CN104326525A - Treatment method of municipal sewage recycled as circulating cooling water of thermal power plants - Google Patents
Treatment method of municipal sewage recycled as circulating cooling water of thermal power plants Download PDFInfo
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- CN104326525A CN104326525A CN201410560354.1A CN201410560354A CN104326525A CN 104326525 A CN104326525 A CN 104326525A CN 201410560354 A CN201410560354 A CN 201410560354A CN 104326525 A CN104326525 A CN 104326525A
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- photocatalyst
- photocatalyst film
- cooling water
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Abstract
The invention relates to a treatment method of municipal sewage recycled as circulating cooling water of thermal power plants, which comprises the following steps: 1) preparation of required photocatalyst film: calcining rutile TiO2 at the temperature of not lower than 1200 DEG C for 3-5 hours, depositing Pt (accounting for 0.1-1.5 wt% of the rutile TiO2) on the rutile TiO2 subjected to high-temperature calcination to obtain a photocatalyst, and fixing the photocatalyst onto a support by a sol-gel process to obtain the required photocatalyst film, wherein the thickness of the photocatalyst film on the support is controlled at 5-10 mu m; 2) preparation of photocatalytic reactor; and 3) photocatalytic degradation, wherein the ultraviolet light intensity is controlled at 1.0-2.2 mW/cm<2>, and the municipal sewage flow rate is controlled at 2.0-6.0 L/hour. The clean and renewable light energy is utilized to thoroughly mineralize and decompose the organic matters under milder reaction conditions, thereby avoiding secondary pollution. The method has the advantages of simple treatment process, wider application range, lower cost, huge development potential and mild photocatalytic reaction conditions, and can be performed at room temperature; and the adopted photocatalyst has the advantages of no toxicity and low price.
Description
Technical field
The invention belongs to urban sewage recycling field, be specifically related to a kind for the treatment of process municipal effluent being used for fuel-burning power plant.
Background technology
As far back as in June, 1998, the Chinese Academy of Sciences is submitting to just proposition in a word in the report of State Council " outlet of China Water problem ": " water problems will become the most outstanding significant problem of 21 century China's Economic development ".Along with the aggravation of water resources crisis and the deterioration of quality of water environment, shortage of water resources has become worldwide energy environment issues.Treated sewage reusing solves water crisis, the important method keeping water body healthy cycle and effectively utilize.In countries such as the U.S., Britain, South Africa and Israel, municipal effluent is generally back to water coolant.
Thermal power plant is process water rich and influential family, and its water loss accounts for 40% of total process water, and this wherein circulating cooling water loss account for more than 70% of total Water.Visible, the shortage of water resources becomes the bottleneck of power industry development gradually.Municipal middle water, because of the reliability and stability at its water source, can become the water of productive use of power plant after advanced treatment.But although this kind of municipal middle water reaches discharging standards, the content of its pollutent is still higher than natural water, and especially organic content, ammonia nitrogen and bacterium equal size are higher, and this will cause the corrosion of metallic substance.In addition, this kind of organic wastewater with difficult degradation thereby BOD/COD ratio is all even lower below 0.3, and thus waste water becomes and is difficult to biochemical treatment, and the treatment effect of traditional conventional treatment method to this type of organic waste water is poor.
Photocatalytic pollutant degradation is the one of high-level oxidation technology (Advanced Oxidation Process, AOP).The concept of high-level oxidation technology is that first the people such as Glaze propose, and refers to and apply various modern technologies by insoluble for the technology such as bio-oxidation toxic organics mineralising to nontoxic degree in the process of water treatment.This hi-tech mainly concentrates on the chemical oxidation of gold that can produce enough hydroxyl radical free radical isoreactivity species.Hydroxyl radical free radical (OH) is a kind of active specy of very active and non-selectivity, and its oxidizing potential is 2.8 V.Most organic DeR in the aqueous solution can be caused.The scope of HO and many organic second order rate constant is 10
7-10
10m
-1s
-1.
In general, the ultimate principle of conductor photocatalysis is: when use energy is more than or equal to semiconductor material energy gap (E
g) rayed time, the electronics in its valence band will be excited, and transits to conduction band and forms conduction band electron (e
cb -), then can form valence band hole (h in valence band
vb +), material is thus formed pair of electrons/hole to (electron-hole pairs), be called as photo-generated carrier.Because the energy interband of semi-conductor exist forbidden band, the life-span of this kind of photo-generated carrier is longer (ns rank), can migrate to the surface of catalyzer.And for the conduction band electron (e produced
cb -) and valence band hole (h
vb +), both all can oxidative degradation organic pollutant: conduction band electron (e
cb -) O of catalyst surface can be attracted to
2catch and form O
2 -, and then reaction formation hydroxyl radical free radical (
.and other a series of active species OH); Valence band hole (h
vb +) electromotive force about about 3.0 eV, there is strong oxidizing property, can by semiconductor surface adsorb oxidation operation decompose.In addition, h
vb +the water that can also adsorb with semiconductor surface reacts and is formed
.oH, and then oxidative degradation organic pollutant.
