CN101219371A - Photocatalysis oxidation treated high concentration organic trade waste - Google Patents
Photocatalysis oxidation treated high concentration organic trade waste Download PDFInfo
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- CN101219371A CN101219371A CNA2007100633004A CN200710063300A CN101219371A CN 101219371 A CN101219371 A CN 101219371A CN A2007100633004 A CNA2007100633004 A CN A2007100633004A CN 200710063300 A CN200710063300 A CN 200710063300A CN 101219371 A CN101219371 A CN 101219371A
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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
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Abstract
The invention relates to a modified loading nano composite photocatalyst which takes titanium dioxide as main part and adopts new reaction technique to degraded the organic industrial wastewater in a water processing system (see attached drawing 1 in Instruction). The main point on preparing the catalyst lies in that titanium dioxide active compounds loaded on different carriers are employed to prepare a loading photocatalyst with grain diameter of 5-40nm; meanwhile, different elements are mixed into the loading photocatalyst to reduce the composition between photoproduciton electron and cavity, which enables the catalyst to move the light absorbing wavelength thereof towards the visible regions, thus effectively improving the degradation rate of organic pollutants as a new environmental-friendly catalyst. As to the new technique of processing the organic industrial wastewater, the invention overcomes the defects that the present photocatalysts are only used for degrading the organic industrial wastewater with low concentration. The catalyst being irradiated respectively or simultaneously under sunbeam and ultraviolet light can decrease COD values of high-concentration organic industrial wastewater from 10000-40000mg/L to less than 100mg/L in short time, thus meeting the national emission standard.
Description
Technical field
What the present invention relates to is load type nano composite photocatalyst and the technique for applying thereof of preparation based on titanium dioxide.Wherein adopt the method for co-precipitation in conjunction with sol-gel, emphasis carries out modification by the load of titanium dioxide on different carriers with the different elements that mix, prepare the nano composite photo-catalyst that particle diameter is 5～40nm, not only improve photocatalytic activity, also reduced the compound degree in light induced electron and hole.This catalyst can adopt ultraviolet light and visible light radiation condition respectively or simultaneously in water treatment facilities (seeing Figure of description 1), effectively degradable organic pollutant is an environmentally friendly catalyst of new generation.This photochemical catalyst has overcome present photocatalysis technology can only be used to the to degrade shortcoming of 10～3000mg/L low concentration organic industrial sewage, as patent " preparation of catalyzing oxidizing degrading organism under sun lighting load type nano composite photocatalyst ", application number: 2005100830380; Patent " a kind of method of photocatalysis degradation organic contaminant and special-purpose solid-phase photocatalyst thereof ", application number: 200510064496.X.Catalyst of the present invention not only can be used for the low concentration organic industrial sewage of degrading, the COD value that also can be used for degrading is the high-concentration organic industrial waste water of 10000～40000mg/L, and by the reaction new technology, not only finished recycling, and COD value of waste water can have been dropped to below the national industrial wastewater discharge standard 100mg/L catalyst.
Technical background
Along with industrial expansion, the quantity of industrial wastewater is increasing, and composition is also increasingly sophisticated, and the last outlet of industrial wastewater has two usually, be the irrigated farmland or enter water body, if can not good treatment, certainly will will cause severe contamination harm environment water body to a large amount of industrial wastewaters.So must before discharging, should suitably be handled, make it reach the sewage drainage standard of country's promulgation.
The modern industry wastewater treatment method mainly is divided into physical treatment process, method of chemical treatment and biological treatment three classes.
Physical treatment process is meant the method that comprises oil film and oil droplet by undissolved suspended state pollutant in physical action separation, the recovery waste water, can be divided into gravitational separation process, centrifugal separation and sieving and hold back method etc.
