CN1261378C - Method for purifying wastewater through magnetic nano TiO2/SiO2/Fe2O3 composite photocatalyst and equipment - Google Patents

Method for purifying wastewater through magnetic nano TiO2/SiO2/Fe2O3 composite photocatalyst and equipment Download PDF

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Publication number
CN1261378C
CN1261378C CNB2004100266995A CN200410026699A CN1261378C CN 1261378 C CN1261378 C CN 1261378C CN B2004100266995 A CNB2004100266995 A CN B2004100266995A CN 200410026699 A CN200410026699 A CN 200410026699A CN 1261378 C CN1261378 C CN 1261378C
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magnetic nano
sewage
catalyst
composite photo
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CN1562817A (en
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陈建军
廖振华
李荣先
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Shenzhen Research Institute Tsinghua University
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Shenzhen Research Institute Tsinghua University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Catalysts (AREA)
  • Physical Water Treatments (AREA)

Abstract

The present invention provides a method for purifying sewage with magnetic nanometer TiO2/SiO2/Fe3O4 compound photocatalysts, and a device thereof. The method comprises the steps that sewage unprocessed by chemical coagulative precipitation is processed by photocatalysis oxidation, the sewage is fully mixed with nanometer photocatalyst powder by a special photocatalysis oxidation device and generates a photocatalysis oxidation reaction under the condition of light irradiation, and thereby, harmful matter is oxidized or reduced. The method has the advantages that compared with the existing sewage treatment means, the effect of purifying sewage by the method and the device for purifying sewage with magnetic nanometer TiO2/SiO2/Fe3O4 compound photocatalysts is good, and the method has high efficiency of purifying the sewage, low cost and no secondary pollution to environment, and conforms to the requirements for environmental protection.

