium alkyl sulfonate, dry, obtain refining 4-sodium sulfonate group-phenyl-(ten four-ten six) sodium alkyl sulfonate；
(3) by products therefrom, 25gCCl in 1.00g step (2)4And 3.00gBr2Being sequentially added into reactor, heating, to backflow, reacts 16h, is the NaHCO of 9% with 100g mass fraction successively3Aqueous solution, 180g distilled water, 150g saturated common salt water washing, dry concentrate dark yellow solid is 4-sodium sulfonate group-phenyl-(13-15)-bromo-(ten four-ten six) sodium alkyl sulfonate；
(4) by 2.50g magnesium metal 2mol L-1The silvery white that HCl treatment surface black oxide is extremely vivid, clean with dehydrated alcohol and absolute ether successively, magnesium metal is poured in the reactor filling 40g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(13-15)-bromo-(ten four-ten six) sodium alkyl sulfonate solid, stir complete to magnesium total overall reaction, it is sequentially added into 6.00mg double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and 3.00g step (1) products therefrom, backflow 18h, pours the 2mol L of 250g10 DEG C into by mixed liquor–1Aqueous hydrochloric acid solution in, sucking filtration, filter cake 650g distilled water wash, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photocatalyst finished product.
Embodiment 3
(1) equipped with 65gCCl4Reactor in add 5.00g nano-TiO2Powder body, after ultrasonic disperse stirs, stirring is warming up to 80 DEG C；By 2.00gPCl3It is dissolved in 35gCCl4In, mixing, by PCl3CCl4Solution adds in reactor, dropwises and is warming up to 90 DEG C, reacts 4h, removes the CCl in reactant liquor4And reclaim, obtain yellow transparent powder body and powder body I；
(2) alpha-olefin sulfonic acid, the 56g benzene that 80g carbon number is C16-C18 it is sequentially added in the reactor, stirring is warming up to 130 DEG C, every 1h sample analysis sulfonic acid content, treat that alpha-olefin sulfonic acid content is constant, obtain brown liquid phenyl-(ten six-ten eight) alkyl sulfonic acid；It is cooled to 10 DEG C, continues stirring, drip 296g oleum, dropwise and reaction 3h is stirred at room temperature, drip 156g0.2mol L-1Dilute hydrochloric acid, adding NaOH aqueous solution to the solution that mass fraction is 20% is neutrality, treatment fluid rotation is steamed, residue paste is dissolved in 208g dehydrated alcohol, filtering, take filtrate and again revolve steaming, removing ethanol obtains white paste and is 4-sodium sulfonate group-phenyl-(ten six-ten eight) sodium alkyl sulfonate, dry, obtain refining 4-sodium sulfonate group-phenyl-(ten six-ten eight) sodium alkyl sulfonate；
(3) by products therefrom, 35gCCl in 1.00g step (2)4And 4.00gBr2Being sequentially added into reactor, heating, to backflow, reacts 20h, is the NaHCO of 9% with 150g mass fraction successively3Aqueous solution, 250g distilled water, 190g saturated common salt water washing, dry concentrate dark yellow solid is 4-sodium sulfonate group-phenyl-(15-17)-bromo-(ten six-ten eight) sodium alkyl sulfonate；
(4) by 1.50g magnesium metal 2mol L-1The silvery white that HCl treatment surface black oxide is extremely vivid, clean with dehydrated alcohol and absolute ether successively, magnesium metal is poured in the reactor filling 30g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(15-17)-bromo-(ten six-ten eight) sodium alkyl sulfonate solid, stir complete to magnesium total overall reaction, it is sequentially added into 5.50mg double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and 2.80g step (1) products therefrom, backflow 20h, pours the 2mol L of 200g5 DEG C into by mixed liquor–1Aqueous hydrochloric acid solution in, sucking filtration, filter cake 580g distilled water wash, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photocatalyst finished product.