Method of chemical treatment is meant by chemical reaction and separates with effect of mass transmitting, removes the method that is dissolving, colloidal state pollutant in the waste water or is translated into innocuous substance.In chemical treatment, coagulation, neutralization, redox etc. are arranged based on the unit that adds medicament generation chemical reaction; And extraction, stripping, stripping, absorption, ion-exchange and electrodialysis and counter-infiltration etc. are arranged based on the processing unit of effect of mass transmitting.The existing chemical action of processing of utilization effect of mass transmitting have again in relevant physical action, so also can from fractionation, branch away, become another kind of facture, be physicochemical treatment method.
Biological treatment makes the organic pollution that is dissolving, colloid and fine suspended state in the waste water be converted into the method for stable, harmless material by the metabolism of microorganism.According to the difference of microorganism, biological treatment can be divided into aerobe again to be handled and anaerobic bio-treated.Biological wastewater treatment is widely used to be the aerobe facture.By tradition, the aerobe facture is divided into activated sludge process and biomembrance process again.The anaerobic bio-treated method has another name called the biological reducing facture, is mainly used in organic wastewater and the mud of handling high concentration.
Pollution in the waste water is diversified, often is difficult to all pollutants are eliminated with a kind of processing unit, needs usually just can reach requirement by after the treatment system processing of being made up of several method and several processing unit.
In decades recently, a kind of new method of degradable organic pollutant-conductor photocatalysis oxidizing process, be subjected to the attention of researcher, various countries have dropped into great amount of manpower and material resources and have launched the basic theory of semiconductor photocatalysis technology and the research of application foundation.
The key issue of support type conductor photocatalysis technology is: under the condition of illumination, semiconductor energy produces light induced electron and hole, and optical excitation electronics and photoproduction high energy holes can be 10
9Compound and lose activity in second.Therefore how to catch the optical excitation electronics fast, it is very important making itself and high energy holes effectively separate to reduce compound efficient to raising conductor photocatalysis degradable organic pollutant.In order effectively to utilize solar energy to improve photocatalytic activity, this research institute has prepared support type high-dispersion nano composite photo-catalyst by doped tin, iron, zinc, cerium, molybdenum, silver, platinum, manganese, tungsten, silicon, vanadium, zirconium, aluminium, copper, cadmium element simultaneously.By doped chemical, active component has reduced the compound of light induced electron and hole, and the optical excitation scope is moved to visible light by ultraviolet light, has made full use of the solar energy of green non-pollution.Reach the catalytic active component high dispersive by carrier, particle diameter has also improved photocatalytic activity simultaneously at 5～40nm.The application started a kind of brand-new stable, firmly, loaded nano composite titanium dioxide photochemical catalyst and use new technology efficiently, developing can be respectively or have highly active multifunctional photocatalysis agent simultaneously under ultraviolet light and solar light irradiation condition, has also set up the new technology of catalyzing oxidizing degrading organic industrial sewage simultaneously.
Summary of the invention
The present invention adopts co-precipitation to make TiO in conjunction with the method for collosol and gel
2Load on the carrier with doped chemical, to prepare a kind of new catalyst, to its objective is that particle diameter is little, decentralization is high, specific area is big in order obtaining, Heat stability is good, catalytic activity are high can respectively or have efficient light activated load type nano composite photocatalyst simultaneously under ultraviolet light and visible light condition.This catalyst can be that the organic industrial sewage COD value of 10000mg/L～40000mg/L is reduced to below the discharging standards 100mg/L with concentration under the water treatment technology condition of design voluntarily.
Advantage of the present invention mainly is:
1, the present invention relates to one or more metal element oxides in doped tin, iron, zinc, cerium, molybdenum, silver, platinum, manganese, tungsten, silicon, vanadium, zirconium, aluminium, copper, the cadmium or sulfide in titanium dioxide, prepare novel load type nano composite photocatalyst, it can make light induced electron at different transition between the energy levels, thereby electronics is separated with the hole, reduce compoundly, improve photocatalytic activity.Simultaneously, titanium dioxide meeting and doped chemical and carrier can form a kind of new chemical bond, have also strengthened the fastness between catalyst and carrier when increasing catalyst activity.
