CN101863548A - Device and method for removing organics from water - Google Patents
Device and method for removing organics from water Download PDFInfo
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- CN101863548A CN101863548A CN 201010227260 CN201010227260A CN101863548A CN 101863548 A CN101863548 A CN 101863548A CN 201010227260 CN201010227260 CN 201010227260 CN 201010227260 A CN201010227260 A CN 201010227260A CN 101863548 A CN101863548 A CN 101863548A
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Abstract
The invention discloses a device and a method for removing organics from water, which remove organic micro-pollutants from a water source through electrochemical light-catalyzed synergic enhancement. In the device, an electrochemical component and a light-catalyze component are arranged in the same reactor to synergically remove the organics from water, wherein the light-catalyze component is arranged in the reactor and comprises a supported catalyst and a light-catalyzed excitation light source which is used for exciting the supported catalyst; the electrochemical component comprises a cathode, an anode and a power supply connecting the anode and the cathode; the anode and the cathode are oppositely arranged on the two sides of the light-catalyzed excitation light source; and the supported catalyst is arranged on the other two sides of the light-catalyzed excitation light source or around the light-catalyzed excitation light source. The device brings synergic enhancement while playing a role in photo-catalysis and electrochemical action respectively. And the device improves the treatment efficiency of the organic micro-pollutants in drinking water.
Description
Technical field
The present invention relates to the Application Areas of water technology, relate in particular to the organic method and apparatus of little pollution in a kind of removal water.
Background technology
Sustainable development along with world economy, especially organic chemical industry, petrochemical complex, medicine, agricultural chemicals and agrochemical industry increases rapidly, organic compound output and kind increase gradually, the below standard discharging of various sewage, earth surface water source even underground water source are all produced great harm, and human " Source of life " is subjected to serious day by day threat.According to China national environmental aspect communique in 2005, in 411 surface water monitoring sections of state environmental monitoring net seven big water systems, account for 59% below the III class water quality, main contamination index is BOD
5, COD
MnWith indexs such as petroleum-type.Little pollution organism in the water body is indirect and hidden to the harm of human body.A lot of material concentrations are low and do not have acute toxicity, but that long-term drinking may produce is carcinogenic, teratogenesis, mutagenesis.Some organism has lipotropy, can put aside in human body, causes long-term effect.In addition, also natural the or artificial organism in the water may be changed into disinfection byproduct (DBP) in the water treatment procedure.American National Environmental Protection Administration is a priority pollutant based on pollutent toxicity, 129 kinds of materials of degraded possibility regulation." drinking water sanitary standard " of China (GB5749-2006) in nearly 53 of organic indexs, and in to single class material strict regulation first with total organic carbon TOC as reference index (the recommendation index is 5mg/L).Little pollution organism has caused extensive attention in the waterhead area water body, and the drinking water safety situation allows of no optimist.
In the face of little pollution organism, conventional coagulation-precipitation-filtration combination process is unable to do what one wishes, and some novel process are just gradually adopted.Activated carbon and relevant improving technology also are short of to some extent for dissolved organic carbon clearance in the water; Pollutent in the middle of the ozone technology oxidation of organic compounds is easy to generate simultaneously, and invalid to partial organic substances; It is strong that membrane filtration technique is removed ability, but other technology production cost is high relatively, is unfavorable for that the economically underdeveloped area promotes on a large scale.Biological process utilizes the microbial metabolism ability to consume organism, and water purification is with low cost, but is subjected to the biological action capabilities limits, and is not good for the difficult for biological degradation pollutant removal.