Embodiment 4
(1) equipped with 50gCCl4Reactor in add 5.00g nano-TiO2Powder body, after ultrasonic disperse stirs, stirring is warming up to 80 DEG C；By 1.67gPCl3It is dissolved in 25gCCl4In, mixing, by PCl3CCl4Solution adds in reactor, dropwises and is warming up to 90 DEG C, reacts 3h, removes the CCl in reactant liquor4And reclaim, obtain yellow transparent powder body and powder body I；
(2) alpha-olefin sulfonic acid (), the 40g benzene that 80g carbon number is C18-C20 it is sequentially added in the reactor, stirring is warming up to 130 DEG C, every 1h sample analysis sulfonic acid content, treat that alpha-olefin sulfonic acid content is constant, obtain brown liquid phenyl-(ten eight-two ten) alkyl sulfonic acid；It is cooled to 20 DEG C, continues stirring, drip 240g oleum, dropwise and reaction 2.5h is stirred at room temperature, drip 80g0.2mol L-1Dilute hydrochloric acid, adding NaOH aqueous solution to the solution that mass fraction is 20% is neutrality, treatment fluid rotation is steamed, residue paste is dissolved in 160g dehydrated alcohol, filtering, take filtrate and again revolve steaming, removing ethanol obtains white paste and is 4-sodium sulfonate group-phenyl-(ten eight-two ten) sodium alkyl sulfonate, dry, obtain refining 4-sodium sulfonate group-phenyl-(ten eight-two ten) sodium alkyl sulfonate；
(3) by products therefrom, 40gCCl in 1.00g step (2)4And 5.00gBr2Being sequentially added into reactor, heating, to backflow, reacts 16h, is the NaHCO of 9% with 200g mass fraction successively3Aqueous solution, 300g distilled water, 200g saturated common salt water washing, dry concentrate dark yellow solid is 4-sodium sulfonate group-phenyl-(17-19)-bromo-(ten eight-two ten) sodium alkyl sulfonate；
(4) by 1.00g magnesium metal 2mol L-1The silvery white that HCl treatment surface black oxide is extremely vivid, clean with dehydrated alcohol and absolute ether successively, magnesium metal is poured in the reactor filling 20g absolute ether, add 10.00g4-sodium sulfonate group-phenyl-(17-19)-bromo-(ten eight-two ten) sodium alkyl sulfonate solid, stir complete to magnesium total overall reaction, it is sequentially added into 5.00mg double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and 2.50g step (1) products therefrom, backflow 18h, pours the 2mol L of 150g10 DEG C into by mixed liquor–1Aqueous hydrochloric acid solution in, sucking filtration, filter cake 500g distilled water wash, dry, obtain yellow crystalline powder, be modified nano-titanium dioxide photocatalyst finished product.
In the present invention, part material and each structural formula walking product are shown in table 1 below:
Part material and each structural formula walking product in table 1 present invention
1, unmodified nano-TiO is used respectively2High concentration benzene homologues in the modified nano-titanium dioxide photocatalyst treatment waste water that powder body and the present invention prepare
(1) phenol in waste water, is processed
At 30 DEG C, by unmodified for 0.12g nano-TiO2Powder body and 0.12g embodiment 1 gained finished product are separately added in the phenol solution that two groups of 50mL concentration is 100000mg/L, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, under light illumination, 24.0h is stirred with the rotating speed of 180r/min, sample time is 0.25h/ time, it is centrifuged treatment fluid under 600r/min rotating speed separating, reclaim photocatalyst powder, take its supernatant, absorbance with UV-6 type ultraviolet-visible spectrophotometer detection residual phenol, calculate its relative concentration (relative value of actual concentrations and saturated concentration, represent with %), and draw relative concentration versus time curve.As seen from Figure 1, unmodified nano-TiO is used2After powder handling, the relative concentration after 2.75h reaches 10.0%, and with modified nano-TiO2After powder handling, 1.0h can be degradable.
(2) parachlorophenol in waste water, is processed
At 30 DEG C, by unmodified for 0.12g nano-TiO2Powder body and 0.12g embodiment 1 gained finished product are separately added in the parachlorophenol solution that two groups of 50mL concentration is 100000mg/L, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, under light illumination, 24.0h is stirred with the rotating speed of 180r/min, sample time is 2.0h/ time, it is centrifuged treatment fluid under 600r/min rotating speed separating, reclaim photocatalyst powder, take its supernatant, absorbance with UV-6 type ultraviolet-visible spectrophotometer detection residual parachlorophenol, calculate its relative concentration, and draw relative concentration versus time curve.From Figure 2 it can be seen that use unmodified nano-TiO2After powder handling, the relative concentration after 10.0h reaches 85.2%, and with modified nano-TiO2After powder handling, 8.0h can reach degradable.
