CN1245147A - Photocatalytic reaction system for treating waste water - Google Patents
Photocatalytic reaction system for treating waste water Download PDFInfo
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- CN1245147A CN1245147A CN 99118053 CN99118053A CN1245147A CN 1245147 A CN1245147 A CN 1245147A CN 99118053 CN99118053 CN 99118053 CN 99118053 A CN99118053 A CN 99118053A CN 1245147 A CN1245147 A CN 1245147A
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Abstract
The present invention discloses a photocatalytic reaction system for treating waste water. The present invention discloses also a photocatalytic reactor and a TiO2 catalyzer recovery device.
Description
Generalized theory the present invention relates to Waste Water Treatment.Specifically, the present invention relates in the photochemical catalytic oxidation system, utilize light-catalyzed reaction to purify liquid waste, even be not that the professional also can stably operate this system, it the organic pollutant that is difficult in the waste water decompose can be oxidized to one suitable can level.
The soil landfill is one of present widely used useless treatment process.After refuse is by landfill, also need to handle well from by the waste water that oozes out the refuse of landfill, because the various organism that wherein contain can serious environment pollutions.But, be difficult to the process standardization of waste water is oozed out in processing, because it is different because of different landfill places to ooze out the characteristic of waste water, and can change in time.
Because the processing of pollutent load is very big with respect to quantum of output, if movement that is produced by herding and waste water can cause serious water to pollute and eutrophication to its water body that finally enters without suitable processing.With regard to trade effluent, if without suitable processing, its harm is enough to the environment and the mankind are caused disaster.Especially waste water and trotyl (TNT) waste water from Electroplate Factory, paper mill, printing and dyeing mill, tannery, chemical plant etc. can pollute underground water and soil earth.
So far, it has been found that the very difficult method of wastewater treatment that utilizes the waste water self-characteristic of selecting and develop.Even this treatment process is selected, it also is difficult to the operating operation, and the person causes technical difficulty.Conventional treatment method can not decompose some organism nearly all based on biology or physical and chemical principle, and has the shortcoming that generation secondary waste need add aftertreatment.
Generalized theory, wastewater treatment roughly are divided into biotechnology and physical chemistry technology.Biologic treating technique is used for the biodegradable organism of oxidation, and the physical chemistry technology then is used for removing and oxidation suspended matter and organic substance.When the water seepage of handling the landfill refuse, the trade effluent waste water and trotyl (TNT) waste water of Electroplate Factory, paper mill, printing and dyeing mill, tannery, petroleum chemical plant etc. (for example from) and animal husbandry, waste water, conventional biologic treating technique organism poisonous and that be difficult to decompose can not be reduced to one suitable can level, and be difficult to operate because these organism are poisonous.Usually handling with the physical chemistry of biological treatment coupling is to remove organism or remove material poisonous and that be difficult to degrade by cohesion, precipitation, membrane sepn and/or absorption, but make water seepage, the trade effluent waste water and trotyl (TNT) waste water of Electroplate Factory, paper mill, printing and dyeing mill, tannery, petroleum chemical plant etc. (for example from) and the animal husbandry waste water of landfill refuse reach emission standard, cost dearly and have technical difficulty.
In high-level oxidation technology/method (AOT/AOP) as one of wastewater processing technology, be to use the stronger OH free radical of efficient at faster speed and higher efficient come oxidation of organic compounds, the oxidation activity of OH free radical outclass the general chemistry oxygenant.Because the OH free radical not only can be with biodegradable material in the water, and organism poisonous in the water and that be difficult to degrade can be completely oxidized to CO
2And H
2O, AOT/AOP have become the hot technology that attracts people's attention.At present, AOT/AOP has been used to handle the lower underground water of pollutant load and colourity and turbidity.
TiO as one of AOT/AOP
2Photocatalytic oxidation, the principle of being utilized are that the luminous energy that catalyzer absorbs surpasses TiO
2Energy gap (380nm or shorter) time electronics and the room that are produced organic substance is decomposed.Semi-conductor has produced electronics from the motion of valence band to conduction band when absorbing luminous energy, produce electronics or room this moment.Oxygen in they and the water, superoxide or the reaction of peroxide radical ion generate the OH free radical with strong oxidation capacity, and the latter is resolved into CO with the pollutent in the water then
2And H
2O.If electronics can not contact with reaction induced thing with the room, they can be bonded to each other soon, so just can not induce photoresponse has taken place.So, at TiO
2In the photocatalyst oxidizes technology, TiO importantly
2Catalyzer can absorb above TiO
2The luminous energy of energy gap produces electronics/double-void that quantity equates thus.In other words, the carrying out of photocatalyst reaction be following mode preferably: the room of generation is used for oxidation, and the electronics that moves to conduction band then reduces, so each other just can not recombine.If catalyzer has produced electronics/double-void through exciting, it will be oxidized to the OH free radical with strong oxidation capacity with the hydroxide ion of absorption.These OH free radicals then can be used to decomposing organic matter.Simultaneously, the electronics that moves to conduction band then produces super oxyradical (O with the electron acceptor(EA) reaction of oxygen and/or hydrogen peroxide and so on
2 -) and/or hydrogen peroxide free radical (HO
2), these free radicals can both decomposing organic matter.Just stoped the recombine between electronics and the room thus.