By comparison, electrochemical process is utilized the redox reaction partner of electronics as cleaning, directly or indirectly carries out the conversion between chemical substance, and need not a large amount of oxygenants or reductive agent, and not influenced by initial chroma, be a kind of method of comparatively environmental protection.The electrochemical degradation organism mainly is divided into the pole plate direct oxidation and produces hydroxyl radical free radical (OH) indirect oxidation, and the indirect oxidation ability is far above direct oxidation.When voltage is higher than the electrode oxygen evolution potential when electrochemical reaction, produce the side reaction that oxygen also takes place to produce hydroxyl radical free radical simultaneously, it is strong that voltage surpasses the big more side reaction Shaoxing opera of oxygen evolution potential, and degraded equivalent organism current consumption is big more, and electrochemical efficiency is low more.During the electrochemical treatment tap water, because conducting material is few in the solution, specific conductivity is low, so required virtual voltage can be very high when wanting to reach the required current value of efficient purification, so the electrochemistry momentary efficiency is extremely low.When handling micro-polluted drinking water,, make electrochemical efficiency extremely low because electroconductibility is relatively poor in the solution.At document: Li etc., Journal of Hazardous Materials, Volume 162, among the pp 455-462, disclose and utilized organic research in the electrochemical process oxidative degradation water, but still need add a large amount of NaCl ionogen, and the water outlet chlorine ion concentration exceeds standard simultaneously and easily generates degradation by-products, and this has limited the practicability of electrochemical process.
And photocatalytic oxidation, especially optically catalytic TiO 2 technology are with low cost, oxidation capacity is strong, and not limited by water body electroconductibility.But its light induced electron-hole is fast to recombination rate, and the shortcoming that quantum yield is not high restricts its large-scale application.And it is bigger that it is influenced by initial chroma.Simultaneously, when micro-polluted water colourity was higher, excitation line is decay in a large number before arriving catalyst surface, causes photocatalytic activity to give full play to.
The technology and the device that utilize UV-light photodissociation and electrochemical electrolysis effect synergistic purification tap water are disclosed among the patent document CN 1477061A, it adopts ultraviolet photolysis and electrochemical degradation process integration, organism absorbs the UV-light energy and is decomposed into small-particle, but ultraviolet photolysis can't thoroughly remove organism, also needs electrochemistry to produce the hydroxyl radical free radical oxidation and finally removes organism.Photodissociation can make electrochemical oxidation speed up, and degradation rate improves, but it can't improve the productive rate of hydroxyl radical free radical, can't solve at all that the electrochemistry momentary efficiency that the tap water poorly conductive causes is low, the shortcoming of detergent power difference.
Summary of the invention
Technical problem to be solved by this invention is to propose organic device and method in a kind of removal water, when solving single electrochemical method advanced treatment micro-polluted drinking water current efficiency lower, need to add a large amount of electrolytical defectives and the low shortcoming of single photocatalysis method active substance productive rate.
For achieving the above object, the present invention proposes organic device in a kind of removal water, and wherein, electrochemical assembly and photochemical catalysis assembly are arranged in the same reactor, the collaborative organism of removing in the water.
Wherein, described photochemical catalysis assembly is arranged in the described reactor, described photochemical catalysis assembly comprises loaded catalyst and is used to excite the photochemical catalysis excitation light source of described loaded catalyst, described electrochemical assembly comprises negative electrode, anode and connects the power supply of anode and negative electrode, described anode and described negative electrode are oppositely arranged in the both sides of described photochemical catalysis excitation light source, and described loaded catalyst is arranged at the other both sides of described photochemical catalysis excitation light source or centers on the setting of described photochemical catalysis excitation light source.
Wherein, described loaded catalyst is a carried titanium dioxide film on tabular, the thread or mesh carrier that is formed by glass, pottery, titanium plate, PVC or activated carbon fiber.
Wherein, described anode is selected graphite, Pt, Ti, RuO for use
2, IrO
2Or RuO
2-Pt, described negative electrode is selected Ti, Pt, Fe, Al, Cu, stainless steel for use.
Wherein, the light source selected for use of described photochemical catalysis excitation light source is the following ultraviolet source of main emission wavelength 365nm.
Wherein, this device also comprises a supply flume, a water circulating pump, described reactor below has a water-in, and the top has a water outlet, described water-in and described water outlet are communicated with described supply flume by exterior line, and described water circulating pump is connected between described water-in and the described supply flume, and described reactor can be cylindrical or square list groove reactor or any tank.
For achieving the above object, the present invention also proposes organic method in a kind of removal water, wherein, the electrochemical assembly and the photochemical catalysis assembly that are arranged in the same reactor carry out electrochemical process and photocatalytic process simultaneously, bring into play the collaborative simultaneously organism of removing in the water that strengthens of effect separately by electrochemical assembly and photochemical catalysis assembly.
