CN104925897A - Magnetic field inductive type photocatalytic reactor and degradation use method therefor - Google Patents
Magnetic field inductive type photocatalytic reactor and degradation use method therefor Download PDFInfo
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Abstract
The present invention discloses a magnetic field inductive type photocatalytic reactor and a degradation use method therefor. The magnetic field inductive type photocatalytic reactor comprises a micro inductive light source, a reaction tank and alternating magnetic fields, wherein the micro inductive light source is arranged inside the reaction tank and the reaction tank is arranged inside the alternating magnetic fields; and the alternating magnetic fields, by means of electromagnetic induction, enable the micro inductive light source to emit light to form the inductive photocatalytic reactor of the alternating magnetic fields and optical coupling effect. The light source of a catalytic reactor can generate illumination in a reaction liquid without the need of an external power line; meanwhile, the light source has high mass-transfer efficiency in the reaction liquid and has low energy consumption and high energy efficiency.
Description
Technical field
The present invention relates to a kind of magnetic field induction photo catalysis reactor, belong to light-catalyzed reaction technical field.
Background technology
Light-catalyzed reaction technology is a kind of wastewater processing technology of high effect cleaning, but is not also applied to reality, and mainly because reaction efficiency is low, the recombination rate being embodied in light induced electron and hole is higher; Uneven illumination, the capacity usage ratio of light source is low etc.In order to improve quantum yield and the capacity usage ratio of photocatalytic process, except carrying out modification (as metal ion mixing to the Nomenclature Composition and Structure of Complexes of photocatalyst, noble metal loading, acid modulation, area load and semiconductors coupling etc.) outward, can also improve photo catalysis reactor, at photochemical catalysis system additional external field, comprise microwave field, electric field, ultrasonic wave field and magnetic field etc., coupling effect is produced to make external energy field and light field, impel effective separation of photo-generated carrier, thus reach its life-span of prolongation, and improve the object of light-catalyzed reaction over-all quantum efficiency.
At present, in order to improve the efficiency of light-catalyzed reaction, have devised various photo catalysis reactor both at home and abroad, having slurry photocatalytic reactor, fixed-bed type photo catalysis reactor, optical-fiber type reactor etc.
Slurry photocatalytic reactor is generally column, TiO
2fill in the reactor with the form of powder, make TiO by the method such as air-blowing or stirring
2powder fully contacts with organic pollutant.Such TiO
2powder specific-surface area detection is large, mass transfer effect good, but light-catalysed degradation rate is lower simultaneously, as increase TiO
2that can reduce light during powder concentration penetrates efficiency, and TiO
2powder is difficult to be reclaimed with solution separating.Puma etc. devise fountain type photo catalysis reactor, by TiO
2powder is mixed in pending solution, and solution stream forms one deck liquid film in atmosphere through nozzle, by the irradiation of UV-light, and degradation of contaminant.The photocatalysis efficiency of this reactor is very high, mass transfer effect good, can not because of TiO
2the increase of powder and reduce the assimilated efficiency of light, but TiO
2more complicated (the Puma G.L. of sepn process of powder and solution, Yuep L., A novelfountain photocatalytic reactor:model development and experimentalvalidation [J] .Chemical Engineering Science, 2001,56 (8): p.2733-2744).
Fixed-bed type photo catalysis reactor mainly will have the packed catalyst of appropriate form in the reactor, carries out light-catalyzed reaction.The people such as Jiang Liwen devise a kind of fixed packed bed photo catalysis reactor (loaded photocatalyst being carrier with common glass sheet and quartzy spiral coil of pilot scale, be placed in inwall and the inside of reactor respectively), carry out using hardly degraded organic substance methylene blue as model pollutant studying (Jiang Liwen, Feng Guizhen, ten thousand treasures. the research [J] of fixed filled composite bed photocatalytic reactor design influence factor. water technology, 2007,33 (8): 23-25).After illumination 180min, solution degradation decolorizing efficiency when not placing loading type film photocatalyst is 23.9%, and degradation and decolorization efficiency when placing common glass sheet and quartzy spiral coil carrier thin film photocatalyst can reach 93.8%, this shows: in order to make full use of the energy of ultraviolet radiation photon, the loaded photocatalyst filler of some amount is reasonably set in the useful space of reactor, can the degradation efficiency of larger raising photo catalysis reactor.But in fixed bed type reactor, the effective affecting acreage of photocatalyst material reduces, and the contact area of catalyzer and reactant is not high.