2, different elements and titanium dioxide mix, because energy level is interlaced, can increase the photoresponse scope of catalyst, and its absorption to light is moved to visible light by ultraviolet region.Solved the shortcoming that titanium dioxide can only absorb ultraviolet light, be able to make full use of the solar energy of green non-pollution, also improved utilizing the purpose of optical absorption intensity.
3, nano-photocatalyst loads on the carrier, makes photocatalytic activity component high degree of dispersion, in order to improve photocatalytic activity.
4, earlier prepare gel, carry out drying again after making it to become alcogel with the water in the ethanol replacing water gel again with the co-precipitation sol-gel process.This is because ethanol is low than water viscosity, the diffusion height, therefore can reduce internal surface of hole tension force, the gel pore structure is difficult for destroyedly in the dry run, avoids the particle duct to subside and reunites, and it is big to obtain specific area, pore capacities is big, density is little, and complicated microcellular structure, high catalytic activity catalyst are arranged.
5, co-precipitation of the present invention has simple to operately in conjunction with the Prepared by Sol Gel Method catalyst, to the less demanding characteristics of equipment, can satisfy industrial requirement.
6, the catalyst of the present invention organic industrial sewage of can effectively degrading under the solar light irradiation condition has utilized solar energy fully, can solve industrial energy demand.
7, the designed industrial reaction device of the present invention is simple in structure, and handling strong, equipment material is less demanding, and very strong industrial applicability is arranged.
The shortcoming that 8, degradation effect can only be arranged low-concentration organic at present patented technology, another characteristics of the present invention are that the manometer load-type photochemical catalyst that makes not only can have degradation to low-concentration organic waste water, the most important thing is can organic matter and their mixture that multiple high concentration COD value is 10000～40000mg/L be carried out mineralising and can reach good effect.
The present invention mainly by the following technical solutions
1, quantitative solvent is fully mixed with titanium-containing compound, stirring condition drips the metal salt solution of one or both a certain amount of concentration down, and the adding certain amount of surfactant makes it to become emulsion, after fully stirring certain hour, the carrier that adds a certain amount of processing is regulated above-mentioned pH of mixed value to alkalescence with certain density alkaline solution simultaneously and is obtained hydrogel.Ageing through 5～72 hours, with above-mentioned hydrogel centrifuge washing to there not being chlorion.Make it to become alcogel with the water in the absolute ethyl alcohol replacing water gel at last, dry under 25～180 ℃ temperature.
2, the catalyst precursor that above-mentioned (1) is obtained is calcined with air or inert atmosphere protection in Muffle furnace; temperature is at 300～900 ℃; calcination time is 0.5～8 hour, makes good dispersion, particle diameter is little, catalytic activity is high manometer load-type binary or ternary support type composite photo-catalyst at last.
3, with the light-catalyzed reaction system of design processing voluntarily photocatalysis performance is tested.There are uviol lamp or fluorescent lamp in the center, adds reactant liquor and oxidant, and catalyst consumption is 2～10Kg/m
3, at reactant liquor bottom bubbling air, its flow is 1～12m
3/ h, 25 ± 1 ℃ of temperature are dispersed in the reactant liquor catalyst, pipette an amount of reactant liquor at regular intervals, after the centrifugation, measure the COD value with potassium dichromate method.
Titanium compound can be the mixture of a kind of, two or more inorganic salts in titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, isopropyl titanate, titanium propanolate, tetrabutyl titanate, iso-butyl titanate, the tetraethyl titanate in the above-mentioned said sol-gal process.
The solvent of above-mentioned said dissolving titanium compound and transition metal has a kind of, two or more mixtures in the following monohydric alcohol dihydroxylic alcohols of dilute hydrochloric acid solution, deionized water, diethanol amine, triethanolamine, absolute ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol and four carbon atom and isomer thereof, glycerine, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, toluene, dimethylbenzene, cyclohexane, alkane, the fragrant alkane.
