CN100371063C - Labyrinth type current-crossing and bubbling photocatalytic reaction device and method for treating organic waste water thereby - Google Patents
Labyrinth type current-crossing and bubbling photocatalytic reaction device and method for treating organic waste water thereby Download PDFInfo
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- CN100371063C CN100371063C CNB2006100126221A CN200610012622A CN100371063C CN 100371063 C CN100371063 C CN 100371063C CN B2006100126221 A CNB2006100126221 A CN B2006100126221A CN 200610012622 A CN200610012622 A CN 200610012622A CN 100371063 C CN100371063 C CN 100371063C
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Abstract
The present invention relates to a labyrinth type flow crossing and bubbling photocatalysis reaction device and a method for treating organic waste water thereof. The present invention is characterized in that parallel plates for deflection of jet are vertically arranged in the reaction device for forming a liquid phase labyrinth type passage; oxygen containing gas enters a reaction zone through the bottom of the reaction device, and the reaction zone are upwards protruded through a distributing plate; the organic waste water flow in from a liquid inlet pipe on the side surface of the reaction device above the distributing plate, flows in the labyrinth type reaction zone along the clearance of the plates for deflection of jet and contacts rising gas bubbles in a flow crossing mode; granular photocatalyst is suspended and dispersed in a gas-liquid mixing phase. A gas phase, a liquid phase and a solid phase have photocatalysis reactions under the irradiation of outer parallel ultraviolet sources above the reaction device, and organic substances are degraded in a photocatalysis mode; the discharged water of the reaction device is separated by an outer solid-liquid separator and has a photocatalysis reaction in a circulatory and continuous mode under the action of a pump. The present invention has the advantages of simple structure, convenient operation, long dwell time for liquid, sufficient contact of the liquid and the solid phases, high mass transfer efficiency, high photocatalysis reaction efficiency, no limitation from light sources on the design enlargement of the reaction device and easy realization for industrial application.
Description
Technical field
The present invention relates to a kind of high efficiency photocatalysis reaction unit and method for processing organic wastewater thereof, especially utilize labyrinth type cross-flow bubbling photocatalytic reaction device and method for processing organic wastewater thereof
Technical background
Photocatalysis oxidation technique is to utilize ultraviolet light or black light activating semiconductor (to use TiO usually
2) photohole on the valence band, in water, produce the extremely strong hydroxyl free radical of oxidability, make and be difficult to the organic pollution permineralization of degrading in the water, degradation process can be carried out and agent non-selectivity almost at normal temperatures and pressures, this method needn't be added chemical reagent in addition, non-secondary pollution is so become current water treatment technology research forward position at home and abroad and exploitation focus.
Reactor, light source and photochemical catalyst are the three elements of realizing photocatalytic process.Powder suspension attitude semiconductor light-catalyst exists and separates and the recovery difficulty, therefore immobilization light-catalyzed reaction system more and more comes into one's own, and preparation high activity and high stability catalyst and exploitation mass-transfer efficiency height and the good novel Photoreactor of separating power are the keys of photocatalysis technology practicability.Compare with general reactor, the design of photo catalysis reactor except to consider to mix with problems such as the installation of the flow condition of the contacting of mass transport process, reactant and catalyst, fluid, kinetics, catalyst and temperature controlling, also must consider configured light sources, the uniformity of light radiation, illumination, high saturating property and light utilization efficiency etc.The researcher generally adopts the annular fluidized bed reactor of built-in light source to realize this purpose at present, but this class reactor need be provided with the inner cooling system heat radiation, when amplifying, design must consider the combination of light source (uviol lamp) and cooling system, complex structure and reduced the dischargeable capacity of reactor, luminous energy need pass through the multilayer coolant jacket could arrive catalyst surface, optical efficiency does not obtain maximum performance yet, sees that patent publication No. is CN1261056; Also have in addition photochemical catalyst is fixed on the plate shaped reactor that reactor bottom utilizes external light source, wastewater treatment capacity is little, the efficiency of light energy utilization is low, reactor efficiency is not high and catalyst is difficult to problems such as reclaiming but this reactor exists, and sees that patent publication No. is CN1431155 and CN1508073.