The configuration of optical-fiber type reactor is proposed by Marinangeli and Ollis at first, is using optical fiber as TiO
2supporting substrate and the transmission medium of UV-light, directly light is conducted to TiO
2, improve the utilization ratio of light, increase TiO
2light application ratio surface-area, and optical-fiber type reactor can utilize sunlight to replace source of artificial light to make Photocatalytic Degradation Process more energy-conserving and environment-protective (Marinangeli R.E., Ollis D.F., Photo-assisted heterogeneous catalysiswith optical fiber:I.Isolated single fiber.AIChE J, 1977,23:415-426).The people such as Hu Yan have devised diffuse type optical fiber reactor (dispersion fiber is made up of quartzy core fibre and silicon rubber covering, adds a certain proportion of disperse means in covering), by Detitanium-ore-type TiO
2load is on novel ultraviolet light type dispersion fiber, and field emission scanning electron microscope (FE-SEM) photo shows TiO
2the associativity of film and dispersion fiber is fine, load TiO
2the degradation results of single dispersion fiber to reactive brilliant red x-3b show, the side-scattered UV-light of dispersion fiber can excite TiO
2generation photocatalysis oxidation reaction (Hu Yan, Xu Jingjing, Yuan Chunwei etc. the application of dispersion fiber in photochemical catalysis wastewater treatment [J] of load nano-titanium dioxide. Science Bulletin, 2005,50 (19): 2169-2173).This load TiO
2novel ultraviolet light type dispersion fiber be that new approaches have been opened up in the application of optical-fiber type reactor in photocatalysis degradation organic contaminant.But optical fiber type reactor still Shortcomings, as expensive, uneven illumination is even, near optical fiber according to comparatively strong, away from optical fiber according to more weak.
Photo catalysis reactor is the core of photocatalysis technology, and its structure directly determines the effect of photocatalysis treatment pollutent.Desirable photo catalysis reactor should have low energy consumption and high Energy efficiency.Therefore we will on the basis of traditional photo catalysis reactor, carry out structure to improve and optimize further, optimize reactor and make the illumination condition of light source in reaction solution, improve the effective rate of utilization of light source, design novel reasonable and practical photo catalysis reactor, to for actual waste water process.Research shows that stationary magnetic field has synergistic effect (Zhang Wen to light-catalyzed reaction, Wang Xuxu, the magnetic field effect research [J] of Fu XianZhi .Pt/TiO2 photocatalytic degradation benzene. chemical journal, 2005,63 (8): 715-719.), externally-applied magnetic field not only extends the life-span of photo-generated carrier, and improves the transformation efficiency of some intermediate, thus improves the activity of photocatalytic degradation reaction.The impact of additional alternating magnetic field on light-catalyzed reaction and the photo catalysis reactor based on electromagnetic induction principle have no bibliographical information.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides a kind of magnetic field induction photo catalysis reactor, catalyticreactor light source of the present invention can produce illumination without the need to circumscripted power line in reaction solution, has low energy consumption and high Energy efficiency simultaneously.
For achieving the above object, the technical solution used in the present invention is:
A kind of magnetic field induction photo catalysis reactor, comprise miniature inductive formula light source, reaction tank and alternating magnetic field, described miniature inductive formula light source is arranged in reaction tank, and described reaction tank is arranged in alternating magnetic field; Described alternating magnetic field makes miniature inductive formula light source luminescent by electromagnetic induction, forms the induction type photo catalysis reactor of alternating magnetic field and optically-coupled effect.
Preferred: described miniature inductive formula light source is evenly distributed in reaction tank.
Preferred: described miniature inductive formula light source comprises miniature inductance coil and two LED, and the pin parallel connected in reverse phase of these two LED, the LED pin after parallel connection is simultaneously connected with miniature inductance coil two output pin.
Preferred: the generator of described alternating magnetic field comprises alternating magnetic field generating coil and high-frequency alternating current origin system; Described reaction tank is arranged in alternating magnetic field generating coil; Described high-frequency alternating current origin system comprises signal source, control unit and power amplifier, and described signal source, power amplifier phase and alternating magnetic field generating coil connect successively, and described control unit is connected with power amplifier with signal source respectively; Described signal source, for generation of sinusoidal ac signal, after power amplifier amplifies, acts on alternating magnetic field generating coil, makes coil produce alternating magnetic field; And control unit is used for the size that control signal source produces sinusoidal ac signal frequency and control power amplifier amplified current.