Description

Magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst purify liquid waste method and device
Technical field
The present invention relates to the treatment process of waste water or sewage, especially utilize magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst is purified liquid waste or the method and the device of sewage.
Background technology
Along with the raising of people's living standard and the reinforcement of environmental consciousness, to the research of waste water or sewage disposal with implement also deepening constantly and developing.Existing waste water or sewage water treatment method generally have physical filtering method, chemical method, biochemical process, chemistry-oxidation style etc.As disclosed Chinese invention patent application that is called " sewage water treatment method that contains organic compound and mineral compound " of CN1120833, its disclosed sewage water treatment method has just comprised the operation of chemical reaction and/or mechanical separation method separate suspended solid thing; Hot alkali treatment technology; Biologic treatment process and ozonize operation.According to existing technique means, disposable processing waste water of these treatment processs or sewage are generally thorough inadequately, in order to improve the index of waste water or sewage disposal, need repeat hot alkali treatment, biological treatment and ozonize, waste water or the sewage handled are carried out secondary treatment, to reach requirement and the environmental requirement that we use, still this processing mode can make cost roll up, and effect is undesirable.And a lot of additives of existing sewage water treatment method are toxic side effects, easily environment are caused secondary pollution, " green " environmental protection ideal that does not satisfy modern society and advocated.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, on the basis of existing sewage water treatment method, provide a kind of processing efficiency height, non-secondary pollution, purification method for effluent and device thereof that cost is low.
Another object of the present invention is to provide a kind of use magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Method that composite photo-catalyst is purified liquid waste and refining plant, this method and apparatus can make harmful particle oxidation or the reduction in waste water or the sewage waste water or sewage are purified effectively, and can not retain objectionable impurities.
In a word, the present invention realizes in the following manner:
A kind of magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The composite photo-catalyst method of purifying liquid waste is characterized in that, waste water or sewage is earlier through pre-treatment, and then to utilizing magnetic Nano TiO through pretreated sewage 2/ SiO 2/ Fe 3O 4Composite photo-catalyst carries out Treatment by Photocatalysis Oxidation, Treatment by Photocatalysis Oxidation be make sewage under the condition of illumination with nano-TiO 2/ SiO 2/ Fe 3O 4Photocatalysis oxidation reaction takes place in the powder thorough mixing of composite photo-catalyst, thereby makes harmful particle oxidized or be reduced.
The principle of photochemical catalytic oxidation is: nano-photocatalyst is under the effect of luminous energy, low energy valence band electronics generation transition, become excited state, transit to the high energy valence band and generate light induced electron, this light induced electron has strong reducing property, and therefore the low energy valence band then photohole occurs, has strong oxidation capacity, but sterilization, sterilization almost can all organic pollutants of oxidation.
Described pre-treatment is meant carries out flocculation treatment earlier to waste water or sewage, selects the mixed flocculation of two kinds of medicaments of polyacrylamide commonly used and Tai-Ace S 150 for use, can carry out second coagulation in case of necessity, can reduce chemical oxygen demand (COD) (COD), the biological oxygen demand (BOD of sewage greatly 5) concentration; And in pretreated sewage COD concentration less than 200 mg/litre, so that magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst carries out Treatment by Photocatalysis Oxidation.
A kind of magnetic Nano TiO that utilizes 2/ SiO 2/ Fe 3O 4The device that composite photo-catalyst purifies, comprise photocatalytic oxidation device, it is characterized in that, described photocatalytic oxidation device comprises water-in, treating pond and water outlet, and be provided with the aeration tube that light source and surface are covered with aperture in described treating pond, this aeration tube can make magnetic Nano TiO when air aeration 2/ SiO 2/ Fe 3O 4The powder of composite photo-catalyst can be in sewage evenly suspends, with waste water or sewage thorough mixing.
Described magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The composite photo-catalyst powder is the magnetic Nano TiO with double-coated structure 2/ SiO 2/ Fe 3O 4Composite photo-catalyst, promptly its microcosmic particle internal core is Fe 3O 4, Fe 3O 4External packets be covered with SiO 2, SiO 2External packets be covered with TiO 2
Described light source is to adopt ultraviolet source, is arranged on the middle position for the treatment of pond, and it can be provided with a plurality of, is uniformly distributed in the middle position for the treatment of pond, so that to magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst carries out ultraviolet radiation and activates; According to the effective radius of quartz burner, adopt two ultraviolet sources just can reach photochemical catalysis effect preferably.
Described aeration tube is generally to adopt plastics to make, acid, alkali, the brine corrosion of plastics aeration tube ability waste water or sewage, but life-time service, and its surface is less scaling.
Above-mentioned aeration tube, it is arranged at the below of described light source, and it is cylindrical structure substantially, and described cylinder surface uniform distribution also offers the spilehole of certain number.These spileholes are used for magnetic Nano TiO by air aeration the time 2/ SiO 2/ Fe 3O 4Composite photo-catalyst and waste water or sewage carry out well-mixed.
Above-mentioned plastics aeration tube, its plastic cylinder body are the identical U type structure of diameter, and the spacing of U type opening is identical with spacing between a plurality of ultraviolet rays, is generally 20-60cm.
