CN1508073A - Fluidized photo catalytic reactor and process for purifying waste water using same - Google Patents
Fluidized photo catalytic reactor and process for purifying waste water using same Download PDFInfo
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Abstract
The present invention relates to a fluidized photocatalytic reactor for photocatalytically-degrading organic pollutant in the water and process for treating water by utilizing said reactor. The main body of said reactor is double-pipe structure, in its inner pipe a light source is set, and the space between inner pipe and outer pie is the cavity portion of said reactor, and the upper and lower proper positions in the reactor cavity body are equipped with porous sintered baffle plates for limiting catalyst granules respectively. The lower portion of main body of said reactor is equipped with air inlet, and external side wall of main body of said reactor is equipped with inlet and outlet of reaction medium, and between them a device capable of making medium implement circulation is set.
Description
Invention field
The present invention relates to water treatment, relate in particular to a kind of fluidized reactor that utilizes light-catalyzed reaction to realize organic pollutant in the high-efficiency and continuous ground degradation water, the invention still further relates to and utilize this reactor to realize the technology of purifying liquid waste.
Background of invention
Enterprises such as oil-refining chemical give off the organic pollutant that contains in a large amount of waste water and mainly contain hydro carbons, water-soluble polar compound for example sulfide, phenol, prussiate, aminated compounds and various microorganisms etc., therefore these waste water have brought huge harm to environment undoubtedly, the improvement of pollutent are wherein also just come into one's own day by day.But the improvement method of some routines, the biological example chemical process, owing to be subjected to handling the restriction of the degree of depth, the shipwreck after feasible the processing is to satisfy the emission standard of increasingly stringent.On the other hand,, press for the discharging that reduces trade effluent, strive for purification and Reutilization of Industrial Waste Water because China's water resources is deficient relatively.So need develop a kind of new purification of waste water reuse technology.
In recent years, the technology that catalysed oxidation processes is handled waste water and waste gas at home and abroad was subjected to paying close attention to widely, and especially photocatalysis oxidation method organic pollutant in the degradation water at normal temperatures and pressures is a kind of low-cost purification of waste water new technology likely.But present photocatalysis oxidation technique also exists reaction process to be difficult to problems such as high-efficiency and continuous is carried out, catalyst separating difficulty, has restricted the industrialization promotion and the application of this method.
The device that utilizes light-catalyzed reaction to handle waste water at present is common slurry reactor, light source places liquid level appropriate location, top or reactor middle part in the operation, be the contact effect of fortifying catalytic agent with waste water, require catalyzer preferably to be dispersed in the reaction medium with fine particle, the catalyzer that uses is generally nano level titanium dioxide fine particles (generally being to tens nanometers in tens nanometers), apply stirring (being generally magnetic agitation) simultaneously, whole reaction system must realize separating of catalyzer and water by other sepn process after reaction is finished, but catalyzer is difficult to separate from the water after the processing, consequently cause secondary pollution, this method also can't make reaction carry out continuously, and processing efficiency is also very low.The work of organic pollutant is laboratory study substantially in the photocatalytic degradation water of at present existing document or patent report, does not still have the industrial application report, and one of deindustrialization factor is the continuity operation on the efficient degradation basis.Because improve light-catalyzed reaction usefulness, except improving catalyst performance, catalyzer also is the significant effects factor with the radiation modality that contacts effect and UV-light of reactant.
Employing is with the mode of catalyst loading on immobilization carrier, as be supported on sheet glass, the cement pool wall is first-class, can avoid the problem of above-mentioned catalyst separating difficulty, but except the defective of described reactor itself, the shortcoming of this loading mode being 1) catalyst preparation process is wayward; 2) catalyzer and reaction medium to contact effect bad, thereby catalytic efficiency is low; 3) the catalyst regeneration performance is not strong.
Before the present invention, do not have to be disclosed for the photo catalysis reactor of successive reaction and reported.In order to overcome above-mentioned the deficiencies in the prior art, must develop a kind of light-catalyzed reaction the high-efficiency and continuous method of handling waste water and photo catalysis reactor and the catalyzer that can realize the high-efficiency and continuous reaction of utilizing.