Above-mentioned different modification ions that mix or element comprise that slaine or transition metal salt are cerous nitrates, cerous sulfate, iron chloride, ferric nitrate, ferric sulfate, zinc chloride, zinc sulfate, zinc nitrate, butter of tin, tin titan, cadmium nitrate, manganese sulfate, silver nitrate, copper chloride, sodium metavanadate and other contain tin, iron, zinc, cerium, molybdenum, silver, platinum, manganese, tungsten, silicon, vanadium, zirconium, aluminium, copper, a kind of in the inorganic salts of cadmium or inorganic compounding salt and the organic salt thereof, two or more mixtures.
Above-mentioned said surfactant or dispersant are a kind of, two or more mixtures in diethanol amine, triethanolamine, absolute ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol, tween, polyvinylpyrrolidone, polyvinyl alcohol, neopelex, odium stearate, lauryl sodium sulfate, acetate, AEO, the oleic acid.
Above-mentioned used carrier is sand, glass pellet, glass fiber, sheet glass, glass fiber mesh, glass fabric, hollow glass micro-ball, glass helix tube, glass infuser, silica gel, silica, quartz sand, pottery, zeolite, aluminium oxide, active carbon, carbon nanotube, molecular sieve, muscovite, metal species.
Above-mentioned said precipitating reagent comprises a kind of, two or more mixtures in NaOH, sodium carbonate, sodium acid carbonate, sodium acetate, vulcanized sodium, potassium hydroxide, potash, saleratus, ammoniacal liquor, the urea.
Above-mentioned said degradation solution is that organic industrial sewage can contain phenol, acrylic acid, acrylate, acetate, formic acid, acetaldehyde, benzene, toluene, nitrobenzene, methyl orange, methyl blue, rhodamine-6G, rhodamine B, hydroxyazobenzene, salicylic acid, disperse scarlet, contain sulfonic polarity azo dyes; Surfactant is as a kind of, two or more mixtures in chloro thing trichloro-ethylene, trichloro-benzene, chloroform, carbon tetrachloride, 4-chlorophenol, tetrachloro biphenyl, fluorine Lyons, Pentafluorophenol, fluoroolefin, fluorinated aromatic hydrocarbon and the floating oils of the water surface such as ten disulfobenzene sodium sulfonates, chlorination Bian Ji ten disulfo dimethyl amines, nonyl polyoxyethylene benzene, ethyoxyl alkyl phenol.
The concrete mode of implementing
Embodiment 1: measure the volumetric flask that the 248.4mL concentrated hydrochloric acid is put into 500mL, add entry and be diluted to graduation mark and shake up and be made into 6mol/L hydrochloric acid.Measure 236.4mLTiCl
4Concentrated solution slowly joins in ventilating kitchen in the 2000mL beaker that is placed in the ice-water bath, slowly adds the hydrochloric acid solution that 263.60mL has prepared simultaneously, and constantly stirs until TiCl fast
4All dissolve, get the TiCl of 4mol/L
4Solution.Accurately measure 9.37mL and put into the 500mL beaker and add water to 114mL, add 5mLAEO-3, the FeCl of 0.01mol/L
3Solution 3.75mL, the 9g active carbon.Slowly drip 3moL/lNH
3To pH value to 8～9.Ageing 10～40 hours is washed to and does not contain Cl
-Get alcogel with the ethanol exchanged water, after 100 ℃ of following dryings, with the catalyst that obtains in Muffle furnace in 600 ℃ of calcination 1h, promptly obtain load type nano composite photocatalyst.The catalyst that obtains is got 4g degrades to the 300mL acrylic acid wastewater.Under the irradiation of ultraviolet light, through the acrylic acid wastewater degraded to the about 30000mg/L of concentration in 18 hours, the COD degradation rate was 99.7%.