Summary of the invention
The purpose of this invention is to provide a kind of labyrinth type cross-flow bubbling photocatalytic reaction device, be characterized in simple in structure, easy to operate, can utilize the external parallel radiating light source, light-catalyzed reaction efficient height and the easy recovery of catalyst use again, wastewater treatment ability and the control of degraded depth-adjustment, but not only intermittently operated but also continuously-running.Another object of the present invention provides utilizes this labyrinth type cross-flow bubbling photocatalytic reaction device continuous degradation to contain the method for treating water of organic pollution waste water.
Labyrinth type cross-flow bubbling photocatalytic reaction device of the present invention comprises photo catalysis reactor main body, outside solid-liquid separator and the circulatory system, its architectural feature is in reactor: the bottom is provided with gas distribution grid, is vertically installed with parallel deflection plate thereon and constitutes the liquid phase labyrinth passage; The bottom is provided with the reactor air inlet; The sidewall of reactor of gas distribution grid top is provided with reactor inlet and reactor overflow mouth; Above reactor, be provided with source of parallel light.
The cross section of above-mentioned described reactor is circular cross section or rectangular cross section; Described parallel deflection plate is three or more parallel deflection plate; Described gas distribution grid is double-layer porous air distribution plate or sintered plate, and its aperture＜0.5mm, percent opening are 0.5%～5.0%; Described source of parallel light is ultraviolet light or black light; Described solid-liquid separator is a conical structure, and its top is provided with separator charging aperture and separator delivery port, and the bottom is provided with the separator discharge gate, and its separator charging aperture is communicated with the reactor overflow mouth.
The present invention is used for the method that labyrinth type cross-flow bubbling photocatalytic reaction device is handled organic wastewater, this method is to be that the particle photochemical catalyst of 0.3mm～0.8mm adds in the reactor with particle diameter, pending organic wastewater feeds in the labyrinth type reaction zone from the reactor inlet, feeds oxygen-containing gas and upwards blasts reaction zone by gas distribution grid from the reactor air inlet simultaneously; Being cross-flow along the liquid of deflection plate Clearance Flow with rising bubble contacts, particle photochemical catalyst suspended dispersed in gas-liquid mixed mutually in, under the irradiation of parallel ultraviolet light source, carry out light-catalyzed reaction, organic matter is by catalytic degradation, and water outlet can directly be discharged or in circulation metering water pump circulation Returning reactor through solid-liquid separator, circulating water chennel are up to standard.
Wherein: the particle photochemical catalyst that separates through solid-liquid separator utilizes density contrast to enter automatically the back with water inlet line of reactor from the separator discharge gate bottom it, is recycled in the reactor with the organic wastewater by circulation metering water pump to recycle; Wherein the particle photochemical catalyst that separates through solid-liquid separator is discharged from the separator discharge gate of its bottom and is carried out the regeneration of catalyst; Wherein the water inlet flow velocity of conditioned reaction device realize the particle photochemical catalyst in reactor the time of staying and water outlet in the drag-out of catalyst.
The present invention is by advantage and the good effect of implementing technique scheme: the effect that reactor bottom feeds oxygen-containing gas is to provide light-catalyzed reaction required oxygen to system on the one hand; Provide energy on the other hand and make particle photochemical catalyst suspended dispersed in reactor content, gas phase, liquid phase are fluidized state with the solid phase three-phase and fully contact; The existence of bubble simultaneously can provide than high voidage be convenient to reactor top incident light go deep in the reactor with the particle photochemical catalyst fully, even contact, thereby whole reaction system has higher light-catalyzed reaction efficient.
Innovation part of the present invention is that organic wastewater flows with plug flow mode in the photo catalysis reactor in labyrinth passage, increased the time of staying of liquid phase in reactor; Organic wastewater and rising bubble are cross-flow passes, and gas phase, liquid phase and solid phase three-phase fully mix the advantage that has the fluidization reaction concurrently; The time of staying of particle photochemical catalyst and drag-out can be controlled by regulating flow of inlet water in the reactor, thus the reproduction speed of controlled controlling catalyst; By the quantity that increases labyrinth passage and the disposal ability and the degraded degree of depth that length can improve organic wastewater.
