KR101282438B1 - Waste Water Treatment Method And Waste Water Treatment Apparatus Using Ultrasound combined Solar Collector - Google Patents
Waste Water Treatment Method And Waste Water Treatment Apparatus Using Ultrasound combined Solar Collector Download PDFInfo
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- KR101282438B1 KR101282438B1 KR20110032742A KR20110032742A KR101282438B1 KR 101282438 B1 KR101282438 B1 KR 101282438B1 KR 20110032742 A KR20110032742 A KR 20110032742A KR 20110032742 A KR20110032742 A KR 20110032742A KR 101282438 B1 KR101282438 B1 KR 101282438B1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The present invention relates to a water treatment method and a water treatment apparatus having a high wastewater treatment efficiency by increasing the efficiency of the photocatalyst by combining the ultrasonic generator and the solar intensive reactor in order to remove contaminated substances in various wastewater.
Description
The present invention relates to a water treatment method and a water treatment apparatus having a high wastewater treatment efficiency by increasing the efficiency of the photocatalyst by combining the ultrasonic generator and the solar intensive reactor in order to remove contaminated substances in various wastewater.
In general, with the development of the industry, the generation of high concentration of hardly degradable wastewater increases significantly and the environmental pollution problem is getting serious. Therefore, regulations on pollutants are also being tightened. In accordance with this trend, various physical, biological and chemical methods have been applied to decompose / remove contaminants such as hardly decomposable substances. However, there are many difficulties in efficient treatment, such as low decomposition efficiency for many kinds of organic materials, and many methods generate many secondary by-products.
Conventional methods for removing contaminants in wastewater include adsorption removal using activated carbon, flocculation, chemical oxidation treatment such as fenton, and biological treatment using microorganisms. However, these methods have a fundamental problem. That is, in the adsorption treatment method using an adsorbent such as activated carbon, not only complete decomposition of contaminants by this method itself is required, but also a second process for removing the adsorbed contaminants is required. In the chemical oxidation treatment, in general, secondary decomposition such as incomplete decomposition of organic substances or a large amount of precipitated sludge is generated. In addition, even in the biological treatment widely used in water treatment, there is a problem that the treatment speed is relatively slow and the treatment conditions in which the entire reaction system exhibits biological activity are difficult. Therefore, these problems have led to an increase in the need for new water treatment technologies that can improve or replace existing water treatment methods.
The water treatment method using photocatalytic reaction, which has recently attracted much attention as a new pollutant treatment technology, is a process of directly decomposing and treating pollutants in water, and the effects of temperature, pH, and concentration of pollutants are relatively small. There is almost no restriction on. Therefore, the water treatment technology using the photocatalytic reaction can completely decompose harmful organic substances into carbon dioxide and water without generating secondary pollutants. Due to these advantages, the treatment of pollutants using photocatalytic reactions is very likely as a new method to replace the existing water treatment technology. The most representative photocatalyst is titanium dioxide (TiO 2 ). When the surface of TiO 2 is irradiated with an energy larger than the band gap, that is, ultraviolet rays of 400 nm or less, in the valence band and the conduction band, a hole (h +) and electrons (e -) is generated, wherein the generated electrons and the major is moved in the photocatalytic surface of the conduction band electrons are the heavy metal ions (Mx +) and oxygen (O 2) adsorbed electrochemically After the photoreduction of heavy metal ions, or to produce a superoxide radical (superoxide radical), the superoxide radical directly decomposes the organic material or generates OH radicals. In addition, holes in the valence band react with water molecules to generate OH radicals, thereby oxidizing organic substances adsorbed on the surface of the photocatalyst particles.
To improve the efficiency of the photocatalyst, first, various photocatalyst manufacturing techniques that can increase the specific surface area, addition of nonmetals such as platinum, which have a high affinity for electrons, and other metal oxides for selectively inducing redox reactions Addition etc. are mentioned.
However, one of the biggest limitations in the treatment of pollutants with photocatalytic reactions is the use of ultraviolet lamps as light sources to induce photocatalytic reactions. The energy cost of using ultraviolet lamps is recognized as the biggest disadvantage of photocatalytic reactions in terms of cost benefits compared to other water treatment methods that can be used to treat hardly contaminated pollutants.
Therefore, the solar reactor used to solve this problem uses photovoltaic or solar heat, or complex photovoltaic and heat as energy sources, and uses photocatalysts of semiconducting properties. There is no problem of secondary environmental pollution.
