CN100575281C - The water treatment method of light concentration organic pollutant - Google Patents

The water treatment method of light concentration organic pollutant Download PDF

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CN100575281C
CN100575281C CN200710065206A CN200710065206A CN100575281C CN 100575281 C CN100575281 C CN 100575281C CN 200710065206 A CN200710065206 A CN 200710065206A CN 200710065206 A CN200710065206 A CN 200710065206A CN 100575281 C CN100575281 C CN 100575281C
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water
pollutant
mesoporous silicon
silicon oxide
organic pollutant
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CN101279802A (en
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陶霞
刘冰
侯倩
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Beijing University of Chemical Technology
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The present invention relates to the method for light concentration organic pollutant in a kind for the treatment of water, this method is that carrier carries out effective enrichment to organic pollutant with mesoporous silicon based material, uses up in the narrow and small zone of enrichment then-Fenton or TiO 2Photocatalysis method makes organic matter degradation, mineralising.The organic silica-base material of enrichment can reclaim, and utilizes again, has avoided the secondary pollution of water quality in the water treatment procedure.The present invention has high-level efficiency, advantage cheaply.The purifying treatment that can be used for trace, trace biology difficult degradation poisonous organic wastewater in trade effluent and the city domestic sewage.

Description

The water treatment method of light concentration organic pollutant
Technical field
The present invention relates to a kind of water treatment method of removing organic pollutant, relate to the method for utilizing micro quantity organic pollutant in absorption and the high-level oxidation technology treating water particularly, can remove the organic pollutant of lower concentration in the water, high toxicity, bio-refractory, be applicable to the advanced processes of contaminated water feeding system in water source or sewage.
Background technology
Because chemical reagent, the universal of medicine are used, a large amount of toxic organic pollutants are entered in the water, become after the dilution trace or ultra-trace pollutent (as hormones, agricultural chemicals, dyestuff, the chloro thing, phenols, tensio-active agent etc.), toxicity is big, be difficult to degraded, long in the nature lifetime, the serious harm human health.At present the water treatment way that contains organic pollutant there are chemical oxidization method, absorption method, photocatalytic oxidation etc.Common chemical process is by reaction between the compound pollutent to be decomposed, so need to add chemical reagent to system in addition, for trace, trace contamination system, has introduced new source of pollution on the contrary.Absorption method is most typical to be active carbon adsorption, utilize that the activated carbon inside holes forms than bigger serface, many functional groups that the surface generates, constitute the active centre, make activated carbon have very strong physics and chemical adsorption capacity, can remove the pollutent in the water, the bioactive carbon method that is further development of of gac, affact from the physical and chemical adsorption of utilizing gac merely promptly that to utilize it be bio-carrier, the biological degradation of performance microorganism, remove degradable organic pollutant in the water, the defective that the bioactive carbon method exists is: gac price height, and intensity is low, regeneration period is long, and loss is big during regeneration, and working cost is higher, and to handling organic pollutant obvious selectivity is arranged.Chinese patent 881000597 in order to reduce working cost, proposes to use quartz sand, zeolite or haydite even-granular inert material as sorbing material, obtains the effect same with gac.Chinese patent 2004100802935, a kind of composite natural micro porous material sewage treating agent is proposed, utilize absorption, flocculation, the filtration compound action of multiple natural micro porous materials such as diatomite, zeolite, wilkinite, for reducing the selectivity of sorbing material, can handle the sewage that contains multiple pollutent, cut operating costs simultaneously.But, polluting for micro-content organism deleterious, bio-refractory in the above-mentioned treatment process, the treatment effect of (comprising the coloured pollution of dyestuff) is undesirable, and the regeneration period of sorbing material is long, and regeneration loss is big.
The high-level oxidation technology that development in recent years is got up is to produce oxyradical, make its attack larger molecular organics and reaction with it, thereby organic molecular structure is destroyed until being decomposed into carbonic acid gas and water, reach the purpose of efficient degradation toxic organic pollutants.Wherein light-Fenton method is one of high-level oxidation technology, and it is under acidic conditions, is catalyzer with the ferrous ion, and the high active oxyradical that is produced by hydrogen peroxide impels C-C or single (two) key oxidation of C-N, the reaction that fracture is decomposed.Oxidizing reaction be because OH has higher oxidizing potential (+2.8), can oxidation most organism.This method can thoroughly be removed anhydrate middle chemical oxygen demand, colourity and organic pollutant.Under visible light or UV-irradiation, the Fenton speed of response can be accelerated greatly, and hydrogen peroxide decomposition speed is fast, thereby rate of oxidation is higher." Journal of Molecular Catalysis magazine " rolled up 77 pages article " light of radiation of visible light-Fenton degradation of dye " (Wu, K. in 1999 144; Xie, Y; Zhao, J.; Hidaka, H.Photo-Fenton degradation of a dye under visible lightirradiation, J.Mol.Catal).The TiO2 photocatalytic oxidation that gets up of development in recent years also belongs to high-level oxidation technology in addition, utilizes the photocatalysis performance of titanium dioxide that organism is degraded.