Wherein, this method improves make a return journey organism in dewatering of the hydroxyl radical free radical that produces in electrochemical process and the photocatalytic process by collaborative enhancing of electrochemical process and photocatalytic process.
Wherein, described photochemical catalysis assembly comprises loaded catalyst and is used to excite the photochemical catalysis excitation light source of described loaded catalyst that described loaded catalyst is for adopting powder sintering, collosol and gel or the liquid deposition method titanium deoxid film in glass, pottery, titanium plate, PVC or the load of active carbon fibre solid material surface.
Wherein, add chlorion compound 0～0.3g/L according to pending water chloride ion-containing concentration.
Wherein, to be suitable for pending water be that total content of organic carbon is the micropollutant water of 5～35mg/L to this method.
For achieving the above object, the present invention also proposes organic device in a kind of portable removal water, comprises electrochemical assembly and photochemical catalysis assembly, and wherein, described electrochemical assembly and described photochemical catalysis assembly are fixed on the retaining plate, the collaborative organism of removing in the water.
Wherein, described electrochemical assembly comprises negative electrode, anode, described photochemical catalysis assembly comprises loaded catalyst and is used to excite the photochemical catalysis excitation light source of described loaded catalyst, described retaining plate is a top board, described anode, described negative electrode, described loaded catalyst and described photochemical catalysis excitation light source all are fixed on the described top board, and described anode and described negative electrode are oppositely arranged in the both sides of described photochemical catalysis excitation light source, and described loaded catalyst is arranged at the other both sides of described photochemical catalysis excitation light source or centers on the setting of described photochemical catalysis excitation light source.
Wherein, a plurality of anchor posts are set on the described top board, described loaded catalyst is netted, described loaded catalyst be wrapped on described a plurality of anchor post and be fixed in described photochemical catalysis excitation light source around.
Electrochemical assembly and photochemical catalysis assembly are staggeredly placed in same reactive tank among the present invention, and electrochemistry and photocatalysis all play a role separately and be coupled enhancing.And the present invention is by electrochemistry and light-catalysed synergy, hydroxyl radical free radical isoreactivity material productive rate height, and exhaustive oxidation pollutent that can non-selectivity, by product generates few.
Description of drawings
Fig. 1 is that collaborative enhancing of electrochemistry photochemical catalysis of the present invention removed the organic device front view of little pollution;
Fig. 2 is that collaborative enhancing of electrochemistry photochemical catalysis of the present invention removed the organic device left view of little pollution;
Fig. 3 is that collaborative enhancing of electrochemistry photochemical catalysis of the present invention removed the organic device right view of little pollution;
Fig. 4 illustrates the collaborative water route connection diagram of removing the organic device of little pollution that strengthens of electrochemistry photochemical catalysis of the present invention;
Fig. 5 strengthens the front view of removing the organic portable unit of little pollution for electrochemistry photochemical catalysis of the present invention is collaborative;
Fig. 6 strengthens the vertical view of removing the organic portable unit of little pollution for electrochemistry photochemical catalysis of the present invention is collaborative;
Fig. 7 strengthens the B-B sectional view of removing the organic portable unit of little pollution for electrochemistry photochemical catalysis of the present invention is collaborative.
Wherein, Reference numeral:
1-reactor 2-anode
3-negative electrode 4-loaded catalyst
5-photochemical catalysis excitation light source 6-water-in
7-water outlet 8-power supply
9-water circulating pump 10-supply flume
11-top board 12-anchor post
13-standing bolt 14-set screw nut
15-seal buckle 16-hanging ring
Embodiment
The present invention proposes the associating of photochemical catalysis and electrochemical oxidation.For electrochemical process, anode produces hypochlorous acid, and the hypochlorous acid photodissociation produces hydroxyl radical free radical, makes interior hydroxyl radical free radical productive rate of identical time promote greatly, and the degraded equivalent organism reaction times shortens, and current consumption descends thereupon.For photocatalytic process, it is different from photodissociation, also can produce hydroxyl radical free radical and thoroughly remove organism.Battery lead plate forms directed electric field in solution, slow down the recombination velocity in photocatalyst surface light induced electron and hole, makes the hydroxyl radical free radical lifetime prolong, thereby has promoted the productive rate of photochemical catalysis hydroxyl radical free radical.The present invention is by photochemical catalysis and electrochemical the associating having formed collaborative enhancement, and degradation rate is greater than the photochemical catalysis and the algebraic sum of electrochemical degradation rate separately separately in the identical time.