Photocatalytic reaction device of the present invention can utilize sources of parallel light such as solar energy, need not cooling system, and luminous energy can directly enter and contact with photochemical catalyst in the three-phase mixed liquor, has improved the effective rate of utilization of light.
The particle photochemical catalyst particle diameter that the present invention adopts is at 0.3mm～0.8mm, and the distribution grid aperture is less than 0.5mm.Less than 0.5mm, in the middle of can adopting, gas distribution grid accompanies the double-deck air distribution plate or the porous sintered plate of 100 order nylon wires or woven wire as grain diameter.
The said particle photochemical catalyst of the present invention can directly adopt metal oxide semiconductor (to be generally TiO
2) particle, also can adopt the loaded catalyst particle, carrier commonly used has particles such as active carbon, silica gel, quartz sand and molecular sieve, can adopt methods such as sol-gel process or powder attachment method to make the surface filming of metal oxide semiconductor at carrier, makes loaded catalyst.
The size of reactor should be according to material treating capacity design among the present invention, to guarantee in the reactor gas, liquid, solid three-phase good mixing and to separate.
In sum, the present invention is with the innovation part by the advantage of implementing technique scheme: (1) labyrinth type cross-flow bubbling photocatalytic reaction device is simple in structure, easy to operate, and inner cooling system need not be set; (2) can utilize the external parallel radiating light source, efficiency of light energy utilization height; (3) organic wastewater flows with plug flow mode in reactor, and the liquid phase time of staying is long, wastewater treatment ability and the control of degraded depth-adjustment; (4) gas, liquid two-phase cross-flow passes, gas phase, liquid phase and solid phase three-phase are fluidized state, light-catalyzed reaction efficient height; (5) photochemical catalyst in the reactor water outlet separates reusable edible, also recyclable regeneration through outside solid-liquid separator; (6) can regulate the time of staying of particle photochemical catalyst in reactor by flow of inlet water; (7) but light-catalyzed reaction system gap operating, also continuously-running; (8) reactor can design amplification separately, is easy to realize commercial Application.
Description of drawings
Fig. 1 is labyrinth type cross-flow bubbling photocatalytic reaction device of the present invention and method of wastewater treatment flow chart thereof
Fig. 2 is a photo catalysis reactor rectangular body labyrinth passage plan structure schematic diagram of the present invention
Fig. 3 is a photo catalysis reactor circular body labyrinth passage plan structure schematic diagram of the present invention
Among the figure: 1: reactor 2: gas distribution grid 3: parallel deflection plate 4: reactor inlet 5: reactor overflow mouth 6: reactor air inlet 7: solid-liquid separator 8: separator charging aperture 9: separator delivery port 10: separator discharge 11: circulating water chennel 12: source of parallel light 13: circulation metering water pump 14: air pump 15: gas flowmeter 16,17,18,19,20: valve
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing and instantiation
Embodiment one
Apparatus of the present invention mainly are made of labyrinth type cross-flow bubbling photo catalysis reactor 1 main body, outside solid-liquid separator 7, the circulatory system and reactor 1 top source of parallel light 12.
Reactor 1 body cross-section of the present invention is circle or rectangle, and porous gas distribution grid 2 is installed in the reactor 1, and distribution grid 2 belows are the gas section of distribution in advance, and the top is a reaction zone.Above reactor 1 inner distribution grid 2, be arranged vertically the parallel deflection plate 3 of polylith and form the liquid phase labyrinth passage.Parallel deflection plate 3 is rectangular, and the lower end is fixed on the parallel distribution grid 2, and parallel deflection plate 3 sides, one end and reactor 1 wall connect fixing, and the other end keeps certain distance formation liquid channel, adjacent two parallel deflection plate 3 interlaced arrangement with reactor 1 wall.Reactor inlet 4 and reactor overflow mouth 5 are arranged on the sidewall of parallel distribution grid 2 top reactors 1, and reactor overflow mouth 5 upright positions are lower than the height of parallel deflection plate 3; The bottom of reactor air inlet 6 reactor 1 below parallel distribution grid 2.Parallel distribution grid 2 is aperture＜0.5mm in the reactor 1, percent opening is double-layer porous air distribution plate in 0.5%～5.0% left and right sides or sintered plate, its effect is gas evenly to be distributed produce small rising bubble stream in reaction zone, is on the other hand to prevent the photocatalyst granular gas section of distribution in advance of bleeding.Outside solid-liquid separator 7 is a conical structure, top is provided with separator charging aperture 8 and separator delivery port 9, the bottom is provided with solid particle separator discharge gate 10, wherein separator charging aperture 8 is communicated with reactor delivery port 9, solid particle separator discharge gate 10 can be communicated with reactor inlet 4, also can set out a mouthful direct discharge in addition.The required light source of light-catalyzed reaction is provided with separately, uviol lamp or near ultraviolet lamp can be set above reactor 1 produce source of parallel light 12, also can utilize the ultraviolet light part in the solar energy.