Utilize molecular sieve carried photocatalyst and by high-level oxidation technology with organic matter degradation, it is the development of Fenton technology, that is: Photo-Fenton method, purpose is the usefulness of performance catalyzer, relevant this type of document is as " water treatment information reports " 2005 6 phases 6 pages of Sun Hong literary compositions, the article of Lv Jungang etc. " Fenton method and light Fenton method degraded 2, the research of 4-D "; The article of the yellow monarch's gift of Zhang Naidong " is strengthened the research of phenol in the UV/Fenton method degradation water " in 20～22 pages of " Techniques and Equipment for Environmental Pollution Control " 2002 32 phases of volume, though above-mentioned advanced oxidization method has Degradation preferably for most organic waste water, but for handling trace or trace organically-polluted water, utilize the Photo-Fenton method can waste a large amount of luminous energy, catalyzer, cost increases greatly, thereby makes this method uneconomical.Therefore improve the luminous energy of high-level oxidation technology and the utilising efficiency of catalyzer is one of this Study on Processing Methods emphasis.
Summary of the invention
The present invention is for improving high-level oxidation technology to containing the treatment efficiency of trace or trace organically-polluted water, adsorption and enrichment is efficiently combined with high-level oxidation technology, provide a kind of processing efficiency height, the water treatment method that is suitable for that process range is wide, cost is low to the organic pollutant that contains lower concentration, poisonous, bio-refractory.
Method of the present invention is based on following research: mesoporous material has mesoporous (2～50nm) ducts, the high-specific surface area (500～2000m of homogeneous 2/ g is 2～5 times of molecular sieve), it than molecular screen material have stronger adsorptive power (adsorptive capacity 2～100mg/g), its hole partition very thin (1～10nm), more help reaction and conduct heat, thereby guarantee the stable of catalyzer.Discover that mesoporous silicon oxide is dispersed in the water, can very fast organism be adsorbed on the surface, do not influence the Fenton reaction result simultaneously, and the carrier after the degraded also possesses adsorptive power, recycle for several times.In addition, contain a large amount of Si-O keys in the mesoporous silicon based material, the hydroxyl of a large amount of Si-OH is contained on the surface, can carry out functional modification, or carry out self-assembly, thereby improve its application performance.
Technical scheme of the present invention: adopt mesoporous silicon based material to organism adsorption and enrichment in the solution, to being limited to the pollutent photoactivation method for oxidation degraded of enrichment in the film micro area, mineralising, mainly comprise: mesoporous silicon oxide is uniformly dispersed in water, obtain the silicon-dioxide suspension liquid, suspension liquid is joined in the water that contains organic pollutant, dioxide-containing silica and pollutent quality are than between 5: 1～100: 1, at room temperature leave standstill organic pollutant in 0.5～3 hour adsorption and enrichment water, supernatant liquid is removed, the system volume-diminished of making is 1/2～1/50 of an original volume, utilizes light-Fenton catalysis or TiO then 2Photocatalysis oxidation method is finished the catalyzing oxidizing degrading process.Silica dioxide granule after the degraded washes with water repeatedly, can drop into next time and use.
Above-mentioned mesoporous silicon oxide is an ordered mesoporous material, and specific surface area is greater than 550m 2/ g, pore volume 1～10cm 3/ g, particle diameter 1～10 μ m, aperture 10.4～20nm.Its pattern is spherical, column, worm shape mesoporous material.Mesoporous silicon oxide prepares with known method, as presses document: 99 years the 1st phases of " inorganic materials " magazine " the mesoporous silicon of controlled architecture and regular morphology " (Gunter Schulz-Ekloff; Mesoporous silicawith controlled porous structure and regular morphology) disclosed method in: in deionized water, add water glass, ethyl acetate, moving to baking oven after leaving standstill under the room temperature leaves standstill more than 40 hours for interior 90 ℃, suction filtration, cleaning, drying, put into the fluidizing air calcination 5～25h of crucible under 600 ℃ of conditions at last, i.e. mesoporous silicon oxide.