(3) paracide in waste water, is processed
At 30 DEG C, by unmodified for 0.12g nano-TiO2Powder body and 0.12g embodiment 1 gained finished product are separately added in the paracide solution that two groups of 50mL concentration is 100000mg/L, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, under light illumination, 24.0h is stirred with the rotating speed of 180r/min, sample time is 1.0h/ time, it is centrifuged treatment fluid under 600r/min rotating speed separating, reclaim photocatalyst powder, take its supernatant, absorbance with UV-6 type ultraviolet-visible spectrophotometer detection residual paracide, calculate its relative concentration, and draw relative concentration versus time curve.As seen from Figure 3, unmodified nano-TiO is used2After powder handling, the relative concentration after 7.0h reaches 93.5%, and with modified nano-TiO2After powder handling, 4.0h can be degradable.
2, the 1,2,4-trichloro-benzenes in gained finished product degrading high concentration waste water in embodiment 1-4 is utilized
(1), matched group
At 30 DEG C, by unmodified for 0.12g nano-TiO2It is the 1 of 100000mg/L that powder body adds 50mL concentration, 2, in 4-trichlorobenzene solution, with constant temperature stirring 10min under 180r/min rotating speed under no light condition, under light illumination, 24.0h is stirred with the rotating speed of 180r/min, sample time is 2.0h/ time, is centrifuged treatment fluid separating, reclaims photocatalyst powder under 600r/min rotating speed, take its supernatant, the absorbance of residual 1,2,4-trichloro-benzenes is detected with UV-6 type ultraviolet-visible spectrophotometer, calculate its relative concentration, and draw relative concentration versus time curve.From fig. 4, it can be seen that the relative concentration after 22.0h reaches 33.6%, 24.0h can be degradable；
(2) the 1,2,4-trichloro-benzenes in embodiment 1 gained finished product degrading high concentration waste water, is utilized
At 30 DEG C, 0.12g embodiment 1 gained finished product is added 50mL concentration is the 1 of 100000mg/L, 2, in 4-trichlorobenzene solution, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, under light illumination, stirring 24.0h with the rotating speed of 180r/min, sample time is 2.0h/ time, it is centrifuged treatment fluid under 600r/min rotating speed separating, reclaim photocatalyst powder, take its supernatant, detect residual 1 with UV-6 type ultraviolet-visible spectrophotometer, 2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration, and draws relative concentration versus time curve.From fig. 4, it can be seen that the relative concentration after 8.0h reaches 5.8%, 10.0h can be degradable.
(3) the 1,2,4-trichloro-benzenes in embodiment 2 gained finished product degrading high concentration waste water, is utilized
At 30 DEG C, 0.12g embodiment 2 gained finished product is added 50mL concentration is the 1 of 100000mg/L, 2, in 4-trichlorobenzene solution, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, under light illumination, stirring 24.0h with the rotating speed of 180r/min, sample time is 2.0h/ time, it is centrifuged treatment fluid under 600r/min rotating speed separating, reclaim photocatalyst powder, take its supernatant, detect residual 1 with UV-6 type ultraviolet-visible spectrophotometer, 2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration, and draws relative concentration versus time curve.From fig. 4, it can be seen that the relative concentration after 8.0h reaches 4.3%, 10.0h can be degradable.