Summary of the invention
The invention provides a kind of fluidisation photo catalysis reactor, utilize this reactor to carry out wastewater treatment, can improve the effect that contacts of catalyzer and reaction medium, thereby realize that continuous high-efficient ground handles waste water, the purpose of organic pollutant in the reduction water.
The present invention also provides the technology of utilizing this fluidisation photo catalysis reactor to realize the continuous industry wastewater treatment.
At first,, the invention provides a kind of novel fluidisation photo catalysis reactor, mainly comprise reactor body and cycle control part present light-catalyzed reaction being handled on the basis that waster water process and reactor study, wherein:
Reactor body is a sleeve structure, outer tube wall is provided with charging bole, in the interior pipe light source is set, the space between inner and outer pipes is the cavity part of reactor, but is respectively arranged with the porous sintered baffle plate of defined catalyst particulate at the intravital suitable position up and down of this reactor cavity;
Bottom at this reactor body is provided with inlet mouth;
The reactor body outer side wall is provided with the fluid inlet and the liquid outlet of reaction medium, and the device that can make medium circulation is set between the two.
Fluidisation photo catalysis reactor of the present invention has designed the reactor body of a sleeve structure, interior pipe is used for ccontaining light source, space between the inner and outer pipes then is the cavity of reactor, catalyzer (or other additives that need) is packed into from the charging bole of outer wall, reaction medium enters through following sintering baffle plate from fluid inlet and contacts with catalyzer in the cavity, under light source irradiation, react, organic pollutant is degraded.By the air-flow (being preferably oxygen) that feeds from the bottom inlet mouth, catalyzer can fully contact with reaction medium under fluidized state, simultaneously reaction system is fully shone by light source.
Under the guidance of above-mentioned design philosophy, preferred design is: reactor body can be the coaxial sleeve structure, more preferably silica glass is made, and what be provided with in the pipe is tubular ultraviolet light source (the present invention selects high voltage mercury lamp for use), and quartz inner pipe can reduce the absorption to UV-light; Inside and outside intertubular space is a reactor volume, and the advantage of this structure design is to improve the utilization ratio of UV-light greatly.
The present invention is provided with the sintered plate that is used for defined catalyst respectively at the two sections of reactor, preferably adopts the cellular quartz sintered plate, guarantees that catalyzer at active fluidization between the sintering baffle plate up and down, also provides catalyzer to contact with the good of reaction medium.For reactor of the present invention, sintered plate and internal and external casing can be fixed as one, and also can be dismountable, or sintered plate and inner sleeve wall or overcoat tube wall fix, according to using catalyst particle size to change and select the sintering baffle plate in suitable aperture.
The cycle control of reactor of the present invention part can the realization response material circulation, speed of circulation can be controlled by recycle pump, the round-robin effect is for the water quality of controlling flow outlet and guarantees the constant of temperature of reaction.
This reactor is not provided with whipping appts especially, but utilizes the air-flow that feeds from the inlet mouth power as catalyst fluidization, so the bottom of this reactor can connect airing system or device.Consider from helping the light-catalyzed reaction process, preferably logical oxygen, the oxygen supply Controlling System can mainly be made up of oxygen storage tank (strap clamp cover), reducing valve, gas meter etc., design philosophy is: by oxygen storage tank by reducing valve through control valve, gas meter to the reactor oxygen supply, oxygen enters the reactor from the quartzy sintered plate of reactor bottom, and this airing system can adopt known device and technology fully.
Utilize fluidisation photo catalysis reactor of the present invention can realize the continuous light catalytic treatment of various waste water or waste liquid, improve the efficient of degraded organic pollutant wherein, because the fluidisation area of catalyzer only limits to by in the space that the sintering baffle plate defines up and down, overcome the problem of catalyst separating difficulty, improve the utilising efficiency of catalyzer, also improved the efficient of water treatment certainly.
On this basis, the present invention also provides the waste water treatment process that more is applicable to above-mentioned reactor: photocatalyst is packed in the reactor cavity by the charging bole of outer tube wall, pending waste water feeds the reactor cavity from fluid inlet, inlet mouth from the bottom makes granules of catalyst keep fluidized state to the reactor cavity Invivo oxyger-supply simultaneously, utilize recycle pump to make the effusive water of liquid outlet realize circular treatment, until reaching purification standard.