Used mesoporous silicon oxide can pass through modification, makes it suit that not only the positively charged organic pollutant is had adsorption, can also be to electrically different more multi-pollutant absorption.The method of modification is according to its constructional feature, be that material surface has a large amount of Si-OH keys to exist, can change surface electrical behavior to its functional modification by condensation reaction, preferable methods is: after the meso-porous titanium dioxide Si powder is uniformly dispersed in water, remove water, get an amount of cationic polyamine salts solution, and regulate pH value to 4.0～8.5,80～97 ℃ of insulations 4 hours with sodium hydroxide solution, promptly get modified product, can be used for electronegative or other organic pollutant adsorption.The add-on of cationic polyamine salt is relevant with the mesoporous silicon oxide treatment capacity of modification, by the silicon-dioxide after the modification is detected and can determine.
Described cationic polyamine salt is the polypropylene amine hydrochloride, polystyrene amine hydrochlorate, polylysine hydrochloride etc.
Light-Fenton method that above-mentioned catalyzing oxidizing degrading process is adopted is known high-level oxidation technology, be catalyzer with the ferric ion promptly, (it is acid that pollutent solution is) adds hydrogen peroxide under acidic conditions, under light source, finish the catalyzing oxidizing degrading process.Described hydrogen peroxide is a hydrogen peroxide, and hydrogen peroxide is 2: 1～100: 1 with the Pollutant levels ratio; Described iron ion (Fe 3+) general consumption is 0.5～10 times of Pollutant levels.The catalyzing oxidizing degrading process is under agitation to carry out; Used degraded light source be visible light source (400～800nm), ultraviolet source (150～400nm) or sunlight.
Above-mentioned degradation process also can adopt known TiO 2Photocatalytic oxidation, i.e. in finite concentration pollutent solution (neutrality or acidic conditions) adds TiO 2Ultrafine powder, an amount of H 2O 2, under visible or ultraviolet source, stir degraded.The TiO that adds 2With the ratio of amount of pollutant be 0.5: 1～10: 1.
Effect of the present invention: the present invention is directed to the catalyzing oxidizing degrading technology, adopt mesoporous silicon oxide at first organic pollutant to be carried out adsorption and enrichment, it is fast that mesoporous particles is adsorbed with organic pollutants speed, high adsorption capacity, can adsorb more than 98% the organic pollutant in the solution, the general processing power 60～90% of specific activity charcoal absorption is high a lot.Therefore simultaneously,, can significantly concentrate the organic pollutant solution of trace or trace, obtain concentrated volume even can reach 1/50, thereby can be that the sewage of 0.01ppb～10ppm is handled the organic contamination substrate concentration based on its enrichment efficiently; Mesoporous silicon oxide is dispersed in the water, can very fast organism be adsorbed on the surface, does not influence the Fenton reaction result simultaneously; Utilize in addition and contain a large amount of Si-O keys in the mesoporous silicon based material, the hydroxyl of a large amount of Si-OH is contained on the surface, carry out functional modification or carry out self-assembly, thereby improve its application performance, the pollutent that kinds of surface such as hormonal compounds, agricultural chemicals, dyestuff, chloro thing, phenolic compound, tensio-active agent is had different electric charges has fine adsorption and enrichment effect, applied range; Mesoporous material has good reaction to conduct heat, and guarantees the stable and reusability of sorbent material.
Combine with high-level oxidation technology with the mesoporous silicon oxide adsorption and enrichment, improved the degradation efficiency of catalyzed oxidation greatly, use less catalyzer, oxygenant, can will be defined in the organic matter degradation in the film micro area, and under photocatalytic Degradation, the absorption life-span of the mesoporous adsorption particle behind the desorption obtains prolonging, and can recycle still to have adsorptive power more than three times, the absorption life cycle is long, makes light source obtain more effective utilization; This mesoporous adsorption material is regenerated easily, and running cost reduces.With the method for the present invention rhodamine B (RhB) that is used to degrade, result such as Fig. 1, Fig. 3, shown in Figure 4, rhodamine B is degraded fully, and with the low concentration solution degradation process of RhB and equivalent RhB solution by SiO 2The contrast of absorption degradation process, under same light source, the present invention degrades and uses Fe (ClO 4) 3, H 2O 2Still less; The present invention is used to the Sumitomo Acridine Orange RK conc of degrading, the result as shown in Figure 2, degraded finishes the remaining surplus liquid in back not to be had Sumitomo Acridine Orange RK conc and exists.Experiment shows that the present invention all has fine enrichment Degradation to Sumitomo Acridine Orange RK conc, the diverse molecule of rhodamine B structure, and therefore method of the present invention has universality, can be used for organic purifying treatment in trade effluent and the municipal effluent.