Embodiment 2: the TiCl of accurately measuring 10mL 4mol/L
4Put into the 500ml beaker and add water to 120mL, add the 10mL triethanolamine, electromagnetic agitation 1 hour; Ce (the NO that adds 0.1mol/L
3)
3Solution makes Ti: the Ce mass percent is 1: 0.03, adds 9g ZSM-5 then, slowly drips 1mol/LKOH to pH and is worth 8～9.Ageing is 10～40 hours then, is washed to not contain Cl
-Get alcogel with the ethanol exchanged water, move to and carry out supercritical reaction in the autoclave, with the catalyst that obtains in Muffle furnace in 550 ℃ of calcination 1h, obtain nano composite photo-catalyst.Formerly the irradiation 6h of ultraviolet light shines 8h through fluorescent lamp again, catalyst amount 3.5g, and measuring 300mL COD value is that 25000mg/L rhodamine-6G, rhodamine B degradation rate are 98%.
Embodiment 3: the TiCl of accurately measuring 9.37mL 4mol/L
4Put into the 500mL beaker and add water to 114mL, add the FeCl of 5mLAEO-9 and 0.1mol/L
3Solution makes Ti: the Fe mass percent is 1: 0.02, adds 9g hollow glass bead again, slowly adds 0.1mol/L KOH to pH value then and is 8～9 and end, and ageing 10～40 hours is washed to no Cl
-The ethanol exchanged water is used in the back, carries out supercritical drying and gets alcogel in 0.5 hour.Alcogel is calcined under 500 ℃ of conditions and was got hollow glass pellet support type composite photo-catalyst in 1.5 hours.Under ultraviolet light and visible light shone simultaneously, catalyst amount 2g degraded for the 20000mg/L salicylic acid to 300mL concentration, and the COD degradation rate reached 95.5% in 8 hours.
Embodiment 4: the TiCl of measuring 8.52mL 4mol/L
4Be diluted to 120mL, behind the adding 5.5mL neopelex, add the ZnCl of 0.1ml/L
2Solution makes Ti: the Zn mass percent is 1: 0.05, adds 9g again and handles clean sand, and slowly adding 0.1mol/L KOH to pH value then is 8～9, and the ethanol exchanged water is used in beginning ageing 10～40 hours, carries out supercritical drying and gets alcogel in 0.5 hour.Alcogel is calcined under 600 ℃ of conditions and was got sand support type composite photo-catalyst in 1 hour.Under the irradiation of ultraviolet light, catalyst amount 3g is that the 4-chlorophenol of 15000mg/L is degraded to 300mL concentration, and the COD degradation rate reached 95% in 6 hours.
Embodiment 5: the TiCl of measuring 8.52mL 4mol/L
4Be diluted to 120mL, behind the adding 5.5mL AEO-3, add the Fe of 0.1mol/L
2(SO
4)
3Solution makes Ti: the Fe mass percent is 1: 0.0003, adds 9g γ-Al again
2O
3, slowly adding 0.1mol/L KOH to pH value then is 8～9, the ethanol exchanged water is used in ageing 10～40 hours, carries out supercritical drying and gets alcogel in 0.5 hour.Alcogel is calcined under 600 ℃ of conditions and was got γ-Al in 1 hour
2O
3The support type composite photo-catalyst.It is 4 that adjusting contains the chloroform pH value of waste water, catalyst amount 2.5g, and formerly through radiation of visible light, again by under the UV-irradiation condition, 12 hours 300mL concentration is that 25000mg/L chloroform waste water COD degradation rate reaches 98.7%.