Embodiment two
A kind ofly be used for labyrinth type cross-flow bubbling photocatalytic reaction device to handle the method for organic wastewater as follows:
(1) gap cycling photocatalytic degradation phenolic waste water
Shown in Fig. 1, be the supported titanium of carrier with granular activated carbon
2(German Degussa P25 adopts infusion process that it is carried on the seed activity carbon surface and makes TiO
2Loaded film, TiO
2The active component consumption is about the 0.2%wt of pending liquid consumption) photochemical catalyst puts into the circular reactor 1 that dischargeable capacity is 0.8L, adding initial phenol concentration in circulating water chennel 11 is the 1000mL simulative organic wastewater of 20mg/L, adopt the 375W high-pressure sodium lamp to produce source of parallel light through the lampshade reflection, the liquid level place light intensity of reactor 1 is 8mW/cm
2 Open valve 18, above-mentioned phenolic waste water is continuously pumped into reactor 1 with the flow of 400mL/min through reactor inlet 4 by circulation metering water pump 13, air enters reactor 1 with the flow of 8L/min from reactor bottom air inlet 6 through gas flowmeter 15 by air pump 14, after disperseing, the micropore of gas distribution grid 2 enters reaction zone, catalyst is carried secretly by bubble and is upwards suspended, and makes gas-liquid-solid three-phase be the fluidization reaction system.Phenol is degraded into CO by light-catalyzed reaction
2And H
2O, gas discharge from reactor 1 top and enter atmosphere; Liquid phase material is expelled to outside solid-liquid separator 7 from reactor overflow mouth 5, continues degraded through circulating water chennel 11, circulation metering water pump 13 Returning reactors 1 again; Externally the particle photochemical catalyst in the solid-liquid separator 7 enters back with water inlet line with water inlet Returning reactor 1 through separator bottom discharging mouth 10, valve 16.Behind the whole system reaction 2h in the water phenol degraded fully.
(2) move the photocatalytic degradation phenolic waste water continuously
With granular activated carbon among the embodiment 1 is carrier TiO
2Photochemical catalyst 6g puts into reactor 1, still adopts the 375W high-pressure sodium lamp as light source.Valve-off 18, open valve 19, the simulative organic wastewater that with initial phenol concentration is 50mg/L is continuously pumped into reactor 1 by circulation metering water pump 13, the liquid phase time of staying remained on about 2 hours in the reactor 1, and air enters reactor 1 through gas flowmeter 15 with the flow of 12L/min by air pump 14.Organic wastewater carries out being expelled to outside solid-liquid separator 7 continuously after the light-catalyzed reaction in reactor 1, is collected in the circulating water chennel 11 then or directly discharging, and the phenol clearance reaches about 60% in the water outlet.Particle photochemical catalyst in the outside solid-liquid separator 7 is with fill cycle Returning reactor 1.
