This application is based upon and claims the benefit of priority from prior Japanese Patent Applications No. 2004-026615, filed Feb. 3, 2004; No. 2004-075043, filed Mar. 16, 2004; No. 2004-121996, filed Apr. 16, 2004; and No. 2005-002932, filed Jan. 7, 2005, the entire contents of all of which are incorporated herein by reference.
1. Field of the Invention
The present invention relates to an apparatus for water treatment using radical generated by electric discharge.
2. Description of the Related Art
Recently, in addition to the water treatment method using chlorine, the water treatment method using the oxidation reaction of ozone (O3) is being applied. Both methods utilize the chemically strong oxidation power of an oxidant to decompose organic matter dissolved in the water.
In oxidation power, ozone is as high as 2.07 electron volts while chlorine is 1.4 electron volts. When chlorine reacts with the organic matter formed in high molecular compounds, by-products such as chloroprene, trihalomethane, haloacetic acid, haloketone, and haloacetonitrile are generated. In some of the by-products, the possibility of a cancer-causing substance is suggested. The by-products of disinfection are harmful to humans.
In contrast, because ozone is formed only by oxygen atoms, the environmental risk is small, and ozone is effective in decomposing the organic matter. Therefore, ozone is widely used in water treatment plants. This is the reason why recently the water treatment method using ozone has become widespread.
However, ozone cannot decompose recalcitrant organic matter like dioxins, agricultural chemicals, and endocrine-disruptors. Further, ozone reacts with organic matter to form aldehydes.
In order to decompose and treat recalcitrant organic matter by using chemical reaction, it is necessary to use an oxidant that has a higher oxidation potential than ozone. Specifically, a hydroxyl radical (OH radical) and an oxygen atom radical (O radical) have oxidation powers of 2.85 electron volts and 2.42 electron volts, respectively, and these values are higher than that of ozone. The OH radical and the O radical have a reaction rate coefficient higher than that of ozone for recalcitrant organic matter. Therefore, the OH radical and the O radical can decompose and treat recalcitrant organic matter like dioxins. Hereinafter the OH radical, the O radical, and the like are collectively called radicals.
The radicals are generated in the electric discharge under conditions of humidity and presence of oxygen. Conventionally, a treatment method using corona discharge to decompose harmful substances has been proposed (for example, see Jpn. Pat. Appln. KOKAI Publication No. 2001-70946).
A treatment method using reactive gas including radicals at low temperature is also proposed (for example, see Jpn. Pat. Appln. KOKAI Publications No. 2003-80059 and No. 2003-80058). Further, the treatment method using radicals generated by plasma in waste water to be treated has also been proposed (for example, see Jpn. Pat. Appln. KOKAI Publication No. 2000-288547).
The radicals obtained by the above-described electric discharge have extremely high reactivity, and are extinguished immediately after being generated. In order to decompose the recalcitrant organic matter dissolved in the water by using the radicals, it is necessary that the radicals be dissolved in the water immediately after being generated. Alternatively, it is necessary that the lifetime of the radicals be lengthened.
However, a technology that lengthens the lifetime of the generated radicals has not been established yet. Accordingly, even if the radical treatment method by electric discharge is simply applied to water treatment, there is a problem in that the efficiency of the water treatment is not so high.
In accordance with an aspect of the present invention, there is provided an apparatus that can improve efficiency of organic matter decomposing treatment in a radical treatment apparatus using electric discharge.
The apparatus for radical treatment comprises a gas unit to introduce gas for generating a radical; a power supply to produce an electric discharge by high voltage; and an electrode unit including an electrode member which discharges at a leading edge opposite to a treatment object matter, the electric discharge being generated according to the electric discharge high voltage in an atmosphere of the gas.
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention, and together with the general description given above and the detailed description of the embodiments given below, serve to explain the principles of the invention.
Referring to the accompanying drawings, preferred embodiments of the invention will be described below.
(First Embodiment)
The main body of the apparatus is a treatment water tank 1 for storing treatment water 2 therein. A typical example of the treatment water 2 stored in the treatment water tank 1 includes the organic matter that is difficult to decompose. Examples of the treatment water 2 also include wastes, leaching water of a disposal site, dioxins, industrial wastewater, wastewater containing house drainage, and treatment water of clean water and sewage. Usually the treatment water 2 is stirred in the treatment water tank 1.