The present invention adopts the collaborative enhanced method of electrochemical process and photocatalytic process, under the lower situation of electrolyte content, little pollution organism is thoroughly removed.
Fig. 1 is that collaborative enhancing of electrochemistry photochemical catalysis of the present invention removed the organic device front view of little pollution; Fig. 2 strengthens the organic device of the little pollution of a removal left side to be looked for electrochemistry photochemical catalysis of the present invention is collaborative; Fig. 3 is that collaborative enhancing of electrochemistry photochemical catalysis of the present invention removed the organic device right view of little pollution.As shown in Figure 1 to Figure 3, the collaborative enhancing of electrochemistry photochemical catalysis of the present invention removed organic device in the water, comprises electrochemical assembly and photochemical catalysis assembly, and electrochemical assembly is arranged in the same reactor 1 organism in the collaborative removal water with the photochemical catalysis assembly.
Wherein, described electrochemical assembly is arranged in the described reactor 1, and it comprises: anode 2, negative electrode 3 and power supply 8, and described negative electrode 3 is oppositely arranged with described anode 2, and described power supply 8 connects described negative electrode 3 and described anode 2.Wherein, described anode 2 is selected graphite, Pt, Ti, RuO for use
2, IrO
2Or RuO
2-Pt, described negative electrode 3 is selected Ti, Pt, Fe, Al, Cu, stainless steel for use.
Wherein, described photochemical catalysis assembly is arranged in the described reactor 1, described photochemical catalysis assembly comprises loaded catalyst 4 and is used to excite the photochemical catalysis excitation light source 5 of described loaded catalyst 4, the described anode 2 and the described negative electrode 3 of described electrochemical assembly are oppositely arranged in the both sides of described photochemical catalysis excitation light source 5, described loaded catalyst 4 is arranged at the other both sides of described photochemical catalysis excitation light source 5 or is provided with around described photochemical catalysis excitation light source 5, preferably, loaded catalyst 4 places described photochemical catalysis excitation light source 5 both sides (as Fig. 3) perpendicular to the battery lead plate direction.And described loaded catalyst 4 is a carried titanium dioxide film on glass, pottery, titanium plate, PVC or the activated carbon fiber carrier.Being shaped as of the carrier of described loaded catalyst 4 is tabular or netted.And, preferably, to implement mode of the present invention and can be arranged to tabularly for the shape of described carrier, described loaded catalyst 4 is 2 and is oppositely arranged the other both sides of described photochemical catalysis excitation light source 5; Perhaps described carrier be shaped as netted, described loaded catalyst 4 be fixed on described photochemical catalysis excitation light source 5 around or be provided with around described photochemical catalysis excitation light source 5.In addition, the light source selected for use of described photochemical catalysis excitation light source 5 is the following ultraviolet source of main emission wavelength 365nm.
Wherein, described reactor 1 can be cylindrical or square list groove reactor 1 or any tank.
Fig. 4 illustrates the collaborative water route connection diagram of removing the organic device of little pollution that strengthens of electrochemistry photochemical catalysis of the present invention, as shown in Figure 4, device of the present invention also comprises a supply flume 10, a water circulating pump 9, described reactor 1 below has a water-in 6, the top has a water outlet 7, described water-in 6 and described water outlet 7 are communicated with described supply flume 10 by exterior line, and described water circulating pump 9 is connected between described water-in 6 and the described supply flume 10.The water source is entered in the reactor 1 via water-in 6 by water circulating pump 9 by supply flume 10, little pollution organism in the synergy removal sewage of electrochemical process and photocatalytic process, turn back in the supply flume 10 by exterior line by water outlet 7 via the clean water after purifying, and this process is carried out in circulation.