(4) the 1,2,4-trichloro-benzenes in embodiment 3 gained finished product degrading high concentration waste water, is utilized
At 30 DEG C, 0.12g embodiment 3 gained finished product is added in 1,2, the 4-trichlorobenzene solution that 50mL concentration is 100000mg/L, under no light condition, stir 10min with 180r/min rotating speed constant temperature, utilize zeta current potential nano particle size instrument to measure the particle size distribution of the emulsion prepared；Under light illumination, 24.0h is stirred with the rotating speed of 180r/min, sample time is 2.0h/ time, is centrifuged treatment fluid separating, reclaims photocatalyst powder under 600r/min rotating speed, take its supernatant, the absorbance of residual 1,2,4-trichloro-benzenes is detected with UV-6 type ultraviolet-visible spectrophotometer, calculate its relative concentration, and draw relative concentration versus time curve.From fig. 4, it can be seen that the relative concentration after 6.0h reaches 13.3%, 8.0h can be degradable；Detection supernatant absorbance when 2.0h, 4.0h, 6.0h, 7.0h and 8.0h respectively, is shown in Fig. 5, as it is shown in figure 5, because solution is supersaturated solution, therefore initially, the curve co-insides of 2h, 4h, after 8h, the absorption of 200-210nm no longer occurs, benzene homologues degraded is completely；When initial, 2.0h and 4.0h, the particle size distribution of emulsion is shown in Fig. 6, as shown in Figure 6, emulsion droplet size scope between 3-30 μm, mean diameter respectively 22 μm, 14 μm and 5 μm, after 6.0h, grain size distribution no longer occurs, high concentration emulsion droplet tapers into disappearance.
(5) the 1,2,4-trichloro-benzenes in embodiment 4 gained finished product degrading high concentration waste water, is utilized
At 30 DEG C, 0.12g embodiment 4 gained finished product is added 50mL concentration is the 1 of 100000mg/L, 2, in 4-trichlorobenzene solution, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, under light illumination, stirring 24.0h with the rotating speed of 180r/min, sample time is 2.0h/ time, it is centrifuged treatment fluid under 600r/min rotating speed separating, reclaim photocatalyst powder, take its supernatant, detect residual 1 with UV-6 type ultraviolet-visible spectrophotometer, 2, the absorbance of 4-trichloro-benzenes, calculates its relative concentration, and draws relative concentration versus time curve.From fig. 4, it can be seen that the relative concentration after 8.0h reaches 3.1%, 10.0h can be degradable.
From fig. 4, it can be seen that with unmodified nano-TiO2Powder body is compared, and embodiment 1-4 gained modified light catalyst is respectively provided with higher catalytic activity, when 6.0-8.0h, 1,2,4-trichloro-benzenes in solution is had comparatively ideal degradation efficiency, and wherein embodiment 3 gained modified catalyst effect is preferably.
3, the solution temperature impact on modified light catalyst activity is investigated
0.12g embodiment 3 gained finished product is added a series of 50mL concentration is the 1 of 100000mg/L, 2, in 4-trichlorobenzene solution, under no light condition, stir 10min with 180r/min rotating speed constant temperature, utilize zeta current potential nano particle size instrument to measure the particle size distribution of the emulsion prepared；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, stirs 4.0h, the particle size distribution of sampling detection emulsion with the rotating speed of 180r/min, and draws emulsion droplet mean diameter variation with temperature curve.As seen from Figure 7, modified light catalyst optimum temperature when degrading 1,2,4-trichloro-benzenes is 35 DEG C, and emulsion droplet size is minimum at this moment, and the activity of photocatalyst is the highest at this moment.
4, the solution ph impact on modified light catalyst activity is investigated
0.12g embodiment 3 gained finished product is added a series of 50mL concentration is the 1 of 100000mg/L, 2, in 4-trichlorobenzene solution, under no light condition, stir 10min with 180r/min rotating speed constant temperature, utilize zeta current potential nano particle size instrument to measure the particle size distribution of the emulsion prepared；It is 3,5,7,9,11 at pH value respectively, under light illumination, stirs 4.0h, the particle size distribution of sampling detection emulsion with the rotating speed of 180r/min, and draw the emulsion droplet mean diameter change curve with pH value.As seen from Figure 8, modified light catalyst optimum pH value when degrading 1,2,4-trichloro-benzenes is 5, and emulsion droplet size is less at this moment, and the activity of photocatalyst is the highest at this moment.