In general, the sun's UV-flux reaching the earth's surface is 20-30 Wm -2 , and the energy of the sun's UV-A (300-400nm) is 0.2-0.3 mol photon m -2 h -1 . This amount of photon is a suitable amount to decompose contaminants in the photocatalytic process. However, the use of such a solar reactor had a difficulty in limiting the treatment efficiency of solar-photocatalysis by changing the light intensity of the sun according to weather or time in using the sun. In order to solve this problem, research is continuously conducted.
Accordingly, an object of the present invention is to provide a water treatment method and a water treatment apparatus having a high wastewater treatment efficiency because the efficiency of photocatalyst treatment is increased by continuously combining the ultrasonic generator and the solar intensive reactor.
In order to solve the above object, the present invention is a method for treating contaminants in waste water,
Introducing a photocatalyst into the wastewater;
Ultrasonic treatment step of irradiating the ultrasonic wave to the wastewater in which the photocatalyst is injected; And
After the sonication, the photocatalyst treatment step of decomposing contaminants in the wastewater by condensing and reflecting sunlight to the wastewater by using a concentrated solar reactor provides a water treatment method.
In addition, the present invention is a device for treating contaminants in waste water,
A reservoir for storing waste water;
An ultrasonic generator coupled to the reservoir;
A circulation pump connected to the storage tank through a pipe, the circulation pump being a means for supplying the wastewater to the solar intensive reactor;
A photovoltaic concentrated reactor connected to a pipe of the storage tank and the circulation pump and condensing and reflecting sunlight to irradiate the wastewater; and
It is connected to the reservoir provides a water treatment apparatus comprising a photocatalyst storage tank for supplying a titanium dioxide photocatalyst.
The water treatment method and water treatment apparatus using the ultrasonically coupled photovoltaic reactor of the present invention increases the efficiency of photocatalyst treatment, and thus has an excellent effect of removing contaminants in wastewater, and is used in combination with the photovoltaic reactor and the ultrasonic generator. And it is possible to continuously effective water treatment using solar light without being limited in time, by using the solar light has the effect of reducing the cost of maintenance and maintenance of the device, energy saving and environmental improvement by replacing artificial ultraviolet rays.
1 is a diagram schematically illustrating a water treatment apparatus using an ultrasonic coupled solar reactor according to one embodiment of the present invention.
FIG. 2 illustrates a side view of complex parabola concentrators (CPCs) as a photovoltaic reactor used in the present invention.
3 shows the results of the photocatalytic reaction by the ultrasonic wave according to Test Example 1, (a) shows the results of the pollutant removal efficiency using the process of Example 1 and Comparative Examples 1 to 3 using the ultrasonic frequency 35kHz (B) shows the result of the pollutant removal efficiency using the process of Example 2 and Comparative Examples 1, 4 and 5 using the ultrasonic frequency 283kHz.
Figure 4 shows the results showing the particle size distribution of the titanium dioxide photocatalyst according to the ultrasonic frequency according to Test Example 2.
Figure 5 (a) is a result showing the average particle size with time for the ultrasonic frequency according to Test Example 2, (b) is a result showing the change in specific surface area with time for the ultrasonic frequency according to Test Example 2. to be.
FIG. 6 shows the results of fruit generation with time by
7 is a graph showing the decomposition result of chloroform over time according to the photocatalyst concentration of Test Example 2 for one embodiment of the present invention.
Figure 8 (a) is a photograph showing the water treatment apparatus according to an embodiment of the present invention, (b) is a photograph of the ultrasonic generator used in one embodiment of the present invention, (c) is an embodiment of the present invention Photographs of the CPC solar intensive reactor used in the photo are shown.
Hereinafter, the present invention will be described in more detail.
The present invention is a water treatment method for removing contaminants in waste water,
Introducing a photocatalyst into the wastewater;
Ultrasonic treatment step of irradiating the ultrasonic wave to the wastewater in which the photocatalyst is injected; And
After the ultrasonic treatment, and a photocatalyst treatment step of decomposing contaminants in the waste water by condensing and reflecting sunlight to the waste water by using a solar intensive reactor.
The solar intensive reactor can be used as long as it is commonly used in the art, preferably compound parabolic concentrators (CPCs), double skin sheet reactor (DSSR), thin film fixed bed (FFFBR) Reactor), and more preferably, using CPCs is the best in terms of solar utilization efficiency.