The most frequently used semiconductor light-catalyst is a titanium dioxide at present, for the catalyst performance that improves titanium dioxide has proposed multiple preparation and method of modifying, for example titanium dioxide made nano particle, made that film is supported on the various carriers, other component of mixing, semiconductor material are compound etc.Utilize in the waste water treatment process of reactor of the present invention and can directly use these catalyzer, need to cooperate the corresponding sintered plate in aperture certainly.The preferred technology according to the present invention, adopt particle size range at 100～400 purpose titanium dioxide granules, compound titanium dioxide one silica oxides particle or cladded type titania/silica oxide particle as photocatalyst.Titanium dioxide granule, compound titania-silica particle can pass through sol-gel-supercritical co drying process, and are prepared from through roasting, moulding and grinding; Cladded type titania/silica particle photocatalyst can be to be prepared from by hydrolysis coating method.
Zhi Bei catalyzer can have good photocatalytic activity according to the method described above, is used with reactor of the present invention, can significantly improve in the wastewater treatment degradation efficiency to organic pollutant.Concrete preparation method is as follows:
With titanium salt and silicon salt, for example butyl (tetra) titanate and tetraethoxy are raw material, C
2～C
4Small molecular alcohol is a solvent, and deionized water is a hydrolytic reagent, and acetate or ammoniacal liquor are catalyzer.At first, add the alcoholic solution of butyl (tetra) titanate then, further obtain light yellow vitreosol after the hydrolysis teos hydrolysis 5～60 minutes.The optimal conditions of this hydrolytic process is: the time of tetraethoxy prehydrolysis is 5～60 minutes, and the preferred time is 10～30 minutes; The small molecular alcohol of selecting for use is ethanol (ROH); Acetate (HAc) is catalyzer; Hydrolysis temperature is 30～36 ℃; Reaction raw materials preferably mixes mol ratio: (Ti+Si): H
2O: ROH: HAc=1: 2.5: 13: 1.8.Colloidal sol is converted into gel at ambient temperature, and gel adopts CO
2The method of supercritical drying obtains TiO
2-SiO
2The composite oxides nanometer powder, with get after nanometer powder roasting, moulding, grinding, the screening particle size range at 100～400 purpose particles as photocatalyst.Only be that raw material can obtain the pure titinium dioxide particle through processes such as hydrolysis and gels with the titanium salt, this process does not comprise tetraethoxy prehydrolysis step, and other operation is identical with condition.
Said process only illustrates, the inventor had formerly proposed a kind of preparation method of catalyst carrier for hydrgenating, China's application number: 01116022.5, though this application is to prepare the proposition that is the theme of a kind of catalyst carrier for hydrgenating, but can find that its disclosed method and product composition is identical in fact with the present invention, so the preparation method that the present invention puts down in writing this application is incorporated herein by reference.
The preferred another kind of catalyzer that uses is a cladded type titania/silica particle photocatalyst in the treatment process of the present invention, be to adopt the porous silica gel particle in titanium salt solution, to flood, and hydrolysis in the damp atmosphere atmosphere, and then dry and roasting is prepared from.Wherein, porous silica gel particle size 50～400 orders of use, specific surface area 300～500m
2/ g, pore volume 0.5～1.0ml/g, aperture 0～15nm; Steeping fluid is the alcoholic solution of titanium salt; Hydrolysis time 4～10 hours, 450～650 ℃ of roastings are 1～4 hour after dry 2～6 hours.
The specific implementation process of aforesaid method is: the ethanolic soln that is core, butyl (tetra) titanate with commercial porous silica gel particle is a steeping fluid, and the method that adopts repeatedly dipping-wet air hydrolysis-drying-roasting makes cladded type TiO at silica gel surface cladding titanium dioxide layer
2/ SiO
2Photocatalyst.The covering amount of titanium dioxide layer is controlled by the dipping number of times.Butyl (tetra) titanate and alcoholic acid mol ratio are 0.05～0.1; The dipping number of times is 1～10 time, preferred 2～5 times; Silica gel sample behind the dipping was placed in the container that the wet air atmosphere is arranged of sealing hydrolysis 4～10 hours; 120 ℃ dry 2～6 hours down, 450～650 ℃ of following roastings 1～4 hour.