Further: described reaction tank is provided with fluid circulation system, described fluid circulation system comprises the liquid-inlet pipe, recycle liquid pump and the drain pipe that connect successively; Described drain pipe is connected with the upper end liquid outlet of reaction tank, and described liquid-inlet pipe is connected with the bottom fluid inlet of reaction tank.
Further: in described reaction tank, be provided with microwell plate, described microwell plate is between the bottom fluid inlet and miniature inductive formula light source of reaction tank.
Further: described reaction tank is provided with inlet system, described inlet system comprises pneumatic pump, and described pneumatic pump is connected with the bottom of reaction tank by inlet pipe.
Further: the wavelength 375-380nm of described LED; The number of turns of described alternating magnetic field generating coil is 100 circles, and the induction reactance of miniature inductance coil is 33mH, and internal resistance is 59 Ω.
A degraded using method for magnetic field induction photo catalysis reactor, comprises the following steps, the first step, imports in reaction tank by waiting to need the waste liquid of degraded; Second step, by catalyzer TiO
2and H
2o
2put in reaction tank; 3rd step, frequency and the size of current passing into alternating magnetic field of adjustment alternating magnetic field; 4th step, opens the generator power supply of alternating magnetic field, degrades.
Preferred: the frequency of described alternating magnetic field is adjusted by the control unit adjustment signal source sinusoidal ac signal frequency of high-frequency alternating current origin system; The size of current passing into alternating magnetic field is adjusted by the size of the amplification after-current of the control unit Modulating Power amplifier of high-frequency alternating current origin system; The alternating magnetic field frequency that signal source sinusoidal ac signal produces is 12KHz, and the amplification after-current of power amplifier is 2.0A.
A kind of magnetic field induction light-catalyzed reaction pond provided by the invention, compared to existing technology, has following beneficial effect:
1. because miniature inductive formula light source is arranged in reaction tank, and described reaction tank is arranged in alternating magnetic field; Described alternating magnetic field makes miniature inductive formula light source luminescent by electromagnetic induction, forms the induction type photo catalysis reactor of alternating magnetic field and optically-coupled effect.Alternating magnetic field makes miniature inductive formula light source luminescent by electromagnetic induction, therefore can produce illumination in reaction solution without the need to circumscripted power line, and avoiding place's LED has fault, the drawback that all LED cannot use.Miniature inductance coil can utilize electromagnetic induction generating lightening LED lamp, and do not need additional light source, the UV-light that the alternating magnetic field that the coil on reaction tank is produced and LED produce produces coupling, and light-catalyzed reaction efficiency is improved greatly.Therefore the mass-transfer efficiency of catalyticreactor light source of the present invention in reaction solution is high, has low energy consumption and high Energy efficiency.
2. described in, miniature inductive formula light source is evenly distributed in reaction tank, distribution of light can be made even, improve the utilization ratio of light source, thus improve the efficiency of light-catalyzed reaction.
3. the miniature used is LED, long service life, and can change wavelength of light as required.
4. owing to being provided with fluid circulation system on reaction tank, because of water circulating pump by reaction solution from reaction tank output suitable for reading, input bottom reaction tank, constantly circulate, repeat light-catalyzed reaction.Improve the purification rate of liquid.
5., due to reaction tank being provided with inlet system, pneumatic pump continues aeration bottom reaction tank, meets the needs of reaction system to oxygen, prevents catalyst particle deposition simultaneously.
In sum: catalyticreactor light source of the present invention can produce illumination without the need to circumscripted power line in reaction solution, the mass-transfer efficiency of light source in reaction solution is high simultaneously, has low energy consumption and high Energy efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of magnetic field induction photo catalysis reactor;
Fig. 2 is the structural representation of miniature inductive formula light source;
The impact of the frequency Degradation of Phenol rate of Fig. 3 alternating magnetic field;
The frequency of Fig. 4 alternating magnetic field is on the impact of methylene blue degradation rate;
The frequency of Fig. 5 alternating magnetic field is on the impact of waste water COD clearance;
The initial pH value of Fig. 6 phenol is on the impact of degradation rate;
The initial pH value of Fig. 7 methylene blue is on the impact of degradation rate;
The initial pH value of Fig. 8 waste water is on the impact of its COD clearance;
Fig. 9 catalyzer TiO
2the impact of amount Degradation of Phenol rate;
Figure 10 catalyzer TiO
2amount on the impact of methylene blue degradation rate;
Figure 11 catalyzer TiO
2amount on the impact of waste water COD clearance;
The impact of the consumption Degradation of Phenol rate of Figure 12 hydrogen peroxide;
The consumption of Figure 13 hydrogen peroxide is on the impact of methylene blue degradation rate;
The consumption of Figure 14 hydrogen peroxide is on the impact of waste water COD clearance;
The impact of Figure 15 air flow quantity Degradation of Phenol rate;
Figure 16 air flow quantity is on the impact of methylene blue degradation rate;
The starting point concentration of Figure 17 methylene blue is on the impact of degradation rate.