Fig. 5 strengthens the front view of removing the organic portable unit of little pollution for electrochemistry photochemical catalysis of the present invention is collaborative; Fig. 6 strengthens the vertical view of removing the organic portable unit of little pollution for electrochemistry photochemical catalysis of the present invention is collaborative; Fig. 7 strengthens the B-B sectional view of removing the organic portable unit of little pollution for electrochemistry photochemical catalysis of the present invention is collaborative.To shown in Figure 7, organic device comprises electrochemical assembly and photochemical catalysis assembly in the portable removal water of the present invention as Fig. 5, and described electrochemical assembly and described photochemical catalysis assembly are fixed on the retaining plate, the collaborative organism of removing in the water.
Wherein, described electrochemical assembly comprises negative electrode 3, anode 2, described photochemical catalysis assembly comprises loaded catalyst 4 and is used to excite the photochemical catalysis excitation light source 5 of described loaded catalyst 4, described retaining plate is a top board 11, described anode 2, described negative electrode 3, described loaded catalyst 4 and described photochemical catalysis excitation light source 5 all are fixed on the described top board 11, and described anode 2 is oppositely arranged in the both sides of described photochemical catalysis excitation light source 5 with described negative electrode 3, described loaded catalyst 4 is arranged at the other both sides of described photochemical catalysis excitation light source 5 or is provided with around described photochemical catalysis excitation light source 5, preferably, described loaded catalyst 4 places described photochemical catalysis excitation light source 5 both sides perpendicular to the battery lead plate direction.
Preferably, to shown in Figure 7, a plurality of anchor posts 12 are set on the described top board 11 as Fig. 5, described loaded catalyst 4 is netted, described loaded catalyst 4 be wrapped on described a plurality of anchor post 12 and be fixed in described photochemical catalysis excitation light source 5 around.Photochemical catalysis excitation light source 5 pipe afterbodys are with seal buckle 15 sealings.Hanging ring 16 is set on seal buckle 15, this portable equipment can be hung in the various small containers works.
Organic device in the above-mentioned portable removal water of the present invention is convenient for carrying, and it can be inserted and carry out organic removal purifying treatment in the water in any water processing reactor whenever and wherever possible.
In addition, the present invention proposes organic method in a kind of removal water, method of the present invention can be than electrochemistry or independent photocatalysis method are more effectively removed little pollution organism in the water separately, it produces collaborative enhancement when bringing into play electrochemistry and photocatalysis respectively, improved little pollution treatment of organic matters of organic efficient in the tap water.The principle that the collaborative coupling of its electrochemistry photochemical catalysis enhancement produces is: photocatalysis takes place under the UV irradiate light, and because battery lead plate produces directed electric field in solution, disturbance the compound path right to light induced electron-hole, improved the quantum yield of photocatalysis hydroxyl radical free radical to a certain extent; Simultaneously, organism is oxidized at electrode anode 2, the Cl in the solution
-Under the effect of electrooxidation and photolysis, produce the stronger hydroxyl radical free radical of oxidisability.Under electrochemistry and light-catalysed collaborative coupling, organism is removed from water completely like this.
Wherein, in this method, the electrochemical assembly and the photochemical catalysis assembly that are arranged in the same reactor 1 carry out electrochemical process and photocatalytic process simultaneously, bring into play the collaborative simultaneously organism of removing in the water that strengthens of effect separately by electrochemical assembly and photochemical catalysis assembly.
Wherein, method of the present invention improves the hydroxyl radical free radical that produces in electrochemical process and the photocatalytic process to remove the organism in the water by collaborative enhancing of electrochemical process and photocatalytic process.
Wherein, described photochemical catalysis assembly comprises loaded catalyst 4 and is used to excite the photochemical catalysis excitation light source 5 of described loaded catalyst 4 that described loaded catalyst 4 is for adopting powder sintering, collosol and gel or the liquid deposition method titanium deoxid film in glass, pottery, titanium plate, PVC or the load of active carbon fibre solid material surface.