In a word, the invention provides a kind of technology that is used for the fluidisation photo catalysis reactor of photocatalytic degradation water organic pollutant and utilizes this reactor enforcement water treatment, according to technical scheme of the present invention, with the waste water that contains organic pollutant is reaction mass, granules of catalyst is dispersed in the reaction mass with the fluidizing form under the effect of reaction medium oxygen, both strengthened contacting of catalyzer and reactant, avoided catalyst fines isolating difficulty from handle back water again, thereby the high-efficiency and continuous that can guarantee light-catalyzed reaction is carried out.
Description of drawings
Fig. 1 is the synoptic diagram of the specific embodiment of a kind of continuous light catalyst reaction device of the present invention.
Among the figure: sintering baffle plate, the quartzy inner sleeve of 9-under 1-water-in, 2-water outlet, 3-inlet mouth and oxygen, 4-ultraviolet lamp, 5-catalyzer material mouth, 6-recycle pump, the last sintering baffle plate of 7-, the 8-.
Specific embodiments
Beneficial effect below in conjunction with drawings and Examples are introduced enforcement of the present invention in detail and had is intended to help the reader to understand essence of the present invention and spiritual place better, but can not constitutes any qualification to the scope of the present invention.
Prepare pure TiO
2Catalyzer, condition is: 30 ℃ of hydrolysis temperatures, butyl (tetra) titanate are raw material, and ethanol is solvent, and deionized water is a hydrolytic reagent, and acetate is catalyzer, the molar ratio of various raw materials is Ti: H
2O: ROH: HAc=1: 2.5: 13: 1.8; Make the colloidal sol after the hydrolysis at room temperature be converted into gel, carry out CO
2Supercritical drying, condition be 40 ℃ of temperature, pressure 12MPa, dry 3 hours; The roasting 3 hours under 500 ℃ of air atmosphere of dried nanometer powder; Get 100～200 order particles after compressing tablet, grinding, the screening as photocatalyst.
Use reactor shown in Figure 1 to carry out wastewater treatment test, inner and outer pipes is coaxial, and interior pipe 9 is a quartz socket tube, and adopting the 500W high voltage mercury lamp is light source 4, places quartz inner pipe 9, quartzy sintering baffle plate 7 and 8 and internal and external casing be the fixed sturcture of one.Reaction system is the simulated wastewater that contains phenol 10～100mg/L, from material mouthfuls 5 catalyzer of packing into, add-on is a 1.5g/kg water, the inlet mouth 3 of reactor is connected (not shown) with the oxygen supply Controlling System of routine, oxygen in the oxygen storage tank by reducing valve through control valve and gas meter to the reactor oxygen supply, adjust oxygen gas flow rate and make granules of catalyst at active fluidization (0.05～0.15m between the sintering baffle plate 7 and 8 up and down
3/ h).Waste water feeds from water-in 1, by cavity generation DeR, flow out from water outlet 2, under the effect of recycle pump 6 at the reactor internal recycle.About 30 ℃ of temperature of reaction, the reaction times is the illumination real time.Measure the phenol content in the water.
Found that the waste water that is respectively 10mg/L, 50mg/L and 100mg/L for phenol concentration, the phenol complete degradation time was respectively 20 minutes, 60 minutes and 120 minutes.
Titanium dioxide that employing embodiment 1 makes and identical reaction conditions, contrast is purchased the photocatalysis performance of sharp attitude type titanium dioxide.
The titanium dioxide that makes according to embodiment 1 is sharp attitude crystal formation after 500 ℃ of roastings, specific surface area is 83m
2/ g, and the specific surface area of the sharp attitude type of commodity titanium dioxide is 13m
2/ g.The starting point concentration of phenol is 50mg/L in the simulated wastewater, it is 60 minutes and commodity titanium dioxide makes the phenol complete degradation time is 80 minutes that the titanium dioxide that the present invention makes makes in the water phenol complete degradation time, shows that the titanium dioxide that method provided by the invention is prepared has photocatalysis performance preferably.