At present, in disposing of sewage, organic main method has: physisorphtion, chemical oxidization method and microorganism treatment etc.Although these methods respectively have advantage, significant role is served to waste water control, all also existing that efficiency is low, energy consumption is high, use range is narrow in varying degrees, can not thoroughly pollutent decomposed and easily produce secondary pollution problems.
Summary of the invention
The problem to be solved in the present invention is for the deficiencies in the prior art, pass through photocatalysis technology, mineralising process is carried out to the organism etc. of the existence in municipal effluent, make municipal effluent can meet the use standard of power plant's water of productive use after this kind of method process, can well realize industrialized application, realize a kind of urban sewage recycling of the recycle of water resources in the treatment process of thermal power generation station-service recirculated cooling water.
Technical scheme of the present invention comprises following preparation process: the photocatalyst film 1) needed for preparation: by rutile TiO
2be not less than the temperature lower calcination 3 ~ 5 hours of 1200 DEG C; In the rutile TiO through above-mentioned high-temperature calcination
2upper modification deposits and accounts for its mass content 0.1 ~ 1.5wt%Pt thus the photocatalyst obtained; Be fixed on carrier by described photocatalyst by sol-gel method, be prepared into required photocatalyst film, on carrier, the thickness of photocatalyst film should control at 5 ~ 10 μm; 2) prepare photo catalysis reactor: reactor is rectangular parallelepiped, be divided into 5 rectangle form pools by 4 pieces of longitudinal baffles, former and later two little Chi and middle three little Chi, then for being provided with the reaction member of photocatalyst film in middle three little Chi; The light source of reactor is UV-light; 3) municipal effluent is flowed into the Municipal Sewage for Circulating obtained after photo catalysis reactor carries out degradation treatment needed for thermal power plant, control ultraviolet ray intensity is 1.0 ~ 2.2mW/cm
2, municipal effluent flow velocity 2.0 ~ 6.0L/h.
The present invention is preferably by rutile TiO
2at the temperature lower calcination of 1200 DEG C ~ 1500 DEG C.
The present invention particularly preferably is in the rutile TiO through high-temperature calcination
2upper modification deposits and accounts for its mass content 0.5wt%Pt; By rutile TiO
2at the temperature lower calcination 3 hours of 1200 DEG C.
The present invention, by utilizing UV-light, uses semiconductor light-catalyst to carry out degraded purifying treatment to municipal effluent, and then is back to fuel-burning power plant recirculated cooling water.Concrete technology scheme is as follows:
(1) photocatalyst film needed for preparation.Carry out purifying treatment for water, first need catalyzer can recycle, the therefore conventional method granular catalyst fines being made suspension just can not meet the demands.Catalyzer is fixed on certain carrier by present method, prepares durable, the photocatalyst film of reusable edible.
Rutile titanium oxide (the Rutile TiO that the photocatalyst used is modified for platinum (Pt)
2, referred to as RT).Preparation process comprises, 1) method precipitated by chemical light prepares PtRT, under magnetic agitation, by methyl alcohol, and H
2ptCl
66H
2o and process are not less than the rutile TiO of calcining at 1200 DEG C
2(RT), after mixing, reaction 3 – 12h is irradiated under ultraviolet light.In PtRT, the content of Pt is within the scope of 0.1 – 1.5wt%.
2) further, by 1) PtRT that obtains of step is fixed on carrier by sol-gel method, and be prepared into PtRT film, carrier selects conduction (common) sheet glass.Its technical process is: original sheet glass prepares → cleans → dry → enter plated film pond → be coated with → dry → enter heat treatment furnace to sinter → come out of the stove cooling down.In present method, by being fixed on sheet glass by PtRT colloidal sol by dip-coating method or single face spraying coating method, on sheet glass, the thickness of catalyst film should control 5 – 10 μm.For different processing requirements, the PtRT film of different size should be prepared.
(2) photo catalysis reactor is prepared.Present method adopts shallow pond type fixed-bed reactor.Reactor is rectangular structure, and size is about 3.4m × 0.9m × 0.4m.This rectangular parallelepiped is divided into 5 rectangle form pools by 4 pieces of longitudinal baffles.Former and later two little Chi (0.2m × 0.9m × 0.4m) play reaction soln and are uniformly distributed and collect effect.Middle three little Chi (1.0m × 0.9m × 0.4m) are then for being filled with the reaction member of photocatalyst.In these 3 reaction tanks, installed baffle respectively, their bottoms are about 5cm at the bottom of distance pond, and in pond, liquid surface total height is 20cm.Arrange the PtRT photocatalyst film of 10 – 20 layers in reaction tank, adjacent double-layer films becomes square crossing to arrange.