Embodiment 6: the TiCl of measuring 10.00mL 4mol/L
4Be diluted to 120mL, behind the adding 3.5mL AEO-3, add the Cd (NO of 0.1mol/L
3)
2Solution makes Ti: the Cd mass percent is 1: 0.0003, adds 9g ZSM-5 again, and slowly adding 3mol/L ammoniacal liquor to pH value then is 8～9, begins ageing 10～40 hours after stirring, and uses the ethanol exchanged water, carries out supercritical drying and gets alcogel in 0.5 hour.Alcogel is calcined under 600 ℃ of conditions and was got the support type composite photo-catalyst in 1 hour.Obtain the manometer load-type composite photo-catalyst, the Pyrogentisinic Acid degrades.Under irradiation of sunlight, catalyst amount 1.2g, through reaction in 6 hours, 200mL phenol COD value was degraded to 96mg/L by original 3000mg/L.
Embodiment 7: the TiCl of measuring 8.52mL 4mol/L
4Be diluted to 120mL, behind the dropping 3.9mL AEO-3, add the Cd (NO of 0.1ml/L
3)
2Solution makes Ti: the Cd mass percent is 1: 0.001, adds 9g γ-Al again
2O
3, slowly add 1.0mol/L Na then
2S to pH value is 8～9, stirs to begin ageing 10～40 hours after 1 hour, gets alcogel with the ethanol exchanged water.Alcogel is calcined under 600 ℃ of conditions and was got γ-Al in 1 hour
2O
3The support type composite photo-catalyst.Under sunshine and ultraviolet light shine simultaneously, catalyst amount 4.5g, through reaction in 18 hours, the COD degradation rate that concentration is about the 400mL acrylic acid wastewater of 30000mg/L reached 99.8%.
Embodiment 8: measure the 10.4mL butyl titanate and be diluted with water to 150mL, slowly add the FeCl of 10mL 0.1mol/L
3And 5mlAEO-3, activated carbon after the adding 9g acid treatment is 8～9 with 2mol/LNaOH regulator solution pH value behind 10～50min, still aging 10～40 hours, gets alcogel with the ethanol exchanged water.Calcined 2 hours down at 650 ℃, obtain load type nano composite photocatalyst.Under irradiation of sunlight, catalyst amount 5g, through reaction in 40 hours, concentration was that the COD degradation rate of the 300mL acrylic acid wastewater of 32000mg/L reaches 99.8%, this moment, the COD value was 64mg/L.
Embodiment 9: measure 10.0mL 4mol/L TiCl
4Be diluted to 130mL with deionized water, slowly drip 7.5mL 0.01mol/LFe (NO
3)
3And 3mLAEO-3, evenly mix and add the 9g activated carbon behind the 30min, be 8～9 with 3mol/L ammoniacal liquor adjusting pH of mixed value then, ageing 10～40 hours gets alcogel with the ethanol exchanged water.In water bath chader dry 12～48 hours then, take out in Muffle furnace in 600 ℃ of calcination 1h, obtain the manometer load-type composite photo-catalyst, be that the methyl orange of 30000mg/L is degraded to 250mL concentration.Under in sunshine and ultraviolet light, shining, catalyst amount 4g, through reaction in 12 hours, the COD degradation rate of methyl orange reached 97%.
Embodiment 10: measure 9.37mL 4mol/L titanium tetrachloride and be diluted with water to 150mL, slowly add the Fe of 7.5mL 0.1mol/L
2(SO4)
3And 4mLAEO-3, add 9g ZSM-5 behind 10～50min, be 8～9 with 3mol/L ammoniacal liquor regulator solution pH value, still aging 10～40 hours, with the alcogel of ethanol exchanged water.In water bath chader dry 24 hours then, take out in Muffle furnace in 600 ℃ of calcination 1h, obtain the manometer load-type composite photo-catalyst, be that the salicylic acid of 24000mg/L is degraded to 300mL concentration.Behind irradiation of sunlight 12h, again through UV-irradiation 24h, catalyst amount 3.5g, through reaction in totally 36 hours, salicylic COD degradation rate reaches 97.8%.
Description of drawings
Fig. 1 is high-concentration organic industrial waste water degradation reaction device systems figure.