Wherein, 1 is control unit, and 2 is signal source, 3 is power amplifier, and 4 is power supply, and 5 is pneumatic pump, 6 is recycle liquid pump, and 7 is inlet pipe, and 8 is liquid-inlet pipe, 9 is drain pipe, and 10 is reaction tank, and 11 is alternating magnetic field generating coil, 12 is miniature inductive formula light source, and 121 is lamp housing, and 122 is miniature inductance coil, 123 is LED, and 13 is microwell plate.
Embodiment
The present invention program is understood better in order to make those skilled in the art person, below in conjunction with embodiment, clear, complete description is carried out to the technical scheme in the present invention, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, should belong to the scope of protection of the invention.
A kind of magnetic field induction photo catalysis reactor, as shown in Figure 1, comprise miniature inductive formula light source 12, reaction tank 10 and alternating magnetic field, described miniature inductive formula light source 12 is evenly distributed in reaction tank 10, and described reaction tank 10 is arranged in alternating magnetic field; Described alternating magnetic field makes miniature inductive formula light source 12 luminous by electromagnetic induction, forms the induction type photo catalysis reactor of alternating magnetic field and optically-coupled effect.
The generator of described alternating magnetic field comprises alternating magnetic field generating coil 11 and high-frequency alternating current origin system; Described reaction tank 10 is arranged in alternating magnetic field generating coil 11; As shown in Figure 1, shown alternating magnetic field generating coil 11 is wrapped on reaction tank 10, described high-frequency alternating current origin system comprises signal source 2, control unit 1 and power amplifier 3, alternating magnetic field generating coil 11 on described signal source 1, power amplifier 3 phase and reaction tank 10 connects successively, and described control unit 1 is connected with power amplifier 3 with signal source 2 respectively; Described signal source 1 is for generation of sinusoidal ac signal, after power amplifier 2 amplifies, act on the alternating magnetic field generating coil 11 of reaction tank 10 outer wall winding, alternating magnetic field generating coil 11 produces alternating magnetic field, the energy of alternating magnetic field responded to by the miniature inductance coil 122 be now uniformly filled in the miniature inductive formula light source 12 in reaction tank 10, generation current lights UV-LED123, send the UV-light of certain wavelength, alternating magnetic field and light field acting in conjunction carry out the organic waste water in catalytic degradation reaction pond 10; And control unit 1 produces sinusoidal ac signal frequency for control signal source 2 and controls the size of power amplifier 3 amplified current.
Described reaction tank is provided with fluid circulation system, and described fluid circulation system comprises the liquid-inlet pipe 8, recycle liquid pump 6 and the drain pipe 9 that connect successively; Described drain pipe 9 is connected with the upper end liquid outlet of reaction tank 10, and described liquid-inlet pipe 8 is connected with the bottom fluid inlet of reaction tank 10.Reaction solution exports from reaction tank 10 upper end liquid outlet by recycle liquid pump 6, from the input of reaction tank 10 bottom fluid inlet, constantly circulates, repeats light-catalyzed reaction.
Be provided with microwell plate 13 in described reaction tank, described microwell plate 13 is between the bottom fluid inlet and miniature inductive formula light source 12 of reaction tank 10.When liquid circulation, filter by microwell plate 13 pairs of liquid.
Described reaction tank is provided with inlet system, and described inlet system comprises pneumatic pump 5, and described pneumatic pump 5 is connected with the bottom of reaction tank 10 by inlet pipe 7.Pneumatic pump 5 continues aeration bottom reaction tank 10, meets the needs of reaction system to oxygen, prevents catalyst particle deposition simultaneously.
The structure of reaction tank 10: reaction tank 10 is the columniform reaction tanks obtained by colourless transparent resin glass, and external diameter is 70.60mm, and internal diameter is 60.72mm, height is 117.30mm; The texture of coil of outer winding is enamel covered wire, and wire diameter is 0.79mm, is wound around 100 circle enamel covered wires outward uniformly at reaction tank.Because the number of stitches be wound around is more, the frequency producing alternating magnetic field is larger, and induction reactance is larger, and time constant by the exchange current of coil, the input voltage of needs is larger, and the enamel covered wire of needs is also more; Otherwise the number of stitches of winding is fewer, the frequency of the alternating magnetic field of generation will be less, induction reactance is less, and the UV-light that magnetic induction lamp produces will be more weak, and photocatalysis effect will be poor, so according to the output rating of power amplifier and output voltage, determine that number of stitches is 100 circles.