(3) the semicontinuous photocatalytic degradation methyl orange aqueous solution of half gap
With molecular sieve is the supported titanium of carrier
2(Prepared by Sol Gel Method TiO
2, adopt infusion process that it is carried on the molecular sieve surface and make TiO
2Loaded film) photochemical catalyst 20g puts into the rectangular reactor 1 that dischargeable capacity is 2L, and adopting the 375W high-pressure sodium lamp is light source.Elder generation's valve-off 18, open valve 19, the simulative organic wastewater that with the methyl orange initial concentration is 40mg/L pumps into reactor 1 by circulation metering water pump 13, and the liquid phase time of staying remained on about 2 hours, and air enters reactor with the flow of 8L/min from reactor 1 bottom by air pump 14.Methyl orange enters circulating water chennel 11 again through being expelled to outside solid-liquid separator 7 after the light-catalyzed reaction degraded, opens this moment and control valve 18 makes and handles water in the circulating water chennel and come water to mix in 1: 1 ratio with valve 19 to degrade through 1 continuation of circulation metering water pump 13 Returning reactors again; The particle photochemical catalyst that separates through outside solid-liquid separator 7 enters back with water inlet line with water inlet Returning reactor 1 through separator bottom discharging mouth 10.The water outlet of circulating water chennel overfall.
Claims (10)
1. labyrinth type cross-flow bubbling photocatalytic reaction device, comprise photo catalysis reactor main body, outside solid-liquid separator and the circulatory system, it is characterized in that in the reactor (1): the bottom is provided with gas distribution grid (2), is vertically installed with parallel deflection plate (3) and constitutes the liquid phase labyrinth passage on gas distribution grid (2); The bottom is provided with reactor air inlet (6); The sidewall of reactor of gas distribution grid (2) top is provided with reactor inlet (4) and reactor overflow mouth (5); Be provided with source of parallel light (12) in the top of reactor (1).
2. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 1, the cross section that it is characterized in that reactor (1) is circular cross section or rectangular cross section.
3. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 1 is characterized in that parallel deflection plate (3) is three or more parallel deflection plate (3).
4. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 1 is characterized in that gas distribution grid (2) is aperture＜0.5mm, and percent opening is 0.5%～5.0% double-layer porous air distribution plate or sintered plate.
5. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 1 is characterized in that source of parallel light (12) is ultraviolet light or black light.
6. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 1, it is characterized in that solid-liquid separator (7) is a conical structure, solid-liquid separator (7) top is provided with separator charging aperture (8) and separator delivery port (9), the bottom is provided with separator discharge gate (10), and the charging aperture (8) of solid-liquid separator (7) is communicated with reactor overflow mouth (5).
7. method of using the described labyrinth type cross-flow of claim 1 bubbling photocatalytic reaction device to handle organic wastewater, it is characterized in that this method is is that the particle photochemical catalyst of 0.3mm～0.8mm adds in the reactor (1) with particle diameter, pending organic wastewater feeds in the labyrinth type reaction zone from reactor inlet (4), feeds oxygen-containing gas and upwards blasts reaction zone by gas distribution grid (2) from reactor air inlet (6) simultaneously; Being cross-flow along the liquid of deflection plate Clearance Flow with rising bubble contacts, particle photochemical catalyst suspended dispersed in gas-liquid mixed mutually in, under the irradiation of parallel ultraviolet (12) light source, carry out light-catalyzed reaction, organic matter is by catalytic degradation, and water outlet can directly be discharged or in circulation metering water pump (13) circulation Returning reactor (1) through solid-liquid separator (7), circulating water chennel (11) are up to standard.
8. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 7 is handled the method for organic wastewater, it is characterized in that the particle photochemical catalyst that separates through solid-liquid separator (7) utilizes density contrast to enter automatically the back with water inlet line of reactor (1) from the separator discharge gate (10) bottom it, is recycled to recirculation in the reactor (1) with the organic wastewater by circulation metering water pump (13).
9. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 7 is handled the method for organic wastewater, it is characterized in that the particle photochemical catalyst that separates through solid-liquid separator (7) is discharged from the separator discharge gate (10) of its bottom to carry out the regeneration of catalyst.
10. labyrinth type cross-flow bubbling photocatalytic reaction device as claimed in claim 7 is handled the method for organic wastewater, the water inlet flow velocity that it is characterized in that conditioned reaction device (1) realize the particle photochemical catalyst in reactor (1) the time of staying and water outlet in the drag-out of catalyst.
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| CN100371063C true CN100371063C (en) | 2008-02-27 |
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