Because absorb luminous energy and electronics and room recombine each other in very short time after being excited at photocatalyst, so TiO
2The key of photocatalyst oxidizes technology be the to slow down process of recombine reduces the energy gap of photocatalyst and saves the luminous energy that uses greater than this energy gap.
Above-mentioned light-catalyzed reaction is following expansion on semi-conductor.
At first, produce electronics and room with the luminous energy vitalizing semiconductor.The electronics of conduction band has reducing power, and the room of valence band then shows oxidation capacity.
Then, electronics and room are separated at semiconductor surface, cause the photochemical catalysis chemical reaction, produce the OH free radical.The speed of carrying out of this light-catalyzed reaction must be faster than the speed of electronics and room recombine, otherwise light-catalyzed reaction just can not take place.
Again then, electronics and room contact with organism on semi-conductive surface and with its oxidation and reduction.At this moment, the OH free radical plays a part strong oxidizer.
At last, organism finally is broken down into CO
2And H
2O.When these end products left semiconductor surface, katalysis was carried out again on the surface.
Following chain reaction takes place in OH free radical and organism that catalyst surface produces simultaneously:
1. the OH free radical of catalyst surface and be adsorbed in reaction between the organism of catalyst surface.
2. leave the OH free radical of catalyst surface and be adsorbed in reaction between the organism of catalyst surface.
3. the reaction between near the organism the OH free radical of catalyst surface and the catalyst surface.
4. leave the OH free radical of catalyst surface and the reaction between near the organism the catalyst surface.
Therefore, TiO
2The oxidation mechanism of photocatalysis oxidation technique utilization may further comprise the steps: vitalizing semiconductor produces electronics/double-void on its surface, prevent electronics/double-void recombine, effect by electronics/double-void produces the OH free radical rapidly, by the abundant decomposing organic matter of OH free radical.This photocatalyst oxidizes technology has proved the effect that it is good in groundwater treatment, but in the water seepage of effectively removing the landfill refuse, trade effluent (for example handling the waste water and the TNT waste water of workshop, petroleum chemical plant etc.) and animal husbandry waste water from electroplating workshop, paper mill, printing and dyeing and leather poisonous and be difficult to degradation material aspect still underuse.
Relevant prior art can be referring to United States Patent (USP) 5,462, and 671 and the disclosed patent application 98-50359 of Korea S.
Above-mentioned U.S. Patent Publication utilize free radical low pressure photocatalyst reactor to handle the method and system of contaminated liquid continuously.Not only the liquid treatment ability is low for this free radical low pressure photocatalyst reactor, so and owing to use the low-voltage light source processing efficiency very poor.But this system can handle underground water be difficult to handle commonly industrial wastewater.
Above-mentioned Korean Patent is disclosed to be a kind of wastewater treatment equipment, allegedly can solve cohesion and reclaim powder in the reactor or the problem of pellet type catalyst.It is said that this device is easy and simple to handle, and can use photocatalyst continuously.But, because slurry stirs with stirring pump, so above-mentioned photocatalyst exists the inefficient problem of light-catalyzed reaction.
The present inventor is carrying out finding TiO after the extensive and deep research to wastewater treatment
2Catalyzer can produce the OH free radical after being subjected to the UV optical excitation, the latter can be with the oxidation operation in the waste water in underground water and various sources to the level that requires.The inventor has grasped TiO
2The mechanism of photocatalysis and the influence that can change the various reaction parameters of adjusting, thus the present invention caused.
One of the object of the invention is to overcome the problems of the prior art, and the Waste Water Treatment that utilizes light-catalyzed reaction is provided, and this system is that non-technical personnel also can stable operation.
The object of the invention also is to provide and need not to consider that wastewater characteristics uses the Waste Water Treatment of light-catalyzed reaction.
The object of the invention is to provide the organic pollutant that is difficult in the waste water degrade at TiO again
2But can be oxidized to suitable level under photocatalyst exists, and not produce the Waste Water Treatment of secondary pollutant.