According to the titanium dioxide of embodiment 1 preparation, but adopted in 650 ℃ of air atmosphere roasting 3 hours, as catalyzer and according to the reaction conditions identical with embodiment 1; The commodity titanium deoxide catalyst of selecting for use embodiment 2 to mention and adopting, the fluidisation photo catalysis reactor of contrast the present invention design and the photochemical catalysis effect of common slurry reactor.
The fluidized reactor of the volume of common slurry reactor, the irradiated area of UV-light and embodiment 1 is suitable substantially, and light source places liquid level top 2 centimeters, and reaction system adopts the magnetic alr mode fully to stir contacting with fortifying catalytic agent and reactant.Reaction system is an actual industrial waste water, its COD
CrValue is 531mg/L.Titanium dioxide with above-mentioned preparation is catalyzer, the COD after fluidized reactor and slurry reactor degraded in 180 minutes
CrValue descends 79.9% and 63.0% respectively; Adopting commodity titanium dioxide is catalyzer, COD under the same conditions
CrValue descends 60.1% and 36.7% respectively.Show that the more common slurry reactor of reactor that the present invention designs has the effect of organic pollutant degradation in the better promotion waste water.
Three kinds of photocatalysts:
1, the pure titinium dioxide that makes of embodiment 1.
2, the Ti/Si atomic ratio is 1: 1 TiO
2-SiO
2Composite oxides.
3, the Ti/Si atomic ratio is 4: 1 TiO
2-SiO
2Composite oxides.
Comprise at first prehydrolysis tetraethoxy among the preparation method of the two kinds of composite oxides in back, hydrolysis time 10～15 minutes adds the butyl (tetra) titanate hydrolysis then, and all the other operations are identical with embodiment 1.
These three kinds of catalyzer are respectively through 500 ℃ and 650 ℃ of roastings 3 hours, and FCC reactor by embodiment 1 and common slurry reactor are to COD respectively
CrValue is that the trade effluent of 531 mg/L carries out catalyzed degradation, obtains result as shown in the table.From table, can see that composite oxides have better photocatalysis performance than pure titinium dioxide, maturing temperature is brought up to 650 ℃, titanium dioxide and TiO from 500 ℃
2-SiO
2The photocatalysis performance of composite oxides all is improved to some extent.Adopt identical catalyzer, the COD of fluidized reactor
CrDegradation effect obviously is better than slurry reactor.
| Catalyzer | Maturing temperature, ℃ | 180min degraded back COD CrValue, mg/L | |
| FCC reactor | Slurry formula catalyticreactor | ||
| TiO 2， | 500 | 106 | 196 |
| 650 | 101 | 194 | |
| TiO 2-SiO 2(Ti/Si＝1) | 500 | 312 | 382 |
| 650 | 90 | 256 | |
| TiO 2-SiO 2(Ti/Si＝4) | 500 | 164 | 294 |
| 650 | 75 | 195 | |
The cladded type activity of such catalysts relatively.
The preparation method: the ethanolic soln that is core, butyl (tetra) titanate with the commercial porous silica gel particle of 100～200 purposes is a steeping fluid, butyl (tetra) titanate and alcoholic acid mol ratio are 0.085, adopt 1 time, 2 times and 3 times dipping respectively, the silica gel behind the dipping was placed in the container that the wet air atmosphere is arranged of sealing hydrolysis 4 hours; 120 ℃ dry 3 hours down, 650 ℃ of following roastings 2 hours make cladded type TiO
2/ SiO
2Photocatalyst.