In this case, the CPCs are collectors that collect and collect solar radiation, and thus the reflector can collect both direct and scattered solar radiation without sun tracking.
The photocatalyst may be used as long as it is commonly used in the art, but preferably titanium dioxide (TiO 2 ) may be used, and more preferably, powdered titanium dioxide (TiO 2 ) is used.
The injection amount of the photocatalyst is preferably 0.2 to 1 g per 1 L of wastewater, more preferably 0.2 to 0.4 g per 1 L of wastewater, and most preferably 0.2 g per 1 L of wastewater. The amount of catalyst injected is optimal in terms of recovery and use cost of the catalyst in the above range.
When the photocatalyst is irradiated with ultraviolet light having a wavelength range of 300 to 400 nm emitted from sunlight or fluorescent lamps, the strong oxidation and reduction reaction proceeds.
In the ultrasonic treatment step of irradiating the ultrasonic wave to the wastewater into which the photocatalyst is added, when titanium dioxide is added as a photocatalyst to the treatment solution (wastewater) and the ultrasonic wave is injected, the contraction and expansion between the molecules of the solution occur for a very short time due to the wave energy. In addition, the phenomenon in which the micro-bubbles are generated and disappeared by the molecular swept phenomenon repeatedly occurs. These bubbles are generated and then disappeared, causing local bubbles to decay.At this time, ultra-high temperature and ultra-high pressure zones are generated, and titanium dioxide is crushed or chemical bonding is possible through melting of the surface of the particles. Is done. The finely divided titanium dioxide is effective in decomposing and removing contaminants in the waste water because the particle size decreases and the specific surface area increases, thereby increasing the catalytic activity.
The frequency of the ultrasonic wave is preferably 20 to 1000 kHz, more preferably 30 to 300 kHz, and most preferably 30 to 40 kHz.
The ultrasonic wave has a main reaction mechanism according to the frequency domain. In the low frequency (20-100 kHz) region, the physical effects of microbubbles such as microstreaming and shock wave predominate, and high frequency (100-1000 kHz). ), Chemical effects such as pyrolysis and radical reaction dominate. In the low frequency region of 30 to 40 kHz, which is the most preferable ultrasonic frequency region of the present invention, the properties (size, specific surface area) of the photocatalyst may be changed according to the physical effects occurring, thereby exhibiting an excellent effect of removing contaminants.
In the water treatment of the present invention, the reaction temperature may be carried out in a range commonly used in the art, but is preferably at room temperature of 15 to 25 ℃.
The water treatment method may remove the hardly decomposable substance in the wastewater by using a photocatalytic reaction, and preferably, may remove the chloroform.
In addition, the present invention is a water treatment apparatus for removing contaminants in waste water,
A reservoir for storing waste water;
An ultrasonic generator coupled to the reservoir;
A circulation pump connected to the storage tank through a pipe, the circulation pump being a means for supplying the wastewater to the solar intensive reactor;
A photovoltaic concentrated reactor connected to a pipe of the storage tank and the circulation pump and condensing and reflecting sunlight to irradiate the wastewater; and
The present invention relates to a water treatment apparatus including a photocatalyst storage tank connected to the reservoir to supply a titanium dioxide photocatalyst, and a schematic diagram of the present invention is shown in FIG. 1.
The ultrasonic generator may be used as long as it is commonly used in the art, but preferably, a cup horn type transducer may be used.
The solar intensive reactor can be used as long as it is conventionally used in the art, preferably compound parabolic concentrators (CPCs), double skin sheet reactor (DSSR), thin film fixed bed reactor (FFFBR) ), And more preferably using CPCs is the best in terms of solar utilization efficiency.
Here, the CPCs are collectors that collect and collect solar radiation, and thus the reflector can collect both direct and scattered solar radiation without sun tracking, so that the CPCs can be fixedly installed, and a side view thereof is shown in FIG. 2.
The injection amount of the photocatalyst is preferably 0.2 to 1 g per 1 L of wastewater, more preferably 0.2 to 0.4 g per 1 L of wastewater, and most preferably 0.2 g per 1 L of wastewater. The amount of catalyst injected is optimal in terms of recovery and use cost of the catalyst in the above range.
When the photocatalyst is irradiated with ultraviolet light having a wavelength range of 300 to 400 nm emitted from sunlight or fluorescent lamps, a strong oxidation and reduction reaction proceeds.