(3) light source of reactor is made up of the ultraviolet sterilization lamp of the 30W of 30 – 40 arranged in parallel.Ultraviolet lamp should be arranged in the lampshade of black.The spacing of adjacent two lamps should control within the scope of 10 – 20cm.The lamp base of all lamps all adopts hermetic design.
(4) reactor and light source are installed and fixing after, municipal effluent is entered reactor, under ultraviolet source, carries out degradation treatment.Intensity (the 1.0 – 2.2mW/cm of water flow velocity (2.0 – 6.0L/h) and UV-light in control
2).
Advantage of the present invention is, rutile titanium oxide (the Rutile TiO of the high-crystallinity obtained through high-temperature calcination modified for platinum (Pt) by the photocatalyst used
2, referred to as RT) effectively improve catalytic efficiency for catalyzer.TiO
2for the most frequently used photocatalyst.Common TiO
2mainly contain two kinds of crystal formations: anatase octahedrite (Anatase) and rutile (Rutile).In general, for organic matter degradation, the activity of anatase octahedrite is higher than rutile.If but contriver finds to use platinum (Pt) modify and particularly through the RT of high temperature (>1200 DEG C) calcination processing, can obtain and possess extremely highly active photocatalyst.Meanwhile, the present invention passes through the setting of the correlation parameter in the strength reinforcing of water flow velocity and ultraviolet in control sewage treatment process, can carry out industrial applications very well, realize the efficient industrial treatment for this special water of municipal effluent.Method of the present invention is relative to additive method, and thorough for organism mineralising, by utilizing clean, reproducible luminous energy, under relatively mild reaction conditions, can be decomposed, can not cause secondary pollution by the inventive method.Process is simple, and range of application is wider.And cost of the present invention is lower, development potentiality is huge; Photocatalytic reaction conditions is gentle; Can carry out under room temperature; The photocatalyst adopted is nontoxic, cheap.
Embodiment
Below in conjunction with specific examples, the present invention is further elaborated.
Embodiment 1
(1) TiCl is passed through
4the method of hydrolysis has prepared rutile TiO
2(referred to as RT), under condition of ice bath, while stirring by 40mL TiCl
4(temperature is lower than 15 DEG C) in the aqueous solution of the dense HCl of 40mL have been dissolved in slow dropping (2mL/min) to 1000mL, obtain lurid settled solution.2h is incubated after this solution is slowly warming up to 60 DEG C.In insulating process, solution engenders that white opacity is to precipitation.Afterwards this turbid solution is positioned in ice bath ageing of spending the night.Without Cl in filtration washing to filtrate
-(use AgNO
3solution detects) and in neutral, after 80 DEG C of oven dry, grinding gained sample also crosses 200 mesh sieves.This sample is referred to as RT.Afterwards RT is calcined 3h at 1200 DEG C.
(2) further, the method precipitated by chemical light prepares the RT (PtRT) that Pt modifies, by methyl alcohol, and H
2ptCl
6certain hour is reacted under ultraviolet light with RT.Under magnetic agitation, by methyl alcohol, H
2ptCl
6after mixing with RT, irradiate reaction 3h under ultraviolet light.In PtRT, the content of Pt is 0.5wt%.
(3) by after PtRT and 5.0wt%PVA aqueous solution, be prepared into colloidal sol, by dip-coating method, PtRT be fixed on conductive glass, prepared PtRT film, at 500 DEG C, calcine 3h.Film thickness is 5 μm.Film is of a size of 0.2m × 0.3m.
(4) be positioned in photo catalysis reactor by PtRT film, wherein, PtRT photocatalyst film has 10 layers, and the light source of reactor is made up of the ultraviolet sterilization lamp of the 30W of arranged in parallel 30.The spacing of adjacent two lamps is 10cm.
(5), after equipment connection, open ultraviolet source, passed into by municipal effluent in equipment, [in municipal effluent, chemical oxygen demand (COD) (COD) is 65.2mg/L, and initial T hydrocarbon is 18.5mg/L] processes.The intensity of light source is 1.5mW/cm
2, middle water flow velocity is 3.0L/h.Organic mineralization rate in municipal effluent, the method by high performance liquid chromatography (HPLC) is tested, and the model of HPLC is Dionex P680, and chromatographic column type is Apollo C18 reverse-phase chromatographic column, and moving phase is CH
3oH:H
2o=3:2, flow velocity 1.0mL/min, detector is UVD 170U UV-detector.
After present method process, in municipal middle water, organic content obviously declines, in municipal effluent, chemical oxygen demand (COD) (COD) is 10.1mg/L, fall is more than 85%, and organism is almost 0.9mg/L after permineralization TOC process, do not produce secondary pollution, the clearance of TOC is 95%; Municipal effluent after process meets the requirement of power plant circulating cooling water.