Description of drawings
Fig. 1 is rhodamine degraded front and back powder and the UV spectrophotometer measuring of reacting surplus liquid, and curve 1 is for being adsorbed on the rhodamine B (4 * 10 on silicon-dioxide (50mg) surface -4Mmol) oven dry is the ultraviolet absorption curve of powder, and there is the characteristic curve of rhodamine B at the 550nm place; Curve 2 is for being adsorbed on the rhodamine B (4 * 10 on silicon-dioxide (50mg) surface under the radiation of visible light -4Mmol), at Fe 3+(10 -3M) and H 2O 2(3 * 10 -3M) degraded complete back oven dry is the ultraviolet absorption curve of powder under the system, and rhodamine B is degraded fully; Curve 3 finishes the ultraviolet absorption curve of the remaining surplus liquid in back for the rhodamine B degraded.
Fig. 2 is the UV spectrophotometer measuring of powder before and after the Sumitomo Acridine Orange RK conc degraded, and curve 1 is silicon-dioxide (50mg) absorption Sumitomo Acridine Orange RK conc (4 * 10 -4Mmol) oven dry is the ultraviolet absorption curve of powder, and 480nm place characteristic peak obviously exists; Curve 2 is silicon-dioxide (50mg) absorption Sumitomo Acridine Orange RK conc (4 * 10 -4Mmol), at Fe 3+(10 -3M)/H 2O 2(3 * 10 -3M)/visible light down degraded fully the back oven dry be the ultraviolet absorption curve of powder, the characteristic peak disappearance; Curve 3 is the ultraviolet absorption curve of the remaining surplus liquid in degraded end back, and no Sumitomo Acridine Orange RK conc exists.
Fig. 3 is a rhodamine B homogeneous phase degradation curve, detects in the degradation process different time points surplus liquid of degrading with the ultraviolet spectrophotometer.Gained curve 1～9th, from beginning degraded to degradation process was every 20 minutes detection gained fully, it has shown 1000ml under visible light, 1 * 10 -6MRhB, 5 * 10 -5M Fe (ClO 4) 3Solution, 2 * 10 -4M H 2O 2Degradation process; By the charateristic avsorption bands of curve 9 no rhodamine Bs as can be known rhodamine B degraded fully;
Fig. 4 tests the equivalent rhodamine B with Fig. 3 to be adsorbed in SiO 2Particle, simmer down to 100ml (1 * 10 -5M) RhB, adding obtains 1 * 10 -4M Fe (ClO 4) 3Solution, 1 * 10 -3M H 2O 2The degradation process of system.Detect in the degradation process different time points surplus liquid of degrading with the ultraviolet spectrophotometer.Degradation condition is tested with Fig. 3, and gained curve 1～8 is to detect gained every degraded in 30 minutes, by the charateristic avsorption band of no rhodamine B shown in the curve 8 as can be known rhodamine B degraded fully;
Embodiment:
Below in conjunction with drawings and Examples embodiment of the present invention are further specified.But the invention is not restricted to listed embodiment.
Embodiment 1: weighing 3.92gC 16(CTAB, cetyl trimethylammonium bromide) adds in the polypropylene vial, adds the 68ml deionized water, 30 ℃ of constant temperature; Add 4.66gNa 2SiO 39H 2O opens stirring, and solution is transparent; Add the 7ml ethyl acetate fast, stirring stops behind the 30s; Gained solution is at room temperature left standstill 6h, in 90 ℃ of baking ovens, place 65h then; Filter with deionized water and ethanol afterwards and clean; Put into crucible calcination 20h under 600 ℃ of conditions.Gained SiO 2Be spherical particle, particle diameter 2～4 μ m, aperture 10.4nm, 1.5cm 3/ g, 583.5cm 2/ g.