The structure of miniature inductive formula light source: as shown in Figure 2, described miniature inductive formula light source 12 comprises miniature inductance coil 122 and two LED 123, and this LED adopts UV-LED lamp; And the pin parallel connected in reverse phase of these two LED 123, LED 123 pin and the miniature inductance coil 122 liang of output pins after parallel connection are simultaneously connected.Described miniature inductive formula light source 12 is provided with lamp housing 121, the sealed enclosure that described lamp housing 121 is formed for clear perspex material sealing miniature inductive formula light source.The wavelength of LED 123 is more short better, but when wavelength is lower than 375nm, the price of LED 123 is higher, so the wavelength that this device selects sexual valence higher is that the LED of 375-380nm is as light source.
The arrangement mode of miniature inductive formula light source 12: be provided with multi-layer mini-type induction type light source 12 in reactor, miniature inductive formula light source 12 presses layer arrangement from top to bottom in reaction tank 10, and every layer arranges 14, adopts close arrangement mode.Electromagnetic induction principle is applied to photo catalysis reactor, and LED, without the need to circumscripted power line, facilitates light source to be uniformly distributed in reactor, and avoiding a place has fault, the drawback that all LED cannot use.
The selection of the miniature inductance coil of miniature inductive formula light source: miniature inductance coil is the commodity coil bought, and induction reactance is 33mH, and internal resistance is 59 Ω.Because telefault can the energy in induction of high frequency magnetic field, generation current lightening LED lamp, sends the UV-light of certain wavelength.Table 1 is the impact of telefault on the strength of current produced, as shown in table 1, and when induction reactance is larger, its internal resistance is also large, and the strength of current of generation is relatively weak, and the UV-light sent is just relatively weak; When induction reactance is less, its internal resistance is little, but the little strength of current causing it to produce of induction reactance is relatively weak, and the UV-light sent is also relatively weak, so select the telefault of induction reactance 33mH.
Table 1 telefault is on the impact of the strength of current produced
Catalyzed degradation principle: light-catalyzed reaction system of the present invention is primarily of high-frequency ac power and photo catalysis reactor two portions composition, and the core of device is induction type photo catalysis reactor.Signal source in high-frequency ac power produces sinusoidal ac signal, after power amplifier amplifies, act on the coil of reaction tank outer wall winding, exchange current makes alternating magnetic field generating coil circle produce alternating magnetic field, now be uniformly filled in the energy of the telefault induction alternating magnetic field in the miniature inductive formula light source in reaction tank, generation current lights UV-LED, send the UV-light of certain wavelength, alternating magnetic field and light field acting in conjunction carry out the organic waste water in catalytic degradation reaction pond, thus define the induction type light-catalyzed reaction pond of alternating magnetic field and optically-coupled effect.
A degraded using method for magnetic field induction photo catalysis reactor, comprises the following steps:
The first step, will wait that the waste liquid needing degraded imports in reaction tank.
Second step, by catalyzer TiO
2and H
2o
2put in reaction tank.
3rd step, frequency and the size of current passing into alternating magnetic field of adjustment alternating magnetic field; The frequency of alternating magnetic field is adjusted by the control unit adjustment signal source sinusoidal ac signal frequency of high-frequency alternating current origin system; The size of current passing into alternating magnetic field is adjusted by the size of the amplification after-current of the control unit Modulating Power amplifier of high-frequency alternating current origin system; The alternating magnetic field frequency that signal source sinusoidal ac signal produces is 12KHz, and the amplification after-current of power amplifier is 2.0A.
4th step, opens the generator power supply of alternating magnetic field, degrades.
Example 1
Use magnetic field induction photo catalysis reactor degradation of phenol waste water of the present invention.