Particularly, the present invention utilizes in the above-mentioned removal water organic device to propose a kind ofly to utilize electrochemistry, the collaborative coupling of photochemical catalysis to strengthen the organic method of little pollution in the water of removing.As a better embodiment, method of the present invention is: the electrochemistry that is crisscross arranged simultaneously in reactor 1 and photochemical catalysis assembly.Wherein, use comprises graphite, Pt, Ti, RuO
2, IrO
2Or RuO
2Electrodes such as-Pt use to comprise electrodes such as Ti, Pt, Fe, Al, Cu or stainless steel as negative electrode 3, working load type TiO as anode 2
2As photocatalyst, the light source that main output wavelength is 254nm is as photochemical catalysis excitation light source 5.Current density was in 5～50mA/cm2 scope, and photochemical catalysis assembly and electrochemical assembly start simultaneously, with polluted-water associated treatment 1～6 hour.
Wherein, method of the present invention is applicable to that handling TOC concentration is the water of 5～35mg/L.
And the method for electrochemistry photocatalysis method provided by the invention collaborative coupling enhancing removal micro-polluted drinking water is the higher water body of saltiness (even brackish water source) as the target water body in treating processes, and its chloride ion content is enough, need not to add chlorine-containing compound; Low excessively as target water body saltiness, can in drinking water sanitary standard GB5749-2006 allowed band, add a small amount of chlorine-containing compound.And, preferred sodium-chlor of described chlorion compound or Repone K.The addition of described chlorion compound is preferably 0-0.3g/L (pending water).
During practical application, can run into following occasion, can be according to occasion different choice processing condition:
(1) when chloride ion content own is higher in the water, can not add sodium-chlor can the efficient degradation organism.
(2) chloride ion content is lower in the aqueous solution, adds chlorion on a small quantity according to national standard, reaches efficient degradation.
(3) even can't add muriate, electrochemical efficiency is lower, but because the existence of photocatalysis, still electrochemistry is removed the efficient height separately.With respect to the photodissociation associating electrochemical techniques of prior art, under the similarity condition, degradation rate is higher.
In one embodiment of the invention, anode 2 is Ti/Pt-RuO
2, Ti/RuO
2, Ti/IrO
2Or Ti/Pt, preferred negative electrode 3 is stainless steel, Ti or Pt.
In one embodiment of the invention, described reactor 1 is the cubic bodily form or cylindrical.
In one embodiment of the invention, described electrolyzer is single flute profile formula.
In one embodiment of the invention, adopting photochemical catalysis excitation light source 5 is the 8w ultraviolet germicidal.
In specific embodiments of the present invention, the shape of electrode can be the various arbitrary shapes of determining according to actual needs such as tabular, netted, round shape or wire.
Employed loaded photocatalyst among the present invention is for adopting the titanium deoxid film of several different methods such as powder sintering, collosol and gel, liquid deposition in the solid material surface load of unharmful substances such as glass, pottery, titanium plate, PVC, activated carbon fiber leaching.The various arbitrary shapes of determining according to actual needs such as it is tabular, netted that support shapes can be.Preferably, described loaded photocatalyst utilizes the commercially available P25 titania powder aqueous solution to form in the load of tabular PVC material surface for adopting the powder sintering method.
Reaction formula in the inventive method mechanism is as follows:
Photocatalytic process:
TiO2+hv→TiO2+h++e- (1)
H2O+h+→·OH+H+ (2)
OH-+h+→·OH (3)
Electrochemical process:
Near the anode
2Cl-→Cl2+2e- (4)
Cl2+H2O→HClO+H++Cl- (5)
HClO→ClO-+H+ (6)
HClO+hv→·OH+·Cl (7)
Near the negative electrode
O2+2H2O+2e-→H2O2+2OH- (8)
H2O2+hv→2·OH (9)
Example 1
As Fig. 1, Fig. 2 and device shown in Figure 3, reactor is a volume 1L cubes acrylic tank, and anode is Ti/Pt-RuO
2Plate electrode (effective usable floor area 58cm
2), negative electrode is a stainless steel electrode, and a direct current stabilizer is as power supply, and its virtual voltage is 0-50V, and watt current is 0-5A.Loaded catalyst adopts the preparation of powder sintering method, and carrier is PVC plate (planar dimension 15cm*5cm, carried titanium dioxide 1.45g altogether), and the 8w ultraviolet germicidal is as the photochemical catalysis excitation power source.Each water yield 3L that handles.