Embodiment 2: take by weighing SiO among the embodiment 1 2Particle 50mg, ultra-sonic dispersion is even, and centrifugation goes out supernatant liquid, adds the polypropylene amide hydrochloride, regulates pH value to 8.5, is warming up to 80 ℃, is incubated 4 hours, promptly gets SiO 2Modified particles;
Embodiment 3: take by weighing SiO among the embodiment 1 2Particle 50mg, ultra-sonic dispersion is even, and centrifugation goes out supernatant liquid, adds the polystyrene amide hydrochloride, regulates pH value to 4, is warming up to 97 ℃, is incubated 4 hours, promptly gets SiO 2Modified particles;
Embodiment 4: take by weighing silica dioxide granule 50mg among the embodiment 1, add an amount of ultrapure water and be uniformly dispersed.Pipette rhodamine B (2mM) (U.S. Aldrich reagent company) the solution 200 μ l that configured, join in the scattered silicon-dioxide suspension liquid, shake up, at room temperature leave standstill.After dyestuff adsorbed fully, in solution, add 1 * 10 -2M Fe (ClO 4) 3(many Fine Chemical Co., Ltd are contained in Shanghai) solution 400 μ l shake up the back and with perchloric acid (celebrating is contained and reached chemical industry technology company limited, Beijing) solution above-mentioned system pH are adjusted to 2.5～3.0.Add 120 μ l hydrogen peroxide (0.1M) (good fortune chemical reagent in morning factory, Tianjin) afterwards, the adjustment volume is 40ml, be placed on light source (＞380nm) under, opened induction stirring reaction 3 hours, degradation results such as near the RhB characteristic peak of Fig. 1 explanation 550nm are through degraded, disappear, promptly RhB is degraded.Through the SiO after the degraded 2After the particle washing three times, it is even to add the water ultra-sonic dispersion, adds RhB, repeats still degradable of above step after the absorption.
Embodiment 5: take by weighing the silica dioxide granule among the 50mg embodiment 1, add an amount of ultrapure water and be uniformly dispersed.Pipette 200 μ l Sumitomo Acridine Orange RK concs (2mM) (Beijing Wei Si chemical reagents corporation) solution that has configured, join in the scattered silicon-dioxide suspension liquid, shake up, at room temperature leave standstill, spend the night.After dyestuff adsorbed fully, in solution, add 1 * 10 -2M Fe (ClO 4) 3Solution 800 μ l shake up the back and with perchloric acid solution above-mentioned system pH are adjusted to 2.5～3.0.Add 80 μ l hydrogen peroxide (0.01M) afterwards, the adjustment volume is 40ml, be placed on light source (＞380nm) under, open induction stirring reaction.Result such as Fig. 2 illustrate.
Embodiment 6: take by weighing silica dioxide granule 60mg among the embodiment 2, add an amount of ultrapure water and be uniformly dispersed.Remove upper solution, the washing both sides.Pipette 200 μ l orange II (2mM) solution that has configured, join in the silicon-dioxide suspension liquid, shake up, at room temperature leave standstill 3 hours.After dyestuff adsorbed fully, in solution, add 1 * 10 -2M Fe (ClO 4) 3Solution 20 μ l shake up the back and with perchloric acid solution above-mentioned system pH are adjusted to 2.5～3.0.Add 400 μ l hydrogen peroxide (0.1M) afterwards, the adjustment volume is 40ml, be placed on light source (＞380nm) under, opened induction stirring reaction 3 hours.Degradation results detects final orange II with the UV-Vis spectrophotometer and is degraded fully.Add the water ultra-sonic dispersion behind the degraded solutions centrifugation after washing 3 times, particle still has adsorptive power to dyestuff, repeats above operation and still can degrade.
Embodiment 7: take by weighing silica dioxide granule 60mg among the embodiment 3, add an amount of ultrapure water and be uniformly dispersed.Pipette 200 μ l Congo red (2mM) solution that has configured, join in the silicon-dioxide suspension liquid, shake up, at room temperature leave standstill 3 hours.After Congo red absorption fully, in solution, add 1 * 10 -2M Fe (ClO 4) 3 Solution 400 μ l shake up the back and with perchloric acid solution above-mentioned system pH are adjusted to 2.5～3.0.Add 100 μ l hydrogen peroxide (0.01M) afterwards, the adjustment volume is 40ml, be placed on light source (＞380nm) under, open induction stirring reaction.Experimental result is known Congo red degraded fully by the detection of UV-Vis spectrophotometer.