By phenol solution as simulated wastewater, investigate under the condition of additional alternating magnetic field, the starting point concentration of phenol, the initial pH value of solution, the dosage of catalyzer, H
2o
2dosage, air flow quantity, alternating magnetic field frequency, by factors such as coil current size and times on the impact of catalytic effect.Experimentally design, get 125mL phenol solution, add a certain amount of TiO
2and H
2o
2be 30 DEG C with constant temperature circulating water management temperature of reaction system, open air compressor and regulate air flow quantity, open water circulating pump and reaction solution is circulated, the intensity of light source is controlled by voltage stabilized source, regulating winding strength of current and alternating magnetic field frequency, open agitator, samples after reaction 1h, put into supercentrifuge, with the centrifugal 8min of 14000r/min, get after supernatant liquid filters and measure phenol content, calculate its degradation rate.
It is the impact of the frequency Degradation of Phenol rate of alternating magnetic field as Fig. 3, along with the increase of frequency, the degradation rate of phenol also increases, the frequency of alternating magnetic field and the degradation rate of phenol roughly linear, but, when 8KHz, its degradation rate is 30%, and the degradation rate of linear relationship display is 26%, the degradation rate that its degradation rate shows much larger than linear relationship, when 14KHz, its degradation rate is 38%, and the degradation rate of linear relationship display is 36%, the degradation rate that its degradation rate shows much larger than linear relationship.
As shown in Figure 6, for the initial pH value of phenol is on the impact of degradation rate, along with the increase of pH value, the degradation rate of phenol also increases, after pH value is greater than 7, along with the increase of pH value, degradation rate declines, and it is when pH=7, and the degradation rate of phenol is the highest, its degradation rate is 30%, but when pH=9, its degradation rate does not decline, be 28%, basic equal with degradation rate during pH=8.
As shown in Figure 9, be catalyzer TiO
2the impact of amount Degradation of Phenol rate, along with TiO
2the increase of amount, the degradation rate of phenol slowly increases, TiO
2amount be increased to a certain amount of after, along with TiO
2the increase of amount, degradation rate reduces rapidly.
As shown in figure 12, for the impact of the consumption Degradation of Phenol rate of hydrogen peroxide, along with the increase of hydrogen peroxide use, phenol degrading rate reduces increase rapidly, hydrogen peroxide use be increased to a certain amount of after, along with the increase of hydrogen peroxide use, degradation rate reduces rapidly, but in the increase along with hydrogen peroxide use, degradation rate slowly reduces.
As shown in figure 15, be the impact of air flow quantity Degradation of Phenol rate, along with the increase of air flow quantity, phenol degrading rate increases sharply, air flow quantity be increased to a certain amount of after, along with the increase of air flow quantity, in slow reduction after phenol degrading takes the lead in reducing rapidly.
In this example, the degradation effect of magnetic field induction photo catalysis reactor Pyrogentisinic Acid simulated wastewater is obvious, its Optimization Technology is: be 15 μ L when phenol solution concentration is 15mg/L, pH=7, H2O2 consumption, TiO2 catalyst levels is 0.18g, air flow quantity is respectively 60L/h, and alternating magnetic field frequency is 12KHz, and passing into coil current is 2.0A, time, when being 1h, phenol degrading rate can reach 47.10%.
Example 2 magnetic field induction photo catalysis reactor degradation of methylene blue waste water
With methylene blue solution as simulated wastewater, investigate under the condition of additional alternating magnetic field, the starting point concentration of methylene blue, initial pH value, the dosage of catalyzer, H
2o
2dosage, air flow quantity, alternating magnetic field frequency, by the factor such as high-frequency ac current size and time of coil on the impact of catalytic effect.Experimentally design, get 125mL methylene blue solution, add a certain amount of TiO
2and H
2o
2be 30 DEG C with constant temperature circulating water management temperature of reaction system, open air compressor and regulate air flow quantity, open recycle pump and reaction solution is circulated, the intensity of light source is controlled by voltage stabilized source, regulating winding strength of current and alternating magnetic field frequency, open agitator, samples after reaction certain hour, put into supercentrifuge, with the centrifugal 8min of 14000r/min, get the absorbance measuring methylene blue after supernatant liquid filters, calculate its degradation rate.
If Fig. 4 is that the frequency of alternating magnetic field is on the impact of methylene blue degradation rate, along with the increase of frequency, the degradation rate of methylene blue increases sharply, frequency be increased to a certain amount of after, along with the increase of frequency, the degradation rate of methylene blue reduces rapidly, but in the increase along with frequency, the degradation rate of methylene blue is tending towards constant, and it is when 12KHz, the degradation rate of methylene blue is the highest, and its degradation rate is 90%.