(phenol content 30mg/L, solution TOC are about 23mg/L with the organically-polluted water 3L of synthetic in the experiment; Na
2SO
42g/L, NaCl 0.3g/L) put into supply flume 10 shown in Figure 4, ON cycle water pump 9 is regulated flow, starts the photochemical catalysis power supply, and the setting current density is 30mA/cm
2Behind the reaction 6h, water outlet phenol does not detect, and TOC concentration is 3.35mg/L, and aromatic series degraded intermediate product is not found in HPLC (high performance liquid chromatography) monitoring.Under same apparatus and the experiment condition, do not open the photochemical catalysis light source, independent electrochemical treatment, TOC of yielding water concentration is 8.2mg/L.
Example 2
This example implementation method such as example 1, the simulated target water quality increases NH on example 1 basis
3-N 5mg/L.After handling 6h, water outlet phenol does not detect, TOC concentration 3.31mg/L, NH
3-N does not detect.
Example 3
The collaborative device (seeing Fig. 5 to Fig. 7) of removing organic pollutant that strengthens of small portable electrochemistry photochemical catalysis is connected and fixed by the Stainless Steel Cloth of PVC top board 11, plate electrode 2,3, carried titanium dioxide and ultraviolet germicidal and forms.Top board is a square, anodic-cathodic is oppositely arranged, be fixed on the top board 11 by standing bolt 13, ultraviolet lamp is fixed on square center, four stainless steel anchor posts 12 are set all around, anchor post 12 is fixed on the top board 11 by set screw nut 14, and mesh load type catalyzer twines pillar and is fixed on around the ultraviolet lamp lamp.The ultraviolet lamp tube afterbody is placed the entry short circuit with the seal buckle sealing.Hanging ring 16 is set on seal buckle 15, this portable equipment can be hung in the various small containers works.
Portable electrochemical photochemical catalysis cooperative device shown in Figure 5 is inserted in the polyethylene cylindrical vessel (high 30cm, diameter 25cm), is that (phenol content 15mg/L, solution TOC are about 11.5mg/L to synthetic organic waste water 10L in the container; Na
2SO
42g/L, NaCl 0.3g/L).Anode 2 adopts Ti/Pt-RuO
2Plate electrode (effective usable floor area 58cm
2), negative electrode 3 is a homalographic titanium plate electrode, and as power supply, its virtual voltage is 0-50V with direct current stabilizer, and watt current is 0-5A.Loaded photocatalyst adopts Prepared by Sol Gel Method, and carrier is 60～80 order Stainless Steel Cloths (catalyzer total loading amount is 0.85g), and the 8w ultraviolet germicidal is as the photochemical catalysis excitation power source.
Behind the reaction 6h, phenol does not detect in the water outlet, and TOC concentration is 1.65mg/L, the big aromatic series intermediate product of detectable toxicity not in the HPLC monitoring solution.
Compared with prior art, characteristics of the present invention are:
(1) electrochemical assembly and photochemical catalysis assembly are staggeredly placed in same reactor among the present invention, and electrochemistry and photocatalysis all play a role separately and be coupled enhancing;
(2) hydroxyl radical free radical isoreactivity material productive rate height of the present invention, exhaustive oxidation pollutent that can non-selectivity, by product generates few.Wherein, photocatalysis takes place under the UV irradiate light, and because battery lead plate produces directed electric field in solution, disturbance the compound path right to light induced electron-hole, improved the quantum yield of photocatalysis hydroxyl radical free radical to a certain extent; Simultaneously, organism is oxidized at electrode anode, and the Cl-in the solution produces the stronger hydroxyl radical free radical of oxidisability under the effect of electrooxidation and photolysis.
When (3) the present invention applied to the low water body of saltiness, the existence of photocatalysis guaranteed the validity of pollutant removal equally;
(4) the present invention removes the organic while, also can apply to other pollutent of oxidation, as ammonia nitrogen etc.
(5) the inventive method can be used in large-scale special purpose reactor, and it is simple, easy to operate to be used to implement reactor making of the present invention, the level of automation height; Simultaneously also can develop the small portable reacting appliance, place various water receptacles to use.