Utilize magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The device that composite photo-catalyst purifies, its outside can be provided with aerating apparatus, the bottom of inner U type cylinder is communicated with extraneous aerating apparatus, with timely make-up gas, make above-mentioned photocatalyst can with waste water or sewage thorough mixing, noxious pollutant particulate with in oxidation to greatest extent, reducing waste water or the sewage fully purifies water.
The present invention utilizes magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst purify liquid waste method and device are by using suspension magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst carries out Treatment by Photocatalysis Oxidation to waste water or sewage, can obtain than the better purifying water effect of existing sewage disposal means, and its cleaning water height, cost is low.
And, implement the Treatment by Photocatalysis Oxidation method, only need by luminous energy and nano-photocatalyst, do not need to add in addition other chemical agents, in the degradation water during organic pollutant, final product is carbonic acid gas, water and inorganic molecules, can not produce secondary pollution to environment, meets " green " environmental protection requirement.
Description of drawings
Fig. 1 is magnetic Nano TiO of the present invention 2/ SiO 2/ Fe 3O 4The purify liquid waste structural representation of an embodiment of device of composite photo-catalyst,
Fig. 2 be A shown in Figure 1 to structural representation.
Embodiment
Shown in Figure 1, in one embodiment of the invention, magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The composite photo-catalyst device of purifying liquid waste is meant the device that carries out photochemical catalytic oxidation again after coagulation pretreatment.
As shown in Figure 1, photocatalytic oxidation device comprises water-in 1, treating pond 3, water outlet 2, aerating apparatus 4 and stretches into aeration tube 401 in the described treating pond 3.In described treating pond 3, be provided with light source 301 and 302.Described light source 301 and 302 is to adopt the UV-lamp light source, evenly is arranged on the middle position for the treatment of pond 3.Described aeration tube is to adopt plastics to make, for placing the uniform cylinder of the diameter that is the U type of described light source below, the surface evenly is covered with the aperture 5 of certain number, can play the effect of stirring action and the required reactant oxygen of additional photochemical catalytic oxidation after the ventilation, aeration can make photocatalyst particles evenly suspend in sewage, described cylinder is the identical U type structure of diameter, and the spacing of U type opening is identical with the spacing of two ultraviolet lamp tubes, is 30cm.The height of the supporting structure 303 of described aeration tube is about 2cm.
In the present embodiment, nano-photocatalyst is to adopt magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst 6.Because nanometer Fe 3O 4Particulate has good magnetic, coats the TiO after preparing 2/ SiO 2/ Fe 3O 4Composite particles has excellent soft magnetic performance, B s=0.62T, B r=0.01T, H c=0.16A/m has good recyclable reusability, and it is poly-to be difficult for producing magnetic.And SiO 2With Fe 3O 4Particle has affinity preferably, is easy at Fe 3O 4Particle surface coats the thin amorphous SiO of one deck 2Isolate transition layer, and then coat TiO thereon 2Coating, SiO 2Isolate transition layer and not only can effectively reduce the interaction between the magnetic core and coated by titanium dioxide layer in the heat treatment process, and reduce Fe greatly 3O 4The degree of kernel selective oxidation also plays reinforced cementitious effect.
Wherein, magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The preparation method of composite photo-catalyst 6 is as follows:
With the nanometer Fe for preparing 3O 4Be mixed and made into colloidal sol shape mixed solution with a certain amount of dehydrated alcohol behind the powder weighing, extract in proportion during preparation and contain 0.2g Fe 3O 4The mixed solution of powder is poured Erlenmeyer flask into, adds a certain amount of water and ammoniacal liquor then in the Erlenmeyer flask, and adding dehydrated alcohol again, to make the mixed solution cumulative volume be 450mL.With (about 20 ℃) the powerful stirring at room temperature of this mixed solution, in mixed solution, slowly drip the 0.004mol tetraethoxy simultaneously, ageing 5h can be at Fe 3O 4The magnetic core surfaces coats one deck SiO 2, after centrifuging, clean three times with dehydrated alcohol again, put into 60 ℃ of dry 15h of loft drier, grind gently and can make SiO 2/ Fe 3O 4Powder.
Take by weighing 0.2g SiO again 2/ Fe 3O 4Powder and is put into ultrasonic cleaner ultra-sonic dispersion 0.5h after the 50mL dehydrated alcohol mixes, and makes SiO 2/ Fe 3O 4Composite particles fully disperses in dehydrated alcohol.In above-mentioned mixed solution, add a certain amount of water and dehydrated alcohol then, control SiO 2/ Fe 3O 4The concentration of composite particles is about 0.45g/L.The Erlenmeyer flask that mixed solution is housed is put into 45 ℃ of water-baths, under intense agitation, dropwise add an amount of tetra-n-butyl titanate (Ti (Obu) 4) ethanolic soln, ageing 5h uses dehydrated alcohol and washed with de-ionized water 3 times respectively after centrifuging, put into 60 ℃ of dry 48h of loft drier, grinds crushing gently.Again powder after the drying is placed retort furnace, be warming up to 450 ℃ with the heating rate of 6 ℃/min, insulation 3h is cooled to room temperature, promptly makes the magnetic Nano TiO that can be used for light-catalyzed reaction 2/ SiO 2/ Fe 3O 4Composite photo-catalyst 6.
In photocatalytic oxidation device, sewage is carried out Treatment by Photocatalysis Oxidation.Under the katalysis of UV-light, magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst absorbs photon, brings out the semiconductor product third contact of a total solar or lunar eclipse and gives birth to electronics and photohole, makes those be difficult to biological degradation or be difficult to can also make poisonous and hazardous mineral ion (as Pb by the oxidized degraded of the organism of chemical process oxidation 2+, Cu 2+, Hg 2+, Cr 6Deng) be reduced.
In treating processes, light source can be selected the ultraviolet source and the light application time of different capacity according to actual needs for use.COD, the low then light source of BOD5 concentration can be selected lower-wattage for use or shorten the optical radiation time, otherwise, then select more powerful light source for use, prolong the optical radiation time or suitably add hydrogen peroxide.
Experiment showed, that COD concentration is about 200mg.L -1Active red dye waste water through Treatment by Photocatalysis Oxidation about 8 hours, COD concentration can be reduced to below 10 mg/litre in the sewage.