As shown in Figure 7, for the initial pH value of methylene blue is on the impact of degradation rate, when 20min, along with the increase of pH value, the degradation rate of methylene blue slowly increases, increasing along with pH value, the degradation rate of methylene blue increases fast, but is increasing along with pH value, and the degradation rate of methylene blue increases slowly, when pH>9, degradation rate when its degradation rate is less than or equal to 8 much larger than pH.
As shown in Figure 10, be catalyzer TiO
2amount on the impact of methylene blue degradation rate, when 20min, along with TiO
2the increase of amount, the degradation rate of methylene blue increases sharply, and its degradation rate is increased to a certain degree, along with TiO
2the increase of amount, the degradation rate of methylene blue reduces.
As shown in figure 13, for the consumption of hydrogen peroxide is on the impact of methylene blue degradation rate, when 20min, along with the increase of hydrogen peroxide use, methylene blue degradation rate also increases, hydrogen peroxide use be increased to a certain amount of after, along with the increase of hydrogen peroxide use, degradation rate is tending towards constant.
As shown in figure 16, for air flow quantity is on the impact of methylene blue degradation rate, when 20min, along with the increase of air flow quantity, phenol degrading rate increases, air flow quantity be increased to a certain amount of after, along with the increase of air flow quantity, phenol degrading rate slowly increases, after being increased to certain depth along with air flow quantity, along with the increase of air flow quantity, phenol degrading rate increases sharply.
As shown in figure 17, for the starting point concentration of methylene blue is on the impact of degradation rate, when 20min, along with the increase of starting point concentration, methylene blue degradation rate increase, starting point concentration be increased to a certain amount of after, along with the increase of starting point concentration, degradation rate reduces, but when 20mg/L, its degradation rate goes up not down.
In this example, magnetic field induction photo catalysis reactor degradation of methylene blue solution achieves good effect, and methylene blue solution can fade very soon, obtains optimum process condition to be: the starting point concentration of methylene blue is 10mg/L, pH=9, drops into TiO
2catalytic amount is 0.20g, H
2o
2amount be 25 μ L, air flow quantity is 60L/h, and alternating magnetic field frequency is 12KHz, pass into the high-frequency ac current of coil for being 2.0A, reaction 120min, degradation rate reaches 98.67%, COD value reduces to 10.81mg/L by 25.68mg/L, and solution colour is become colorless by blueness.
Embodiment 3 magnetic field induction photo catalysis reactor degraded dyeing waste water
Select the actual dying of the printing and dyeing mill in Xuzhou as degraded object, with homemade novel induction type photo catalysis reactor, photocatalytic degradation is carried out to it, investigate under the condition of additional alternating magnetic field, the initial pH value of actual waste water, the dosage of catalyzer, H
2o
2dosage, alternating magnetic field frequency, by the factor such as high-frequency ac current size and time of coil on the impact of catalytic effect.Experimentally design, water sample takes from composite waste pond, is mazarine suspension liquid, because its turbidity is large, can affect UV-light through and reduce light-catalyzed reaction speed, therefore before treatment it to be filtered.Get 125mL actual waste water, add a certain amount of TiO
2and H
2o
2be 30 DEG C with constant temperature circulating water management temperature of reaction system, open air compressor and regulate air flow quantity, open recycle pump and reaction solution is circulated, the intensity of light source is controlled by voltage stabilized source, regulating winding strength of current and alternating magnetic field frequency, open agitator, samples after reaction certain hour, put into supercentrifuge, with the centrifugal 8min of 14000r/min, get after supernatant liquid filters and measure COD, calculate its COD clearance.
If Fig. 5 is that the frequency of alternating magnetic field is on the impact of waste water COD clearance, along with the increase of frequency, waste water COD clearance increases sharply, frequency be increased to a certain amount of after, along with the increase of frequency, waste water COD clearance slowly reduces, and it is when 12KHz, waste water COD clearance is the highest, and its degradation rate is 40%.
As shown in Figure 8, for waste water ph is on the impact of its COD clearance, along with the increase of pH value, COD clearance increases sharply, but after pH is greater than 2, its COD clearance increase is very slow, equal gradually.
As shown in figure 11, be catalyzer TiO
2amount on the impact of waste water COD clearance, along with TiO
2the increase of amount, waste water COD clearance increases sharply, TiO
2amount be increased to a certain amount of after, along with TiO
2the increase of amount, degradation rate slowly reduces.
As shown in figure 14, for the consumption of hydrogen peroxide is on the impact of waste water COD clearance, along with the increase of hydrogen peroxide use, waste water COD clearance increases sharply, hydrogen peroxide use be increased to a certain amount of after, along with the increase of hydrogen peroxide use, waste water COD clearance slowly reduces.