The frequency of the ultrasonic wave is preferably 20 to 1000 kHz, more preferably 30 to 300 kHz, and most preferably 30 to 40 kHz.
The ultrasonic wave has a main reaction mechanism according to the frequency domain. In the low frequency (20-100 kHz) region, the physical effects of microbubbles such as microstreaming and shock wave predominate, and high frequency (100-1000 kHz). ), Chemical effects such as pyrolysis and radical reaction dominate. In the low frequency region of 30 to 40 kHz, which is the most preferable ultrasonic frequency region of the present invention, the properties (size, specific surface area) of the photocatalyst may be changed according to the physical effects occurring, thereby exhibiting an excellent effect of removing contaminants.
The water treatment apparatus of the present invention can remove hardly decomposable substances in wastewater by using a photocatalytic reaction, and preferably can remove chloroform.
However, the present invention will be described in more detail with reference to the following examples and test examples. These examples and test examples are merely illustrative of the present invention, the content of the present invention is not limited by the following examples and test examples.
Examples 1-2 and Comparative Examples 1-5
Chloroform (Chloroform, C2432, Sigma-Aldrich, USA) was used as the target material. Commercially available TiO 2 powder (Degussa, P25, Germany) was used as catalyst.
Figure 1 is an embodiment of the present invention, schematically shows a configuration for the experiment. As a light source, two pairs of metalhalide lamps (400W, 250W, Osram, Slovakia) as artificial solar light sources were installed on the ceiling of the
The CPCs reactor is composed of an acrylic module having one quartz tube (120 cm long, 3 cm in diameter, 1.5 mm thick) and a reflector made of polished aluminum. 4 L of treatment solution is recycled from the reservoir to the CPCs reactor by a magnetic centrifugal pump (MD-40, Iwaki, Japan). This system was implemented in a closed loop to prevent volatile loss of chloroform. Two ultrasonic transducer modules (Mirae Ultrasonic Tech, South Korea) at 35 kHz and 283 kHz were placed under the reservoir. The ultrasonic power supply is 80 W, and the power density is 0.02 W / ml. The temperature of the water was maintained at 20 ± 3 ° C. using a circulating cooling system. The concentration of chloroform was measured by gas chromatography (6890N, Agilent, USA) with purge & trap (Velocity XPt, Teledyne Tekmar, USA) and flame ionization detector (FID).
Figure 8 (a) is a photograph showing the water treatment apparatus according to an embodiment of the present invention, (b) is a photograph of the ultrasonic generator used in one embodiment of the present invention, (c) is an embodiment of the present invention Photographs of the CPC solar intensive reactor used in the photo are shown.
As shown in Table 1, the experiments were conducted in the configurations of Examples 1 to 2 and Comparative Examples 1 to 5. (+: Ultrasonic irradiation, solar intensive reactor on, titanium dioxide injection,-: No ultrasonic irradiation, solar intensive off, no titanium dioxide injection)
Test Example 1. Contaminant Removal Efficiency by Ultrasonic Coupling
Using Example 1 to 2 and Comparative Examples 1 to 5 were measured the removal efficiency of the contaminants due to the photovoltaic reactor and ultrasonic coupling. As a contaminant, the experiment was performed using chloroform. Wastewater containing 10 ppm of chloroform (C2432, Sigma-Aldrich, USA) was treated in a process consisting of Examples 1-2 and Comparative Examples 1-5, respectively.
At this time, the frequency of the ultrasonic (Ultrasound, US) was used at 35kHz or 283kHz, the concentration of TiO 2 is 0.2g / L, the removal efficiency of the chloroform with respect to the time according to the process of Examples and Comparative Examples 3 and Table 2 is shown.
Figure 3 (a) shows the results of the pollutant removal efficiency using the process of Example 1 and Comparative Examples 1 to 3 using the ultrasonic frequency 35kHz, (b) Example 2 using the ultrasonic frequency 283kHz; And it shows the results of the pollutant removal efficiency using the process of Comparative Examples 1, 4, 5.
As shown in FIG. 3, when comparing Example 1 and Comparative Examples 1 to 3 using the frequency of 35 kHz shown in (a), the chloroform removal efficiency after 200 minutes was 80% in Example 1. , Comparative Examples 1, 2 and 3 were found to be 22.5%, 49% and 46%, respectively.