An electrode unit is provided in the treatment water tank 1. The electrode unit includes a plurality of first electrodes (projection members) 4 and a second electrode 3. The first electrodes 4 having hollow cylindrical structures are arranged near a surface (water surface) 20 of the treatment water 2, and the first electrodes 4 have electric discharge portions 40. The second electrode 3 is arranged in the treatment water 2, and the second electrode 3 constitutes a ground electrode.
In the electrode unit, a high voltage is applied between the first electrode 4 and the second electrode 3 from a power supply 5 to generate corona discharge. The electrode unit is attached to the treatment water tank 1 made of, for example, stainless steel through an insulating portion 6. It is possible that a pulse power supply that generates a high-voltage pulse is used as the power supply 5.
A gas tank 9 that accumulates gas 70 is provided on the treatment water tank 1. The gas tank 9 includes a gas inflow pipe 7 and a gas outflow pipe 8. The gas 70 that is of air containing moisture or oxygen flows into the gas tank 9 through the gas inflow pipe 7, and the gas 70 flows out of the gas tank 9 through the gas outflow pipe 8.
(Functional Effect of First Embodiment)
Referring to
The gas 70 such as air containing moisture is caused to flow in the gas tank 9 through the gas inflow pipe 7. As shown in
The first electrodes 4 are arranged on the water surface 20 of the treatment water 2 at even intervals, so that the gas 70 is evenly blown onto the water surface 20 of the treatment water 2. Therefore, the gas 70 can be efficiently blown onto the treatment water 2.
When the high voltage is applied to the electrode unit from the power supply 5, the electric discharge such as the corona discharge is occurred in the electric discharge portion 40 that is located at the tip of the first electrode 4. The electric discharge portion 40 is arranged near the water surface 20 of the treatment water 2. Accordingly, both the gas 70 from the gas flow path 41 and a radical generated by the electric discharge, portion 40 are blown so as to impinge on the water surface 20 of the treatment water 2.
As used herein, the term “radical” means a general term for the radicals, such as an OH radical, which is generated through a reaction of the gas 70 by the electric discharge.
Thus, according to the apparatus of the embodiment, before the radical generated by the electric discharge disappears, the radical can be dissolved in the treatment water 2 for a short time by actively blowing the gas 70 from the gas flow path 41 to the treatment water 2. Accordingly, the dissolved radical can react with the organic matter, which is dissolved in the water and difficult to decompose, to efficiently decompose the organic matter while the dissolved radical is in the valid state before disappearance.
Next, the principle of a process for generating the radical by the electric discharge from the electrode unit will be described.
When the electric discharge is occurred in an atmosphere of air containing oxygen (O atom), an oxygen atom O(3P) in a ground state or an oxygen atom O(1D) in a excited energy level are generated by a collision between an electron e and a gas molecule in the electric discharge. This state is expressed by the following chemical formula (1):
e+O2→O(1D)+O(3P) (1)
wherein O(1D) reacts with a water molecule. Then OH is produced. .OH means a hydroxyl radical (hereinafter referred to as OH radical) Namely, the following chemical formula (2) is valid:
O(1D)+H2O→2.OH (2)
The O(3P) atom generates ozone 03 by a triple collision of O(3P), an O2 molecule, and a natural molecule M. Namely, the following chemical formula (3) is valid:
O(3P)+O2+M→O3+M (3)
A hydrogen atom H and the OH radical are generated by the direct collision between the water molecule and the electron. This state is expressed by the following chemical formula (4):
e+H2O→H+.OH (4)
Hydrogen peroxide H2O2 is also generated from the OH radical. This state is expressed by the following chemical formula (5):
.OH+.OH→H2O2 (5)
The O atom, the OH radical, the ozone, and the hydrogen peroxide, which are generated above-described reactions, are dissolved into the treatment water by diffusion, and gas flow as the radical, thereby the treatment is performed.
In direct treatment, the OH radical generated by the electric discharge is dissolved into the treatment water 2, and the OH radical reacts immediately with the recalcitrant organic matter, and the OH radical resolve the organic matter to water H2O, carbon dioxide CO2, and hydrogen peroxide H2O2. This state is expressed by the following chemical formula (6):
.OH+R→H2O+CO2+H2O2 (6)
On the other hand, in indirect treatment, the OH radical is generated by the reaction of the ozone and hydrogen peroxide, which are generated from the electric discharge, and the OH radical resolves the recalcitrant organic matter.