With the titanium dioxide of embodiment 1, above-mentioned cladded type TiO
2/ SiO
2(n) (n be dipping number of times) 650 ℃ of roastings 3 hours in air atmosphere.Adopt the fluidisation photo catalysis reactor (as described in Example 1) of the present invention's design, catalyzer add-on 1.5g/kg water, reaction system is an actual industrial waste water, its COD
CrValue is 531mg/L, and the gained result is as shown in the table.Data are seen TiO from table
2/ SiO
2The cladded type catalyzer is the same with titanium dioxide to have the performance that reduces the COD value preferably, the preparation cladded type TiO that this explanation the present invention proposes
2/ SiO
2The method of photocatalyst, not only simple, the easy handling of process, employing half inorganic (inorganic silica gel particle) preparation route cost are lower, and prepared catalyzer has good photocatalysis performance, conveniently are used for the fluidisation photo catalysis reactor that the present invention proposes again.
| Catalyzer | Specific surface area (m 2/g) | Pore volume (ml/g) | TiO 2Content (%) | 180min degraded back COD (mg/L) |
| TiO 2 | 94.5 | 0.33 | 100 | 107 |
| TiO 2/SiO 2(1) | 410 | 0.83 | 10.8 | 128 |
| TiO 2/SiO 2(2) | 385 | 0.72 | 20.2 | 108 |
| TiO 2/SiO 2(3) | 357 | 0.64 | 26.8 | 139 |
Claims (10)
1, a kind of fluidisation photo catalysis reactor, comprise reactor body and cycle control part, wherein: reactor body is a sleeve structure, outer tube wall is provided with charging bole, in the interior pipe light source is set, space between inner and outer pipes is the cavity part of reactor, but is respectively arranged with the porous sintered baffle plate of defined catalyst particulate in the intravital appropriate location up and down of this reactor cavity;
Bottom at this reactor body is provided with inlet mouth;
The reactor body outer side wall is provided with the fluid inlet and the liquid outlet of reaction medium, and the device that can make medium circulation is set between the two.
2, the described fluidisation photo catalysis reactor of claim 1, wherein, reactor body is the coaxial sleeve structure.
3, claim 1 or 2 described fluidisation photo catalysis reactors, wherein, the interior pipe of reactor body is that silica glass is made.
4, the described fluidisation photo catalysis reactor of claim 1, wherein, what be provided with in the interior pipe is the tubular ultraviolet light source.
5, the described fluidisation photo catalysis reactor of claim 1, wherein, the sintering baffle plate between inner and outer pipes is the cellular quartz sintered plate.
6, utilize light-catalyzed reaction to handle the processing method of waste water, utilize each described fluidisation photo catalysis reactor of claim 1～5 to realize, photocatalyst is packed in the reactor cavity by the charging bole of outer tube wall, pending waste water feeds the reactor cavity from fluid inlet, inlet mouth from the bottom makes granules of catalyst keep fluidized state to the reactor cavity Invivo oxyger-supply simultaneously, utilize recycle pump to make the effusive water of liquid outlet realize circulation, until reaching purification standard.
7, the described processing method of claim 6, wherein, employed photocatalyst is titanium dioxide granule, compound titania-silica particle or cladded type titania/silica particle, particle size range is at 100～400 orders.
8, the described processing method of claim 7, wherein, described titanium dioxide granule or compound titania-silica particle photocatalyst pass through sol-gel-supercritical co drying process, and are prepared from through roasting, moulding and grinding.
9, the described processing method of claim 7, wherein, described cladded type titania/silica particle photocatalyst is to adopt the porous silica gel particle to flood in titanium salt solution, hydrolysis in the damp atmosphere atmosphere, and then dry and roasting is prepared from.
10, the described processing method of claim 9, wherein, porous silica gel particle size 50～400 orders of use, specific surface area 300～500m
2/ g, pore volume 0.5～1.0ml/g, aperture 0～15nm; Steeping fluid is the alcoholic solution of titanium salt; Hydrolysis time 4～10 hours, 450～650 ℃ of roastings are 1～4 hour after dry 2～6 hours.
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| CN110330073A (en) * | 2019-08-13 | 2019-10-15 | 陕西师范大学 | A kind of organic wastewater degraded catalytic separation device and method |
| CN110330073B (en) * | 2019-08-13 | 2024-06-04 | 陕西师范大学 | Organic wastewater degradation catalytic separation device and method |
| CN113683153A (en) * | 2021-08-06 | 2021-11-23 | 沈阳工业大学 | Device for treating waste water by utilizing photocatalytic reaction |
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