According to the present invention, provide one to utilize the Waste Water Treatment of light-catalyzed reaction to achieve the above object, the flow process of this system comprises: preprocessing process, this moment is by cohesion and precipitate the solid matter of removing in the waste water, and carries out pH regulator and slough ammonia; Mixing process, this moment through pretreated waste water in mixing pit with TiO
2Powder and reaction promoter mix; Photo-oxidation process, introduce at least one photocatalyst reactor through above-mentioned mixed waste water from the inlet that is positioned at reactor lower part this moment, along with waste water upwards operation and circulation in the photocatalyst reactor, pollutent wherein is by photoxidation and decomposition, described photocatalyst reactor has a cylindrical shell, the turbulent flow plate that wherein has two center drillings at least, each plate is arranged along the inwall of housing according to certain interval, by the hole on these turbulent flow plates the silica tube of establishing the UV lamp in one is housed; The catalyst recovery process, removed the waste water of pollutent at 3-5kg/cm this moment
2Pressure down by a TiO
2Catalyst recovery devices is purified water, described TiO
2Clay filter is housed in the catalyst recovery devices, and it is with TiO
2Powder is retained down and allows waste water filter, and also has some scraper plates, and they will be trapped in the lip-deep TiO of clay filter
2Powder scrapes off; Catalyzer utilizes process again, the TiO that scraped this moment
2Powder recirculation turns back in the above-mentioned mixing pit.
Read following detailed description the in detail in conjunction with the accompanying drawings, will have more clearly above-mentioned purpose of the present invention, feature and other advantage and understand, in the accompanying drawing:
Fig. 1 is that the present invention utilizes TiO
2The entire flow figure of the Waste Water Treatment of photocatalysis oxidation technique;
Fig. 2 is TiO of the present invention
2The schema of photochemical catalytic oxidation equipment;
Fig. 3 is TiO of the present invention
2Light is urged the sectional view of oxidation reactor;
Fig. 4 is TiO
2The schema of preprocessing process before the photochemical catalytic oxidation;
Fig. 5 reclaims TiO from processed waste water
2The sectional view of the catalyst recovery devices of powder.
Describe the present invention in detail below with reference to these accompanying drawings.
The present invention relates to utilize TiO2Photocatalysis oxidation technique is processed the method for waste water, described waste water comprises water seepage, industrial wastewater (such as from waste water and trinitrotoluene (TNT) waste water of electroplating workshop, paper mill, printing and dyeing and leather processing workshop, petrochemical plant etc.), animal husbandry waste water and the contaminated underground water of landfill refuse, utilize this method, at TiO2Under the existence condition, be subjected to UV-irradiation, poisonous and hard degradation has in the waste water The machine thing is oxidized to the stable material of environmental sound, does not produce secondary pollution in the method.
It is pointed out that " waste water " herein if not illustrate in addition, comprise water seepage, the worker of landfill refuse Industry waste water is (such as the waste water of processing workshop, petrochemical plant etc. from plating workshop, paper mill, printing and dyeing and leather And trinitrotoluene (TNT) waste water), animal husbandry waste water and contaminated underground water.
Generally speaking, TiO2Light is urged oxidation technology to have photochemical catalytic oxidation efficient with fluid colourity, turbidity and is had The machine substrate concentration raises and the tendency of reduction. In order to utilize TiO2Light is urged oxidation technology to process and is obtained effective treatment effect in the waste water of high chroma, turbidity and organic concentration, must carry out TiO2Light carries out suitably before urging oxidation Processing.
According to the present invention, this step preliminary treatment comprises for the chemical coagulation process of removing suspended material and removes ammonia The deamination process of gas nitrogen. In the chemical coagulation process, with flocculating agent FeCl for example3Reduce colourity in the waste water, Turbidity and organic concentration. This coacervation process is that the inventive method is necessary. Then to having removed thus pulpous state The waste water of thing carries out pH to be regulated, and forces then to be blown into air and removes ammonia. Deamination can carry out, and also can not advance OK. If deamination is not to carry out in preliminary treatment, can after photooxidation, carry out so. Above-mentioned preprocessing process In each step all be well known in the art, can all or part ofly omit, also can mend according to the characteristics of waste water Fill other process.
Fig. 1 and Fig. 4 are overall process and the preprocessing process of wastewater treatment of the present invention.
As shown in the figure, earlier waste water is introduced Flow-rate adjustment pond 1, be transported to coagulating basin 2, add H therein by means of pump
2SO
4And FeCl
3Be adjusted to pH3.5-4.5.The waste water that contains condensation product after cohesion is introduced in the settling tank 3 and leaves standstill for some time.The mud that produces in settling tank 3 is sent to water trap 11 and carries out last processing, and the water of deviating from from mud turns back to the Flow-rate adjustment pond 1 again and continues scrubbing.Then, waste water enters pH regulator pond 4 again, adds NaOH therein with the pH regulator to 10.7 of waste water or higher, enters deammoniation tower again and sloughs ammonia.Then, waste water flows into mixing pit 6, adds H therein
2SO
4, the reaction promoter H in addition that adds together
2O
2, wastewater pH is maintained 3-4.In this pH scope, can obtain the most stable oxidation efficiency.