When the hydrogen peroxide is dissolved in the water, the hydrogen peroxide is dissociated to form HO2− and a hydrogen ion H+. This state is expressed by the following chemical formula (7):
H2O2HO2−+H+ (7)
The generated HO2− reacts with O3 to form O3− and an HO2 radical. This state is expressed by the following chemical formula (8):
HO2−+O3→O3−+HO2. (8)
The generated HO2. is dissociated to form O2− and H+. This state is expressed by the following chemical formula (9):
HO2.O2−+H+ (9)
The generated O2− reacts with the ozone to form O3−. This state is expressed by the following chemical formula (10):
O2−+O3→O3−+O2 (10)
O3− reacts with H+ to form HO3. This state is expressed by the following chemical formula (11):
O3−+H+→HO3 (11)
HO3 is dissociated to form the OH radical. This state is expressed by the following chemical formula (12):
HO3→.OH+O2 (12)
Thus, the radicals generated by the electric discharge are dissolved into the treatment water 2, and the water treatment performed on the treatment water 2 by the radical in the two stages of the direct treatment and the indirect treatment.
(Second Embodiment)
The apparatus of the second embodiment has a configuration in which a periphery of the hollow cylindrical structure main body having the gas flow path 41 is covered with a dielectric member 11 such as quartz glass in each first electrode 4. The electric discharge portion 40 located at the leading edge of each first electrode 4 is arranged in the treatment water 2. Because a gas space is formed at the leading edge of the first electrode 4, the leading edge is not in direct contact with the treatment water 2.
The functional effect of the second embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the gas tank 9 through the gas inflow pipe 7. According to internal pressure of the gas tank 9, the gas 70 flows into the gas flow paths 41 of the first electrodes 4.
When the high voltage is applied to the electrode unit from the power supply 5, the electric discharge such as the corona discharge is generated in the electric discharge portion 40 located at the leading edge of the first electrode 4. Although the electric discharge portion 40 is arranged in the treatment water 2, a gas space is formed by the cover of the dielectric member 11 and the gas 70 blown so as to impinge in the treatment water 2 through the gas flow path 41. Namely, the electric discharge is generated at the portion 40 in the gas space formed at the leading edge of the first electrode 4.
In the electric discharge portion 40, the radical is generated from the gas 70 through the gas flow path 41 by the electric discharge. Both the radical and the gas 70 are blown into the treatment water 2. Therefore, bubbles 10 are generated by the gas 70 at the leading edge of the first electrode 4.
Thus, according to the second embodiment, the electric discharge portion 40 is arranged in the treatment water 2, so that the blown gas 70 and the radical can be dissolved into the treatment water 2 while the radical is in the valid state. Accordingly, the radical generated by the electric discharge can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Third Embodiment)
In the apparatus of the third embodiment, the electrode unit is provided in a lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. The electrode unit is attached to a bottom portion of the treatment water tank 1 made of, for example, stainless steel through the insulating portion 6.
The first electrode 4 includes a needle-shaped electrode member to which the high voltage necessary to the electric discharge is applied from the power supply 5. The second electrode 3 is formed by a plate member, and an opening 30 is formed at a position opposite to the leading edge of each first electrode 4. Since the gas space is formed at the leading edge of the first electrode 4, the leading edge is not in direct contact with the treatment water 2.
In the apparatus of the third embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the third embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to inflow pressure, the gas 70 is blown into the treatment water 2 from the openings 30 provided in the second electrode 3, which allows the gas space to be formed at the leading edge of the first electrode 4 opposite to the opening 30.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated by the gas 70 at the leading edges of the first electrodes 4.
Thus, according to the third embodiment, the leading edge of the first electrode 4 which is of the portion as electric discharge is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the blown gas 70 and the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
Further, in the third embodiment, since the first electrode 4 to which the high voltage is applied is the needle-shaped (pin) electrode, an electric field can concentrate on the leading edge of the first electrode 4, which allows the electric discharge to be generated at a relatively low voltage.
(Fourth Embodiment)
In the apparatus of the fourth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank-1. The electrode unit includes the first electrode 4 and the second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged parallel to the first electrode 4 in the treatment water 2. As shown in
The first electrode 4 of the fourth embodiment is formed by the electrode member having a metal mesh structure to which the high voltage necessary to the electric discharge is applied from the power supply 5. The second electrode 3 is formed by the plate-shaped member and arranged parallel to the first electrode 4, and the plurality of openings 30 are formed in the second electrode 3. Since the gas space is formed in the first electrode 4, the leading edge is not in direct contact with the treatment water 2.
In the apparatus of the fourth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
A functional effect of the fourth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the mesh of the first electrode and the openings 30 provided in the second embodiment 3, which allows the gas space to be formed at the leading edge of the first electrode 4 near the openings 30.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is produced from the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated by the gas 70 at the leading edges of the first electrodes 4.