5, the reusability of modified light catalyst of the present invention
At 30 DEG C, by unmodified for 0.12g nano-TiO2It is the 1 of 100000mg/L that powder body and 0.12g embodiment 3 gained finished product are separately added into two groups of 50mL concentration, 2, in 4-trichlorobenzene solution, 10min is stirred with 180r/min rotating speed constant temperature under no light condition, the former is 8.0h, 24.0h sample time, under light illumination, with the rotating speed stirring reaction of 180r/min, sample time is 8.0h, after be centrifuged treatment fluid under 600r/min rotating speed separating, after reclaiming photocatalyst powder, take its supernatant, detect residual 1,2 with UV-6 type ultraviolet-visible spectrophotometer, the absorbance of 4-trichloro-benzenes, calculates its relative concentration.Catalyst muffin is dried through 300Pa and 120 DEG C, is again separately added in 1,2, the 4-trichlorobenzene solution that two groups of 50mL concentration is 100000mg/L, the like, the reusability of photocatalyst have been investigated, result is in Table 2.
Table 2 modified light catalyst reusability data of the present invention
From table 2, unmodified nano-TiO2Powder body is when 8.0h, and in solution, the concentration of 1,2,4-trichloro-benzenes is about 100.00%, for saturated concentration, even if what just can reach 1,2,4-trichloro-benzenes when 24.0h is degradable, and gained modified Nano TiO of the present invention2When 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 is held essentially constant, illustrate that product of the present invention has good catalysis activity and stability, the industrial wastewater of the benzo pollutants processing high concentration, difficult degradation, complicated component is had good effect, it may be achieved efficient, qualified discharge.
Claims (7)
1. modified nano-titanium dioxide photocatalyst, it is characterised in that prepared by following steps and obtain:
1) by nano-TiO2Powder body adds CCl4In, after stirring, it is warming up to 80 DEG C, obtains mixture A；By PCl3It is dissolved in CCl4In, mixing, by PCl3CCl4Solution drops in mixture A, after be warming up to 90 DEG C, react 2-4h, reclaim the CCl in reactant liquor4, obtain powder body I, wherein: be used for dissolving nano-TiO2The CCl of powder body4, nano-TiO2Powder body, PCl3、PCl3CCl4The mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10)；
2) being added by benzene in alpha-olefin sulfonic acid, stirring is warming up to 130 DEG C, treats that alpha-olefin sulfonic acid content is constant, obtains phenylalkyl sulfonic acid；It is cooled to 10 DEG C-20 DEG C, continues stirring, drip oleum, dropwise, stirring reaction 2-3h at 25 DEG C, drip 0.2mol L-1Dilute hydrochloric acid, rear addition mass fraction is the NaOH aqueous solution of 20%, to solution in neutrality, remove solvent, obtain paste II, paste II is dissolved in dehydrated alcohol, filter, take filtrate, remove solvent, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, 4-sodium sulfonate-phenyl sodium alkyl sulfonate must be refined, wherein: alpha-olefin sulfonic acid, benzene, oleum, dilute hydrochloric acid, dehydrated alcohol mass ratio be 1:(1/2-1): (3-5): (1-3): (2-4)；
3) by step 2) gained refining 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl4And Br2Being sequentially added into reactor, heating, to backflow, reacts 12-20h, is the NaHCO of 9% with mass fraction successively3Aqueous solution, distilled water, saturated common salt water washing, dry, obtain 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, wherein: refining 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl4、Br2、NaHCO3Aqueous solution, distilled water, saturated aqueous common salt mass ratio be 1:(20-40): (2-5): (50-200): (100-300): (100-200)；
4) with the oxide of HCl treatment metallic magnesium surface, clean with dehydrated alcohol and absolute ether successively, after magnesium metal is poured in the reactor filling absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, stirring, to magnesium total overall reaction, is sequentially added into double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and step 1) gained powder body I, backflow 15-20h, pours the 2mol L of 5 DEG C-10 DEG C into by reactant liquor-1Aqueous hydrochloric acid solution in, sucking filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photocatalyst finished product, wherein: the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, double; two (1,3-diphenylphosphine) propyl group Nickel Chloride, step 1) mass ratio of gained powder body I, 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 photocatalyst, it is characterised in that comprise the following steps:
1) by nano-TiO2Powder body adds CCl4In, after stirring, it is warming up to 80 DEG C, obtains mixture A；By PCl3It is dissolved in CCl4In, mixing, by PCl3CCl4Solution drops in mixture A, after be warming up to 90 DEG C, react 2-4h, reclaim the CCl in reactant liquor4, obtain powder body I, wherein: be used for dissolving nano-TiO2The CCl of powder body4, nano-TiO2Powder body, PCl3、PCl3CCl4The mass ratio of solution is (10-20): 1:(1/2-1/3): (5-10)；
2) being added by benzene in alpha-olefin sulfonic acid, stirring is warming up to 130 DEG C, treats that alpha-olefin sulfonic acid content is constant, obtains phenylalkyl sulfonic acid；It is cooled to 10 DEG C-20 DEG C, continues stirring, drip oleum, dropwise, stirring reaction 2-3h at 25 DEG C, drip 0.2mol L-1Dilute hydrochloric acid, rear addition mass fraction is the NaOH aqueous solution of 20%, to solution in neutrality, remove solvent, obtain paste II, paste II is dissolved in dehydrated alcohol, filter, take filtrate, remove solvent, obtain 4-sodium sulfonate-phenyl sodium alkyl sulfonate, dry, 4-sodium sulfonate-phenyl sodium alkyl sulfonate must be refined, wherein: alpha-olefin sulfonic acid, benzene, oleum, dilute hydrochloric acid, dehydrated alcohol mass ratio be 1:(1/2-1): (3-5): (1-3): (2-4)；
3) by step 2) gained refining 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl4And Br2Being sequentially added into reactor, heating, to backflow, reacts 12-20h, is the NaHCO of 9% with mass fraction successively3Aqueous solution, distilled water, saturated common salt water washing, dry, obtain 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, wherein: refining 4-sodium sulfonate-phenyl sodium alkyl sulfonate, CCl4、Br2、NaHCO3Aqueous solution, distilled water, saturated aqueous common salt mass ratio be 1:(20-40): (2-5): (50-200): (100-300): (100-200)；
4) with the oxide of HCl treatment metallic magnesium surface, clean with dehydrated alcohol and absolute ether successively, after magnesium metal is poured in the reactor filling absolute ether, add step 3) gained 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, stirring, to magnesium total overall reaction, is sequentially added into double; two (1,3-diphenylphosphine) propyl group Nickel Chloride and step 1) gained powder body I, backflow 15-20h, pours the 2mol L of 5 DEG C-10 DEG C into by reactant liquor-1Aqueous hydrochloric acid solution in, sucking filtration, filter cake washes with water, dry, obtain modified nano-titanium dioxide photocatalyst finished product, wherein: the absolute ether in magnesium metal, reactor, 4-sodium sulfonate-phenyl bromo sodium alkyl sulfonate, double; two (1,3-diphenylphosphine) propyl group Nickel Chloride, step 1) mass ratio of gained powder body I, 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 photocatalyst as claimed in claim 2, it is characterised in that step 1) described in PCl3CCl4The rate of addition of solution is 0.13333-0.26667g/min, step 2) described in oleum and 0.2mol L-1The rate of addition of dilute hydrochloric acid is 0.16667-0.33333g/min.
4. the preparation method of modified nano-titanium dioxide photocatalyst as claimed in claim 2, it is characterised in that described nano-TiO2The particle diameter < 20nm of powder body.
5. the preparation method of modified nano-titanium dioxide photocatalyst as claimed in claim 2, it is characterised in that the carbon number range of described alpha-olefin sulfonic acid is C12-C20.
6. the application in the benzene homologues wastewater treatment of concentration 2000 to 100000mg/L of the modified nano-titanium dioxide photocatalyst described in claim 1.
7. modified nano-titanium dioxide photocatalyst application in the benzene homologues wastewater treatment of concentration 2000 to 100000mg/L as claimed in claim 6, it is characterised in that described benzene homologues is 1,2,4-trichloro-benzenes, paracide, parachlorophenol or phenol.
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| 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 |
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| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
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