That Fig. 2 and Fig. 3 show is TiO of the present invention
2Wastewater treatment process in the photocatalytic oxidation device.As shown in Figure 2, an available pump with waste water from mixing pit 6 in the suction photocatalysis oxidation reaction device 7.In order to handle waste water better, must be with itself and photocatalyst thorough mixing.For this reason, photocatalysis oxidation reaction device portion's turbulization within it.That Fig. 3 shows is the TiO of turbulization of the present invention
2The photocatalysis oxidation reaction device.In the garden cylindrical shell of reactor 7 lamp protective tube 13 is arranged, made by quartz, UV lamp 12 is equipped with at its center.Between the inwall of reactor 7 housings and lamp protective tube 13 is some turbulent flow plates 14 around lamp protective tube 13, and they are near inner walls but separate certain distance with the outer wall 13 ' of lamp protective tube 13.So, between every block of turbulent flow plate 14 and outer wall 13 ', form a gap, be called annulus, with numeral 14 ' expression, sewage or waste water this annulus of flowing through.Be preferably, turbulent flow plate 14 and the outer wall 13 of the lamp protective tube 5-12mm of being separated by, like this, will turbulization when waste water is flowed through this this annulus.
In the top and the bottom of reactor 7 housings of representing with A and B respectively, the internal surface welding of upper sealing panel 23 and lower seal plate 23 ' and housing sidewall.Lamp protective tube 13 vertically is positioned at the medullary ray of reactor 7, and cooperates with the centre hole of upper-lower seal plate 23 and 23 ', by the removable cover 21 and the 21 ' supporting at two ends up and down.Two removable covers 21 are connected with the sealing plate bolt with 21 '.O ring D or D ' closely are contained in the annular space between lamp protective tube 13 and two sealing plates and seal.
Be fixed on the upper-lower seal plate in order to cover 21 and 21 ' with bolt 22, go up some appropriate locations at lid 21 and 21 ' and open several lock holes, simultaneously, several internal thread holes are opened in the corresponding position on sealing plate 23 and 23 '.For the last lower end with lamp 12 is fixed in the protective tube 13, will closely be contained at the dish-shaped cap 20 and 21 ' that one side has a middle part boss and cover in 21 and 21 ' the centre hole, and with several bolts with cover 21 and be connected with 21 '.
Below will describe the present invention two running and the effects of turbulent flow photoreactor with one heart in detail.
At the bottom of reactor shell B and top A inlet E and outlet F are arranged respectively, waste water therefrom flows through under the pressure of pump.Under pressure, flow through the outer wall 13 ' of lamp protective tube 13 and the annulus between the turbulent flow plate from the sewage or waste water that enters of inlet E, turbulization at this moment makes waste water and TiO
2Powder and H
2O
2Thorough mixing.
After causing turbulent flow, sewage or waste water is operation upwards, is filled in the space between lamp protective tube 13 outer walls 13 ' and the inner walls, forms continuously and fast in this space and flows.As a result, pollutants in waste water is subjected to the stirring of each turbulent flow plate, can not be deposited on the lamp protective tube outer wall, also can not be deposited on the inwall of reactor.So this burst turbulent flow makes lamp protective tube and reactor shell to keep clean in considerable time, therefore, in this same long time, photoactivation agent (TiO
2) purifying liquid waste to keep higher efficient.
In addition, can use a plurality of reactors 7 with parallel connection or series connection form.At this moment, pollutants in waste water has more opportunity near the lamp protective tube, so the UV rayed that they receive is more abundant.The result is in these a plurality of reactors, and granules of catalyst can cause photoresponse continuously, makes processing efficiency reach maximum thus.
In turbulization granules of catalyst having been eliminated in waste water pressurization is deposited on the base plate and causes the problem that temperature raises; and formation flowing fast continuously along the lamp protective tube; this has just been avoided the contaminated thing of lamp protective tube outer wall to pollute, and does not therefore need to be keeped in repair in addition.Exceeded the processing power of design in advance if waste water becomes a mandarin, can add some equipment easily and handle overflow.
Get back to Fig. 2, the UV lamp in the reactor 7 sends UV light, makes and waste water blended TiO
2Catalyzer and H
2O, oxygen and H
2O
2Reaction generates the OH free radical with strong oxidation capacity at catalyst surface.Then, the OH free radical is completely oxidized to H with material poisonous and that be difficult to decompose
2O and CO
2Can partly turn back to mixing pit 6 and do further scrubbing with pump photo catalysis reactor 7 waste water after handling of will flowing through, all the other then flow into neutralization tank 8, therein with pH regulator to 6.5-8.5, the inflow catalyst pond for recovering 9 then.Perhaps, if do not carry out deamination when pre-treatment, the waste water after the photo catalysis reactor 7 of flowing through is handled preferably carries out deamination one time.