Claims (10)
1. adopt coprecipitation to combine and prepare the load type nano composite photocatalyst that is used to handle high-concentration organic industrial waste water with sol-gal process, it is characterized in that: it is evenly mixed to get titanium-containing compound and metal salt solution, add surfactant and carrier, dripping alkali liquid, regulate the pH value between 8～10, get hydrogel, again through ageing, dry, 300～900 ℃ of calcinings down, make load type nano composite photocatalyst, this catalyst has that particle diameter is little, good dispersion, characteristics that photocatalytic activity is high, and composition is by several composition the: TiO down
2The quality percentage composition is 10.0%～80.0%, and carrier quality percentage composition is 80.0%～20.0%, and doped metallic elements or nonmetalloid quality percentage composition are 0.01%～20.0%.
2. the invention provides a kind of new technology of photocatalysis oxidation treated high concentration organic trade waste, it is characterized in that: adopt change illumination condition and light application time, adjusting pH value of waste water, catalyst amount, adding oxidant in apparatus for photoreaction, to handle the organic industrial sewage of high concentration, COD value of waste water is dropped to below the national industrial wastewater discharge standard 100mg/L.
3. catalyst according to claim 1 is characterized in that titanium-containing compound is selected from a kind of, two or more mixtures in titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, isopropyl titanate, titanium propanolate, tetrabutyl titanate, iso-butyl titanate, the tetraethyl titanate.Carrier is selected from sand, glass pellet, glass fiber, sheet glass, glass fiber mesh, glass fabric, hollow glass micro-ball, glass helix tube, glass infuser, silica gel, silica, quartz sand, pottery, zeolite, aluminium oxide, active carbon, carbon nanotube, molecular sieve, muscovite.
4. catalyst according to claim 1 is characterized in that metal salt solution is selected from a kind of, two or more mixtures in cerous nitrate, cerous sulfate, iron chloride, ferric nitrate, ferric sulfate, zinc chloride, zinc sulfate, zinc nitrate, butter of tin, tin titan, cadmium nitrate, manganese sulfate, silver nitrate, copper chloride, the sodium metavanadate.
5. catalyst according to claim 1 is characterized in that nonmetalloid is selected from a kind of, two or more mixing among N, P, Si, S, Cl, the C.
6. catalyst according to claim 1 is characterized in that surfactant is selected from a kind of, two or more mixtures in diethanol amine, triethanolamine, absolute ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, butanols, the tert-butyl alcohol, tween, polyvinylpyrrolidone, polyvinyl alcohol, neopelex, odium stearate, lauryl sodium sulfate, acetate, AEO, the oleic acid; Used alkali lye is a kind of, two or more mixtures in NaOH, sodium carbonate, sodium acid carbonate, sodium acetate, potassium hydroxide, potash, saleratus, ammoniacal liquor, the urea.
7. catalyst according to claim 1 is characterized in that high-concentration organic industrial waste water that this catalyst is used for handling contains a kind of, two or more mixtures of phenol, acrylic acid, acrylate, acetate, formic acid, acetaldehyde, benzene, toluene, nitrobenzene, methyl orange, methyl blue, rhodamine-6G, rhodamine B, hydroxyazobenzene, salicylic acid, disperse scarlet.
8. new technology according to claim 2 is characterized in that the high-concentration organic industrial waste water concentration of degrading is 10000mg/L～40000mg/L, and catalyst amount is 2～10Kg/m
3, degradation time 6～48h.
9. new technology according to claim 2 is characterized in that nano composite photo-catalyst at ultraviolet light and visible light separately, simultaneously or under the alternating action condition, regulate pH value of waste water 1～7, the degraded organic industrial sewage.
10. new technology according to claim 2 is characterized in that oxidant is selected from potassium permanganate, H
2O
2, potassium bichromate, clorox, Cl
2, a kind of, two or more mixtures in the ozone, nitric acid, sodium sulfite, manganese dioxide, perchloric acid, potassium sulfide, KI.
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-
2007
- 2007-01-08 CN CNA2007100633004A patent/CN101219371A/en active Pending
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