Referring to the results shown in (b) of FIG. 3, the chloroform removal efficiency after 200 minutes was 64.4% in Example 2, and Comparative Examples 1, 4, and 5 were 22.5%, 52.6%, and 47%, respectively. Appeared.
In addition, when comparing similar primary reaction rate constants (k) as shown in Table 2, the solar / ultrasound / TiO 2 process was used rather than the comparative examples of the ultrasonic, ultrasonic / TiO 2 and solar / TiO 2 processes. Chloroform removal rate was shown to be fast, and the efficiency was higher when the ultrasound frequency of 35 kHz was injected than 283 kHz.
Thus, Examples 1 to 2 were found to remove chloroform, which is a contaminant in the wastewater, more efficiently than Comparative Examples 1 to 5, and contaminant removal at 35 kHz was more effective than 283 kHz.
Test Example 2 Comparison of Catalyst Particle Size and Specific Surface Area According to Ultrasonic Frequency
A particle size analyzer (Particle size analyzer, Mastersizer micro, Malvern, USA) was used to measure the photocatalyst particle size and specific surface area change.
Figure 4 shows the particle distribution of the catalyst according to the ultrasonic frequency of the present invention.
As a result, it was found that the catalyst particles treated at the ultrasonic frequency of 35 kHz were distributed more in a smaller particle size than the particles of the catalyst treated at 283 kHz.
Figure 5 (a) is the result showing the average particle size with time with respect to the ultrasonic frequency, (b) is the result showing the change in specific surface area with time with respect to the ultrasonic frequency. As shown in FIG. 5, the catalyst treated with an ultrasonic frequency of 35 kHz was found to have a small average particle size over time, and the specific surface area was increased.
FIG. 6 shows the results of hydrogen peroxide generation with time by
Test Example 3 Contaminant Removal Efficiency According to Photocatalyst Concentration
In order to determine the efficiency of removing contaminants according to the concentration of the photocatalyst, the injection concentration of the catalyst was adjusted to 0.1 g / L, 0.2 g / L, 0.5 g / L and 1.0 g /, respectively, using the process configured in Example 1. Comparison was made by injection into L. At this time, as a pollutant, wastewater containing 10 ppm of chloroform (C2432, Sigma-Aldrich, USA) was treated, and the results are shown in FIG.
According to the results of FIG. 7, the concentration of the photocatalyst showed similarly effective removal efficiency at 0.2 to 1 g per 1 L of wastewater, and according to the cost of use, contaminant removal efficiency was optimal at the concentration of 0.2 g / L. appear.
Claims (7)
Miniaturizing the photocatalyst by irradiating ultrasonic waves having a frequency of 30 to 40 kHz to the wastewater into which the photocatalyst is introduced; and
After the ultrasonic irradiation, the photocatalyst treatment step of decomposing contaminants in the waste water by condensing and reflecting sunlight to the waste water by using a solar intensive reactor,
The solar intensive reactor is a water treatment method, characterized in that the combined parabola concentrators (CPCs).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104528871A (en) * | 2015-01-04 | 2015-04-22 | 安徽理工大学 | Solar photocatalytic degradation device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003251341A (en) | 2002-03-05 | 2003-09-09 | Mitsubishi Heavy Ind Ltd | Water treatment apparatus |
| KR20030094948A (en) * | 2002-06-10 | 2003-12-18 | (주)크로바 환경 | A Process and a machine for a waste Water disposal Plant |
| JP2004148285A (en) | 2002-10-29 | 2004-05-27 | Kiyoaki Yoshii | Fresh water sterilization device |
| KR20100098582A (en) * | 2010-07-17 | 2010-09-08 | 임광희 | Method to treat municipal/industrial wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003251341A (en) | 2002-03-05 | 2003-09-09 | Mitsubishi Heavy Ind Ltd | Water treatment apparatus |
| KR20030094948A (en) * | 2002-06-10 | 2003-12-18 | (주)크로바 환경 | A Process and a machine for a waste Water disposal Plant |
| JP2004148285A (en) | 2002-10-29 | 2004-05-27 | Kiyoaki Yoshii | Fresh water sterilization device |
| KR20100098582A (en) * | 2010-07-17 | 2010-09-08 | 임광희 | Method to treat municipal/industrial wastewater |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528871A (en) * | 2015-01-04 | 2015-04-22 | 安徽理工大学 | Solar photocatalytic degradation device |
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