Must be to UV lamp and TiO
2Catalyzer carries out appropriate selection.The UV luminous energy that sends when the UV lamp is 1KW, and when wavelength was 253.7-380nm, wastewater treatment was the most effective.The length of the used UV lamp of the present invention is 670mm.Anatase octahedrite TiO
2The catalyzer that is used as light-catalyzed reaction.Consider TiO from reaction efficiency and economic interests angle
2Consumption be 0.1 weight % or higher, % is advisable with 0.1-0.5 weight.
In order to activate UV light and TiO
2Reaction produces electronics and room, where necessary, can add an amount of reaction promoter suitable concerning wastewater treatment, for example H
2O
2, KBrO
3, (NH
4)
2S
2O
8And/or 2KHSO
3KHSO
4K
2SO
4We find that dissolved oxygen is not suitable as this type of reaction promoter.Under the situation that dissolved oxygen exists, TiO
2Be difficult to produce electronics and room actively with the photoresponse of UV light, even produced electronics and room, they also can recombine, thereby can not well bring into play the function of decomposing pollutant.On the contrary, we find, H
2O
2Help to produce actively electronics and room, and can produce the OH free radical, be able to the organism that oxidation fully is difficult to decompose by electronics and room.
Used catalyst TiO
2Can utilize again after the recovery.So, need TiO of design
2Catalyst recovery devices.
That Fig. 5 shows is TiO
2 Catalyst recovery devices 9.
As shown in the figure, TiO
2Catalyst recovery devices 9 comprises and is used for filtered wastewater and it is entered first mechanism of next purification tank for liquid waste.There is the axle 17 of a hollow in this first mechanism, and it is vertically fixed on the center of device 9 case top.Along its length, many oval-shaped water vents have been opened in some predetermined positions of quill shaft 17 outer walls.On the outer wall of axle 17, several for example two collars are installed around water vent.Utilize each collar, clay filter 15 is fixedly secured on axle 17.Device 9 is used for second mechanism that catalyzer is struck off from clay filter 15 surfaces in addition.Second mechanism comprises a rotating cylindrical shell, and it surrounds axle 17 with one heart, and in clay filter 15 is enclosed in.Fixed many scraper plates 16 on the inwall of rotary barrel, the position at its place makes the upper and lower surface of their tight contacted filters 15.Device 9 comprises that also one is utilized the turning force of motor to drive the driving mechanism that cylindrical shell rotates.Driving mechanism comprises a follower gear.Follower gear is fixed on axle 17 tops with rotary way, and utilizes the roof of a plurality of bolts and rotary barrel to fix.Cooperate with follower gear with the driving gear that rotary way is connected with motor, by follower gear the turning force of motor is passed to rotary barrel and make it rotation.So when device 9 runnings, rotary barrel rotates round axle 17 by means of the turning force of motor, scraper plate 16 strikes off catalyzer from the upper and lower surface of strainer 15.
40-50 weight % clay is mixed with 50-60 weight % porous material, be prepared into clay filter.The indefiniteness example that porous material is described has gac and/or diatomite.If the porous material that uses is less than 50 weight %, the drainage rate of clay filter is too low, can reduce processing efficiency.On the contrary, porous material surpasses the intensity that 60 weight % can reduce clay filter.In order to obtain finely dispersed raw mix, the most well 100 purposes sieve of used clay.
The clay mixture of above acquisition is molded as dish earlier, leaves standstill seasoning.Coat contained porous material particle diameter and aperture all than previous used little clayish solution, the clayish solution that does not contain porous material or glaze, seasoning again in the one side of dish then.More than coating and drying process repeat 2 to 6 times, have certain thickness coating until formation.Below table 1 provided and can be used for porous material example of the present invention.But according to the characteristic of processing waste water, those skilled in the art can be easily to the particle diameter of these porous materials and the thickness correct of aperture and coating, so it is limitation of the present invention that the porous material that exemplifies in the table 1 should not be understood as that.
Table 1
Porous material median size (μ m) mean pore size (μ m) is annotated
Celite545 36.2 17.0 clays
Celite560 55 22.0 clays
Celite500 14.7 1.5 coatings
Celite577 14.6 2.5 coatings
Then, through the dish of above-mentioned coating at 950-1,300 ℃ of sintering 5 to 12 hours.If as coating, above temperature range is preferably with the clayish solution that mixed porous material or pure clay solution.If as coating, because glaze can be at about 1,300 ℃ of tight burning, this moment, sintering temperature was preferably in 1000 to 1100 ℃ with glaze.Avoided the tight burning of glaze like this, strainer has certain intensity and lackluster with regard to making.