Comparative example 1
Other step is with embodiment 1, and difference is, RT calcines 3h at 1000 DEG C.After treatment, the chemical oxygen demand (COD) (COD) of middle water sample drops to 26.7mg/L from 64.8mg/L, and fall is 59%, and initial TOC is 18.5mg/L, and process is 4.1mg/L, TOC clearance is afterwards 78%.
Comparative example 2
Other step is with embodiment 1, and difference is, does not have the moditied processing of Pt.After treatment, the chemical oxygen demand (COD) (COD) of middle water sample drops to 52.7mg/L from 64.8mg/L, and fall is 18.7%, and initial TOC is 18.5mg/L, is that the clearance of 14.6mg/L, TOC is 21% after process.
Claims (3)
1. urban sewage recycling is in a treatment process for the recirculated cooling water in fuel-burning power plant, it is characterized in that, comprises following preparation process:
1) photocatalyst film needed for preparation: by rutile TiO
2be not less than the temperature lower calcination 3 ~ 5 hours of 1200 DEG C; In the rutile TiO through above-mentioned high-temperature calcination
2upper modification deposits and accounts for its mass content 0.1 ~ 1.5%Pt thus the photocatalyst obtained; Be fixed on carrier by described photocatalyst by sol-gel method, be prepared into required photocatalyst film, on carrier, the thickness of photocatalyst film should control at 5 ~ 10 μm;
2) prepare photo catalysis reactor: reactor is rectangular parallelepiped, be divided into 5 rectangle form pools by 4 pieces of longitudinal baffles, former and later two little Chi and middle three little Chi, then for being provided with the reaction member of photocatalyst film in middle three little Chi; The light source of reactor is UV-light;
3) municipal effluent is flowed into the recirculated cooling water obtained after photo catalysis reactor carries out photocatalytic degradation process needed for thermal power plant, in photocatalytic degradation treating processes, control ultraviolet ray intensity is 1.0 ~ 2.2mW/cm
2, municipal effluent flow velocity 2.0 ~ 6.0L/h.
2. treatment process according to claim 1, is characterized in that, by rutile TiO
2at the temperature lower calcination of 1200 DEG C ~ 1500 DEG C.
3. treatment process according to claim 1, is characterized in that, in the rutile TiO through high-temperature calcination
2upper modification deposits and accounts for its mass content 0.5wt%Pt; By rutile TiO
2at the temperature lower calcination 3 hours of 1200 DEG C.
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|---|---|---|---|
| CN201410560354.1A CN104326525B (en) | 2014-10-21 | 2014-10-21 | A kind of urban sewage recycling is in the treatment process of the recirculated cooling water in fuel-burning power plant |
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|---|---|---|---|
| CN201410560354.1A CN104326525B (en) | 2014-10-21 | 2014-10-21 | A kind of urban sewage recycling is in the treatment process of the recirculated cooling water in fuel-burning power plant |
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| Publication Number | Publication Date |
|---|---|
| CN104326525A true CN104326525A (en) | 2015-02-04 |
| CN104326525B CN104326525B (en) | 2015-12-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001286757A (en) * | 2000-04-05 | 2001-10-16 | Sumitomo Electric Ind Ltd | Photocatalyst powder and photocatalyst carrier |
| JP2009018282A (en) * | 2007-07-13 | 2009-01-29 | Japan Organo Co Ltd | Ultraviolet oxidation device and ultraviolet oxidation method |
| CN102500363A (en) * | 2011-03-10 | 2012-06-20 | 中国科学院福建物质结构研究所 | Noble metal orientation load titanium dioxide photocatalyst and preparation method thereof |
| CN103118987A (en) * | 2010-10-26 | 2013-05-22 | 英派尔科技开发有限公司 | Water treatment apparatus and systems |
-
2014
- 2014-10-21 CN CN201410560354.1A patent/CN104326525B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001286757A (en) * | 2000-04-05 | 2001-10-16 | Sumitomo Electric Ind Ltd | Photocatalyst powder and photocatalyst carrier |
| JP2009018282A (en) * | 2007-07-13 | 2009-01-29 | Japan Organo Co Ltd | Ultraviolet oxidation device and ultraviolet oxidation method |
| CN103118987A (en) * | 2010-10-26 | 2013-05-22 | 英派尔科技开发有限公司 | Water treatment apparatus and systems |
| CN102500363A (en) * | 2011-03-10 | 2012-06-20 | 中国科学院福建物质结构研究所 | Noble metal orientation load titanium dioxide photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 林万舟等: "TiO2纳米膜光催化深度处理城市污水的实验研究", 《环境科学与管理》 * |
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