Embodiment 8: take by weighing SiO among the embodiment 1 2Particle 50mg adds an amount of ultrapure water and is uniformly dispersed.Pipette 200 μ lRhB (2mM) solution that configured, join in the silicon-dioxide suspension liquid, shake up, at room temperature leave standstill 3 hours.After RhB adsorbed fully, in solution, add nano-TiO 2(analytical pure) 5mg.Add 300 μ l hydrogen peroxide (0.1M) afterwards, the adjustment volume is 40ml, is placed under the ultraviolet source, opens the induction stirring reaction.Experimental result is known Congo red degraded fully by the detection of UV-Vis spectrophotometer.

Claims (5)

1. light concentration organic pollutant treatment process, it is characterized in that: by trace or organic micro-pollutant in the mesoporous silicon based material enrichment water, with the catalyzed oxidation technology pollutent is degraded in limiting film micro area, mineralising, comprise: mesoporous silicon oxide is uniformly dispersed in water, obtain the silicon-dioxide suspension liquid, suspension liquid is joined in the water that contains organic pollutant, dioxide-containing silica and pollutent quality are than between 5: 1～100: 1, at room temperature leave standstill organic pollutant in 0.5～3 hour adsorption and enrichment water, supernatant liquid is removed, the system volume-diminished of making is 1/2～1/50 of an original volume, places then under the light source, utilizes light-Fenton or TiO 2Photocatalysis oxidation method is finished degradation process.
According to the treatment process of claim 1, it is characterized in that 2, described mesoporous silicon oxide is an ordered mesoporous material, specific surface area is greater than 550m 2/ g, pore volume 1～10cm 3/ g, 1～10 micron of particle diameter, aperture 10.4～20nm.
3, according to the treatment process of claim 1, it is characterized in that described mesoporous silicon oxide is the mesoporous silicon oxide through modification, method is: after the meso-porous titanium dioxide Si powder is uniformly dispersed in water, remove water, add cationic polyamine salt, and regulate pH value to 4.0～8.5,80～97 ℃ of insulations 4 hours with sodium hydroxide solution, promptly get modification mesoporous silicon oxide product, described cationic polyamine salt is the polypropylene amine hydrochloride, polystyrene amine hydrochlorate, or polylysine hydrochloride.
4, according to the treatment process of claim 1, it is characterized in that, described light-Fenton catalysis method is to be catalyzer with the ferric ion, the iron ion consumption is 0.5～10 times of Pollutant levels, under acidic conditions, add hydrogen peroxide, hydrogen peroxide is 2: 1～100: 1 with the Pollutant levels ratio, under light source, finish the catalyzing oxidizing degrading process.
5, according to the treatment process of claim 1, it is characterized in that described TiO 2Photocatalytic oxidation is under neutrality or acidic conditions, adds hydrogen peroxide, with TiO 2Be catalyzer, TiO 2With the ratio of amount of pollutant be 0.5: 1～10: 1, light source is under ultraviolet or the visible light, constantly stirs the catalyzing oxidizing degrading process of finishing.
CN200710065206A 2007-04-06 2007-04-06 The water treatment method of light concentration organic pollutant Expired - Fee Related CN100575281C (en)

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CN101423226B (en) * 2008-11-27 2011-12-07 复旦大学 Method for removing organic template from ordered mesoporous material at normal temperature
TWI551551B (en) * 2010-04-30 2016-10-01 三菱瓦斯化學股份有限公司 Peroxide activator and method for purifying soil and/or underground water
CN102826707A (en) * 2011-06-16 2012-12-19 云南大学 Three-stage tandem photocatalysis treatment technology of marigold wastewater
CN104771857B (en) * 2014-01-13 2018-07-20 中国科学院上海微系统与信息技术研究所 A kind of purposes of mesoporous silicon oxide nanomaterial
CN105836871A (en) * 2016-05-06 2016-08-10 南昌大学 Method for improving efficiency of degrading organic pollutants in water by homogeneous-phase UV-Fenton system
CN107298474A (en) * 2017-06-20 2017-10-27 山东理工大学 A kind of degraded under sunshine is discharged from silica adsorbent to the method for the methylene blue of alkaline solution
CN107731336B (en) * 2017-09-29 2019-11-12 西南科技大学 The method of combination of ultrasound wet oxidation Fenton method processing radioactive wastewater
CN107857408B (en) * 2017-12-08 2023-05-19 暨南大学 Purifying device and treatment method for PPCPs in drinking water source
CN109052547A (en) * 2018-08-31 2018-12-21 南京林业大学 A kind of method of visible light-responded homogeneous light Fenton processing organic wastewater

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