Many so dish-shaped screen plates are overlaped, and the middle expanding metal net (not showing) that inserts is used C shape plate, sealing agent or tackiness agent built-in edge then, and recycle silicon glue is sealed to clay filter 15.Filterable water flows through by the hole of expanding metal net, and wire netting is connected with water vent on the fixed quill shaft 17.
According to the present invention, can be according to the content of the characteristic of sewage or waste water and pollutent to the strainer correct.For example, can two clay screen plates are overlapping, the middle expanding metal plate that inserts, its objective is and bear the pressure that puts on the strainer 15 and the screen plate of metal sheet both sides is separated, fix its edge with C shape plate, sealing agent or tackiness agent then, make resistance to air loss clay filter 15 with silica gel sealing at last.For this strainer 15 is installed on the fixed quill shaft 17, a collar and rubber sheet gasket or O ring are installed on axle 17 outer walls around water vent.In case of necessity, can after being installed, clay filter 15 refill a rubber sheet gasket or O ring.The number of overlapping screen plate depends on the quality of the waste water of handling, and is advisable with 10 to 18.
(suitable is 2 to 4kg/cm under certain pressure
2), treating water flows into clay seam from coatingsurface, by whole clay filter 15, flows through the passage that the expanding metal is defined, the water vent on fixing quill shaft 17.Then, the treating water that flows through water vent is discharged from exporting 18.In the longitudinal direction, the oval water vent that keeps at a certain distance away is relatively being arranged on the outer wall of quill shaft 17, and it is overlapping the hole can be arranged in hole and following hole.So, can be as required at TiO
2The clay filter as much as possible of packing in the catalyst recovery devices.
When treating water flow through the coating of clay filter, impurity can not be held back by porous material by strainer.Along with the accumulation of impurity at coatingsurface, the filtration efficiency of clay filter reduces.In order to prevent the reduction of filtration efficiency, the effect of scraper plate is exactly to strike off these impurity that are accumulated.Perhaps, also can in quill shaft, blow and clean clay filter.In order to play upper and lower surface collection catalyst that strikes off strainer 15 and the effect of removing impurity, scraper plate 16 is installed in the certain position on the rotary barrel inwall, the scraper plate 16 of make suring closely contacts with the upper and lower surface of strainer 15, simultaneously, scraper plate is subjected to drive mechanism, driving mechanism comprises the follower gear that cooperates with driving gear, and this mechanism is fixed on axle 17 top and can rotates, on a plurality of roofs that are bolted to rotary barrel.
After being scraped, catalyzer and impurity falls at the bottom of the pond.After they are accumulated to certain degree, discharge, get back to mixing pit 6 by catalyst recovery mouth 19.After having experienced above cleaning course, clay filter has recovered initial filtration efficiency again.Clay filter can effectively be handled the fine particulate material (0.1-1 μ m) of organic or inorganic.
The present invention may be better understood by following examples, these embodiment only for the purpose of description, can not be understood as is limitation of the invention.
Embodiment 1
The preparation clay filter
In raw clay impouring water, cross 100 mesh sieves, be prepared into the 45kg fine clay, then with 55kg diatomite (available from Celite Korea, Korea, commodity be called " Celite 560 ") mixing.In a jar, mix above mixture, with vacuum pump jar is taken out with vacuum simultaneously, form hole in matrix (clayish solution) inside in order to avoid diatomite.
The matrix of above preparation is poured in the gypsum mold, left standstill and dry in the shade one day.After the demoulding, allow the matrix that is shaped dry in the shade again one day, make the dryness factor of matrix reach 80%.If this clay dish unfairness then is processed into smooth to it.One side at smooth clay dish applies coating.For this reason, slurry that will sieve through 100 orders and diatomite are (available from Celite Korea, Korea, commodity are called " Celite 500 ") press 4.5: 5.5 clays: Celite500 weight ratio thorough mixing is coated in this suspension on the surface of clay plate thinly with brush then.
After being coated with, allow plate thoroughly dry in the shade with 2 day time, sinter screen plate at about 1200 ℃ then.A wire netting is inserted in the middle of two above-mentioned screen plates, fixes its edge with C shape plate then, use silica gel sealing at last.
With several clay filters of embodiment 1 preparation, in the following catalyst recovery devices that is assembled into Fig. 5.Earlier an O ring is packed into and be positioned at the support of stationary shaft bottom.On support, place the clay filter of one deck embodiment 1 preparation.Then, on this clay filter, place the collar of a band O ring.After in the manner described above the assembling of 10 strainers and stationary shaft being finished, on stationary shaft, load onto a length adjustment collar, lock with stationary shaft then.On the other hand, many scraper plates are loaded onto at certain intervals position on the rotary barrel inner side-wall, and these scraper plates are inwardly stretched towards stationary shaft by the wall of rotary barrel.At this moment, the rotary barrel that is rotatably connected above stationary shaft and the follower gear of driving mechanism are fixed, and be promptly rotatable by driving mechanism.