Claims (6)

1, a kind of magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The composite photo-catalyst method of purifying liquid waste is characterized in that, waste water or sewage is earlier through pre-treatment, and then to utilizing magnetic Nano TiO through pretreated sewage 2/ SiO 2/ Fe 3O 4Composite photo-catalyst carries out Treatment by Photocatalysis Oxidation; Described pre-treatment is meant to be adopted polyacrylamide and the mixed flocculation of two kinds of medicaments of Tai-Ace S 150 or mixes flocculation treatment through secondary waste water or sewage.
2, magnetic Nano TiO as claimed in claim 1 2/ SiO 2/ Fe 3O 4The composite photo-catalyst method of purifying liquid waste is characterized in that described secondary mixed flocculation, makes in pretreated sewage COD concentration less than 200 mg/litre.
3, a kind of magnetic Nano TiO that utilizes 2/ SiO 2/ Fe 3O 4The device that composite photo-catalyst purifies comprises photocatalytic oxidation device, it is characterized in that, described photocatalytic oxidation device comprises water-in, treating pond and water outlet, and in described treating pond, be provided with light source, magnetic Nano TiO 2/ SiO 2/ Fe 3O 4Composite photo-catalyst and surface are covered with the aeration tube of aperture; Described light source adopts ultraviolet source, is provided with a plurality ofly, is uniformly distributed in the middle position for the treatment of pond; Described aeration tube is arranged at the below of light source, and it is cylindrical structure substantially, and this cylinder is the identical U type structure of diameter, and the spacing of U type opening is identical with spacing between a plurality of ultraviolet sources, be generally 20-60cm,, evenly offer a plurality of spileholes on described cylinder surface.
4, the magnetic Nano TiO that utilizes as claimed in claim 3 2/ SiO 2/ Fe 3O 4The device that composite photo-catalyst purifies is characterized in that magnetic Nano TiO 2/ SiO 2/ Fe 3O 4The powder of composite photo-catalyst is the magnetic Nano TiO with double-coated structure 2/ SiO 2/ Fe 3O 4Composite photo-catalyst, promptly its microcosmic particle internal core is Fe 3O 4, Fe 3O 4External packets be covered with SiO 2, SiO 2External packets be covered with TiO 2
5, the magnetic Nano TiO that utilizes as claimed in claim 3 2/ SiO 2/ Fe 3O 4The device that composite photo-catalyst purifies is characterized in that described aeration tube generally adopts plastics to make.
6, the magnetic Nano TiO that utilizes as claimed in claim 3 2/ SiO 2/ Fe 3O 4The device that composite photo-catalyst purifies is characterized in that its outside is provided with aerating apparatus, and the bottom of inner U type cylinder is communicated with extraneous aerating apparatus.
CNB2004100266995A 2004-04-01 2004-04-01 Method for purifying wastewater through magnetic nano TiO2/SiO2/Fe2O3 composite photocatalyst and equipment Expired - Fee Related CN1261378C (en)

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Publication number Priority date Publication date Assignee Title
CN100509160C (en) * 2005-11-17 2009-07-08 南京航空航天大学 Synthesis technology of magnet carried photocatalyst composite particle, sewage purification method and device
CN101856628A (en) * 2010-04-30 2010-10-13 北京科技大学 Conducting polymer modified magnetic photocatalyst and preparation method thereof
CN103359868A (en) * 2013-04-12 2013-10-23 西北大学 Sewage treatment photocatalysis reactor
CN103241812B (en) * 2013-05-29 2014-07-30 江苏大学 Photomagnetic composite flocculant and preparation method thereof
CN103464161A (en) * 2013-09-29 2013-12-25 河北麦森钛白粉有限公司 Method for preparing nano-TiO2 modified photocatalyst for sewage treatment
CN104609595B (en) * 2014-12-25 2016-06-15 河南正佳能源环保股份有限公司 The method processing organic wastewater with difficult degradation thereby worked in coordination with by using polypropylene amide flocculation catalyst
CN105214665A (en) * 2015-11-04 2016-01-06 河海大学 The recyclable magnetic titanium dioxide photochemical catalyst and preparation method thereof of bisphenol-A in a kind of fast degradation waste water
CN106315960B (en) * 2016-10-10 2020-01-17 西南石油大学 Method for treating oil and gas field wastewater
CN107055850A (en) * 2016-11-25 2017-08-18 南宁市黑晶信息技术有限公司 A kind of flocculant sewage water treatment method
CN109264909B (en) * 2018-10-29 2024-03-12 南京高正农用化工有限公司 Pesticide organic wastewater continuous treatment device
CN112062206B (en) * 2020-09-04 2022-04-05 兰州大学 Method for treating antibiotics in water by using strong hematite activated persulfate

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