In this example, magnetic field induction photo catalysis reactor has good degradation effect to actual dying, at optimum conditions: the pH=2.80 of waste water, drops into TiO
2catalytic amount is 0.20g, H
2o
2amount be 25 μ L, air flow quantity is 60L/h, alternating magnetic field frequency is 12KHz, the high-frequency ac current passing into coil is 2.0A, after reaction 40h, the COD value of waste water reduces to 248.50mg/L by initial 597.99mg/L, and the COD clearance of waste water is 58.45%, waste water color is become faint yellow from yellow-green colour, close to colourless.
From the above, magnetic field induction photo catalysis reactor of the present invention effectively can process the photocatalytic oxidation reactor of organic pollutant, has application prospect.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a magnetic field induction photo catalysis reactor, is characterized in that: comprise miniature inductive formula light source, reaction tank and alternating magnetic field, and described miniature inductive formula light source is arranged in reaction tank, and described reaction tank is arranged in alternating magnetic field; Described alternating magnetic field makes miniature inductive formula light source luminescent by electromagnetic induction, forms the induction type photo catalysis reactor of alternating magnetic field and optically-coupled effect.
2. magnetic field induction photo catalysis reactor according to claim 1, is characterized in that: described miniature inductive formula light source is evenly distributed in reaction tank.
3. magnetic field induction photo catalysis reactor according to claim 1, it is characterized in that: described miniature inductive formula light source comprises miniature inductance coil and two LED, and the pin parallel connected in reverse phase of these two LED, the LED pin after parallel connection is simultaneously connected with miniature inductance coil two output pin.
4. magnetic field induction photo catalysis reactor according to claim 1, is characterized in that: the generator of described alternating magnetic field comprises alternating magnetic field generating coil and high-frequency alternating current origin system; Described reaction tank is arranged in alternating magnetic field generating coil; Described high-frequency alternating current origin system comprises signal source, control unit and power amplifier, and described signal source, power amplifier phase and alternating magnetic field generating coil connect successively, and described control unit is connected with power amplifier with signal source respectively; Described signal source, for generation of sinusoidal ac signal, after power amplifier amplifies, acts on alternating magnetic field generating coil, makes coil produce alternating magnetic field; And control unit is used for the size that control signal source produces sinusoidal ac signal frequency and control power amplifier amplified current.
5. magnetic field induction photo catalysis reactor according to claim 1, is characterized in that: described reaction tank is provided with fluid circulation system, described fluid circulation system comprises the liquid-inlet pipe, recycle liquid pump and the drain pipe that connect successively; Described drain pipe is connected with the upper end liquid outlet of reaction tank, and described liquid-inlet pipe is connected with the bottom fluid inlet of reaction tank.
6. magnetic field induction photo catalysis reactor according to claim 5, is characterized in that: be provided with microwell plate in described reaction tank, and described microwell plate is between the bottom fluid inlet and miniature inductive formula light source of reaction tank.
7. magnetic field induction photo catalysis reactor according to claim 1, it is characterized in that: described reaction tank is provided with inlet system, described inlet system comprises pneumatic pump, and described pneumatic pump is connected with the bottom of reaction tank by inlet pipe.
8. magnetic field induction photo catalysis reactor according to claim 1, is characterized in that: the wavelength 375-380nm of described LED; The number of turns of described alternating magnetic field generating coil is 100 circles, and the induction reactance of miniature inductance coil is 33mH, and internal resistance is 59 Ω.
9. based on a degraded using method for the magnetic field induction photo catalysis reactor described in claim 1-9, it is characterized in that, comprise the following steps, the first step, importing in reaction tank by waiting to need the waste liquid of degraded; Second step, by catalyzer TiO
2and H
2o
2put in reaction tank; 3rd step, frequency and the size of current passing into alternating magnetic field of adjustment alternating magnetic field; 4th step, opens the generator power supply of alternating magnetic field, degrades.
10. magnetic field induction photo catalysis reactor according to claim 9, is characterized in that: the frequency of described alternating magnetic field is adjusted by the control unit adjustment signal source sinusoidal ac signal frequency of high-frequency alternating current origin system; The size of current of alternating magnetic field is adjusted by the size of the amplification after-current of the control unit Modulating Power amplifier of high-frequency alternating current origin system; The alternating magnetic field frequency that signal source sinusoidal ac signal produces is 12KHz, and the amplification after-current of power amplifier is 2.0A.
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| CN104925897B (en) | 2017-07-18 |
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