What be used for testing apparatus of the present invention is water seepage from the refuse landfill, and its characteristic is as shown in table 2.After typical biological treatment, water seepage is introduced into the Flow-rate adjustment pond, is pumped to coagulating basin again.In coagulating basin, add the H of 4000mg/l
2SO
4FeCl with 1300mg/l
3, make that pH is 4.Again waste water is sent into settling tank by coagulating basin, left standstill 90 minutes.Then, the mud that forms is delivered to water trap finally handle, the water of deviating from from mud turns back to the further scrubbing in Flow-rate adjustment pond.Waste water is introduced into the pH regulator pond, and the NaOH that adds 4000mg/l enters pH regulator to 11 again deammoniation tower and gets rid of ammonia.Then, waste water flows into mixing pit, adds the H of 4500mg/l at this
2SO
4, 1000mg/l reaction promoter H
2O
2, the pH of waste water is remained on 3.5.With pump waste water is delivered to 6 placed in-line photocatalysis oxidation reaction devices shown in Figure 3, make waste water carry out to a certain degree circulation therein.Each photocatalysis oxidation reaction device all has the UV fluorescent tube of a long 670mm diameter 150mm.The circumferential surface of baffle plate (turbulent flow plate) and silica tube outside surface be 7mm at interval.The UV lamp sends the light of 253-380nm.The TiO that adds 0.1-0.2 weight %
2Then, the water after the processing flows through embodiment 2 described catalyst recovery devices (aperture of filter media is 0.1-1 μ m) discharges, and the catalyzer of recovery collects to turn back in the mixing pit and uses.The waste water that has passed through processes such as above-mentioned chemical coagulation, deamination, photochemical catalytic oxidation and catalyst recovery after measured, COD
CrBe 289mg/l.The results are shown in Table 2.
Table 2
Project is handled the standard of approving after the pre-treatment
COD
cr 1.394 289 800
BOD 134.3 40.7 70
SS 446.7 8.3 70
T-N 2,342.4 108 -
T-P 8,294 0.624 8
NH
3-N 1.632 49 100
Colourity 1,841 29 300
As previously mentioned, the invention provides a kind of water treatment method, utilize this method poisonous in the waste water and organism that be difficult to decompose fully can be oxidized to legal environmentally safe level.For this reason, the present invention has utilized the strong oxidation activity of OH free radical, and the OH free radical is UV lamp, TiO
2The product that reacts to each other between catalyzer and the oxidation promoter.The OH free radical can change into CO with target substance
2And H
2O, the two all is an environmental sound.In addition, utilize catalyst recovery devices of the present invention, catalyzer can recycle, and remarkable economic efficiency is provided.In addition, apparatus of the present invention are installed in only needs very little space in the water treatment system.And, owing to the photocatalysis oxidation reaction device is made of standardized unit, so easy maintenance.Compare with conventional water treatment procedure, process of the present invention can not produce a large amount of mud and secondary waste product.And water treatment system structure of the present invention was both compact, can be continuously and automatic operating, again can remote monitoring, and the operator need not very high educational background, and required number is very few.And even the flow of water seepage changes between 5 to 100%, system still can effectively operate.Another advantage of system is, because its manufacturing can be adopted component pattern, amplifies or dwindles so can carry out ratio easily according to the difference of flow.
More than be to explanation of the present invention, term wherein is illustrative rather than determinate.Can carry out multiple modification and change according to the above description.So the present invention can also otherwise implement except that above-mentioned concrete mode, these all belong within the scope of claims.
Claims (8)
1. photocatalytic reaction system for treating waste water, it comprises:
Preprocessing process, this moment is by cohesion and precipitate the solid matter of removing in the waste water, and carries out pH regulator and slough ammonia;
Mixing process, this moment through pretreated waste water in mixing pit with TiO
2Powder and reaction promoter mix;
Photo-oxidation process, introduce at least one photocatalyst reactor through above-mentioned mixed waste water from the inlet that is positioned at reactor bottom this moment, along with waste water upwards operation and circulation in the photocatalyst reactor, pollutent wherein is by photoxidation and decomposition, described photocatalyst reactor has a cylindrical shell, the turbulent flow plate that wherein has two center drillings at least, each plate is arranged along the inwall of housing according to certain interval, by the hole on these turbulent flow plates the silica tube of establishing the UV lamp in one is housed;
The catalyst recovery process, removed the waste water of pollutent at 3-5kg/cm this moment
2Pressure down by a TiO
2Catalyst recovery devices is purified water, described TiO
2Clay filter is housed in the catalyst recovery devices, and it is with TiO
2Powder is retained down and allows waste water filter, and some scraper plates also are housed, and they will be trapped in the lip-deep TiO of clay filter
2Powder scrapes off;
Catalyzer utilizes process again, the TiO that scraped this moment
2Powder is recycled and turns back in the above-mentioned mixing pit.