(6) the inventive method is removed the pollution degradation beyond the region of objective existence, and the sterilization bacteriostatic action is very obvious, is used for can saving sterilization process behind the drink water purifying.
(7) method of the present invention can be used for disposing of sewage, the organic water body of various little pollution of drinking water source.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (13)
1. remove organic device in the water for one kind, it is characterized in that electrochemical assembly and photochemical catalysis assembly are arranged in the same reactor, the collaborative organism of removing in the water.
2. device according to claim 1, it is characterized in that, described photochemical catalysis assembly is arranged in the described reactor, described photochemical catalysis assembly comprises loaded catalyst and is used to excite the photochemical catalysis excitation light source of described loaded catalyst, described electrochemical assembly comprises negative electrode, anode and connects the power supply of anode and negative electrode, described anode and described negative electrode are oppositely arranged in the both sides of described photochemical catalysis excitation light source, and described loaded catalyst is arranged at the other both sides of described photochemical catalysis excitation light source or centers on the setting of described photochemical catalysis excitation light source.
3. device according to claim 2 is characterized in that, described loaded catalyst is a carried titanium dioxide film on tabular, the thread or mesh carrier that is formed by glass, pottery, titanium plate, PVC or activated carbon fiber.
4. device according to claim 2 is characterized in that described anode is selected graphite, Pt, Ti, RuO for use
2, IrO2 or RuO
2-Pt, described negative electrode is selected Ti, Pt, Fe, Al, Cu, stainless steel for use.
5. device according to claim 2 is characterized in that, the light source that described photochemical catalysis excitation light source is selected for use is the following ultraviolet source of main emission wavelength 365nm.
6. device according to claim 1, it is characterized in that, also comprise a supply flume, a water circulating pump, described reactor below has a water-in, and the top has a water outlet, and described water-in and described water outlet are communicated with described supply flume by exterior line, and described water circulating pump is connected between described water-in and the described supply flume, wherein, described reactor can be cylindrical or square list groove reactor or any tank.
7. remove organic method in the water for one kind, it is characterized in that, the electrochemical assembly and the photochemical catalysis assembly that are arranged in the same reactor carry out electrochemical process and photocatalytic process simultaneously, bring into play the collaborative simultaneously organism of removing in the water that strengthens of effect separately by electrochemical assembly and photochemical catalysis assembly.
8. organic method in the removal water according to claim 7 is characterized in that, improves make a return journey organism in dewatering of hydroxyl radical free radical output in electrochemical process and the photocatalytic process by collaborative enhancing of electrochemical process and photocatalytic process.
9. organic method in the removal water according to claim 7, it is characterized in that, described photochemical catalysis assembly comprises loaded catalyst and is used to excite the photochemical catalysis excitation light source of described loaded catalyst that described loaded catalyst is for adopting powder sintering, collosol and gel or the liquid deposition method titanium deoxid film in glass, pottery, titanium plate, PVC or the load of active carbon fibre solid material surface.
10. according to right 7 described methods, it is characterized in that, add chlorion compound 0～0.3g/L according to pending water chloride ion-containing concentration.
11. organic device in the portable removal water is characterized in that, comprises electrochemical assembly and photochemical catalysis assembly, wherein, described electrochemical assembly and described photochemical catalysis assembly are fixed on the retaining plate, the collaborative organism of removing in the water.
12. according to organic device in the portable removal water of claim 11, it is characterized in that, described electrochemical assembly comprises negative electrode, anode, described photochemical catalysis assembly comprises loaded catalyst and is used to excite the photochemical catalysis excitation light source of described loaded catalyst, described retaining plate is a top board, described anode, described negative electrode, described loaded catalyst and described photochemical catalysis excitation light source all are fixed on the described top board, and described anode and described negative electrode are oppositely arranged in the both sides of described photochemical catalysis excitation light source, and described loaded catalyst is arranged at the other both sides of described photochemical catalysis excitation light source or centers on the setting of described photochemical catalysis excitation light source.
13. according to organic device in the portable removal water of claim 12, it is characterized in that, a plurality of anchor posts are set on the described top board, described loaded catalyst is netted, described loaded catalyst be wrapped on described a plurality of anchor post and be fixed in described photochemical catalysis excitation light source around.
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