2. system according to claim 1, described waste water comprises the water seepage in landfill refuse place, from waste water and trotyl waste water, animal husbandry waste water and/or the contaminated underground water of electroplating workshop, paper mill, printing and dyeing mill, tannery, petroleum chemical plant etc.
3. system according to claim 1, the periphery of described silica tube and described central space is separated by 5 to 12mm.
4. system according to claim 1 also comprises N-process, and the waste water of handling through described photo-oxidation process in this process is neutralized.
5. system according to claim 1, the long 670mm of described UV lamp, the energy of the UV light of emission is 1KW, wavelength is 253.7-380nm.
6. system according to claim 1, described TiO
2Catalyst recovery system comprises:
Filter and discharge first mechanism from the waste water of purification tank for liquid waste, there is the axle of a hollow in described first mechanism, it is vertically fixed on the center at device case top, along its length, has opened many oval-shaped water vents in some predetermined positions of quill shaft 17 outer walls.On the outer wall of axle 1, several collars are installed, are utilized the described collar that several clay filters are fixed on the axle around water vent;
Be used to strike off second mechanism of clay filter surface catalyst, described second mechanism comprises a rotating cylindrical shell, it surrounds quill shaft with one heart, and in clay filter is enclosed in, fixed many scraper plates on the rotary barrel, the position at its place makes the upper and lower surface of their tight contacted filters;
Be used to rotate the 3rd mechanism of rotatable cylindrical shell, described the 3rd mechanism is made of a follower gear and a driving gear, follower gear is fixed on the top of described quill shaft with rotary way, and utilize the roof of a plurality of bolts and rotary barrel to fix, driving gear cooperates with follower gear, utilizes the turning force of motor that rotary barrel is rotated.
7. system according to claim 1, described reaction promoter is at least a following material: oxygen, H
2O
2, KBrO
3, (NH
4)
2S
2O
8And 2KHSO
3KHSO
4K
2SO
4
8. system according to claim 1, described deamination carries out behind described photo-oxidation process.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR199834180 | 1998-08-19 | ||
| KR1019980034180A KR19980082089A (en) | 1998-08-19 | 1998-08-19 | Clay filter and its manufacturing method |
| KR2019990007414U KR19990033555U (en) | 1999-05-03 | 1999-05-03 | Annulus type turbulent flow photo reactor |
| KR19997414 | 1999-05-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1245147A true CN1245147A (en) | 2000-02-23 |
Family
ID=26634037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99118053 Pending CN1245147A (en) | 1998-08-19 | 1999-08-19 | Photocatalytic reaction system for treating waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1245147A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303000C (en) * | 2004-12-29 | 2007-03-07 | 南京大学 | Method and apparatus for treating waste water by microwave photocatalysis |
| CN100406094C (en) * | 2004-07-15 | 2008-07-30 | 北京航空航天大学 | Photo-catalytic water purification post |
| CN103011501A (en) * | 2012-11-27 | 2013-04-03 | 常州大学 | High efficiency treatment method for leather industry sewage |
| CN103575671A (en) * | 2012-07-19 | 2014-02-12 | 西班牙碳化物金属股份公司 | Method for predicting the efficiency of a TiO2 photocatalyst |
| CN114516673A (en) * | 2022-01-12 | 2022-05-20 | 浙江万里学院 | Plane tube type continuous flow-photocatalytic oxidation degradation water treatment device, system and method |
-
1999
- 1999-08-19 CN CN 99118053 patent/CN1245147A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406094C (en) * | 2004-07-15 | 2008-07-30 | 北京航空航天大学 | Photo-catalytic water purification post |
| CN1303000C (en) * | 2004-12-29 | 2007-03-07 | 南京大学 | Method and apparatus for treating waste water by microwave photocatalysis |
| CN103575671A (en) * | 2012-07-19 | 2014-02-12 | 西班牙碳化物金属股份公司 | Method for predicting the efficiency of a TiO2 photocatalyst |
| CN103011501A (en) * | 2012-11-27 | 2013-04-03 | 常州大学 | High efficiency treatment method for leather industry sewage |
| CN114516673A (en) * | 2022-01-12 | 2022-05-20 | 浙江万里学院 | Plane tube type continuous flow-photocatalytic oxidation degradation water treatment device, system and method |
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