Thus, according to the fourth embodiment, the leading edge of the first electrode 4 which is of the portion is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can further efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
Further, in the fourth embodiment, since the first electrode 4 has the metal mesh structure, the electric discharge can be generated in the wide range, which allows electric discharge efficiency to be relatively improved.
(Fifth Embodiment)
In the apparatus of the fifth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the first electrode 4 and the second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged parallel to the first electrode 4 in the treatment water 2. As shown in
The first electrode 4 of the fifth embodiment is formed by the plate-shaped electrode member to which the high voltage necessary to the electric discharge is applied from the power supply 5. The second electrode 3 is formed by the plate-shaped member, and the plurality of openings 30 are formed in the second electrode 3. Since the gas space is formed in the first electrode 4, the first electrode 4 is not in direct contact with the treatment water 2.
In the apparatus of the fifth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the fifth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the openings 30 provided in the second embodiment 3, which allows the gas space to be formed at a part of the first electrode 4, which is located near the opening 30.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the part of the first electrode 4. Accordingly, at the part of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated by the gas 70 at the openings 30 provided in the second electrode 3.
Thus, according to the fifth embodiment, the first electrode 4 which is of the electric discharge portion is in the same state as the state in which the first electrode 4 is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Sixth Embodiment)
In the apparatus of the sixth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the first electrode 4 and the second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged parallel to the first electrode 4 in the treatment water 2. As shown in
The first electrode 4 of the sixth embodiment is formed by the plate-shaped electrode member to which the high voltage necessary to the electric discharge is applied from the power supply 5, and a plurality of openings 42 are formed in the first electrode 4. The second electrode 3 is formed by the plate-shaped member, and the plurality of openings 30 are formed in the second electrode 3. Since the gas space is formed in the first electrode 4, the first electrode 4 is not in direct contact with the treatment water 2.
In the apparatus of the sixth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the sixth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the openings 42 provided in the first electrode 4 and the openings 30 provided in the second embodiment 3, which allows the gas space to be formed at the openings 42 of the first electrode 4, which are located near the openings 30.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the openings 42 of the first electrode 4. Accordingly, at the openings 42 of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated by the gas 70 at the openings 30 provided in the second electrode 3.
Thus, according to the sixth embodiment, the first electrode 4 which is of the electric discharge portion is in the same state as the state in which the first electrode 4 is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the recalcitrant organic matter dissolved in the water can efficiently be decomposed by the radical.
(Seventh Embodiment)
In the apparatus of the seventh embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the first electrode 4, the dielectric member 11 made of the quartz glass, and the second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged parallel to the first electrode 4 in the treatment water 2. As shown in
The electrode unit of the seventh embodiment includes the first electrode 4 and the dielectric member 11. The high voltage to occur the electric discharge is applied from the power supply 5 to the first electrode 4. The dielectric member 11 is located between the plate-shaped first electrode 4 and the plate-shaped second electrode 3 arranged in parallel with the first electrode 4. Through-holes 90 which pierce through the first electrode 4, the dielectric material 11, and the second electrode 3 are made in the electrode unit. The through-hole 90 forms the gas flow path which blows the gas 70 from the opening 42 located on the side of the first electrode 4 to the opening 30 located on the side of the second electrode 3. Since the gas space is formed in the through-hole 90, the through-hole 90 is not in direct contact with the treatment water 2.
In the apparatus of the seventh embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the seventh embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 flows into the through-holes 90 from the openings 42 provided in the first electrode 4, and the gas 70 is blown into the treatment water 2 from the openings 30 provided in the second electrode 3, which allows the gas space to be formed in the through-hole 90.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the through-holes 90. Accordingly, in the through-hole 90, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated by the gas 70 at the openings 30 provided in the second electrode 3.
Thus, according to the seventh embodiment, the through-hole 90 which is of the electric discharge portion is in the same state as the state in which the first electrode 4 is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the recalcitrant organic matter dissolved in the water can efficiently be decomposed by the radical.
(Eighth Embodiment)
In the apparatus of the eighth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the first electrode 4 and the second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged parallel to the first electrode 4 in the treatment water 2. As shown in
The first electrode 4 of the eighth embodiment is formed by the linear electrode member (wire electrode) to which the high voltage necessary to the electric discharge is applied from the power supply 5. The second electrode 3 is formed by the plate-shaped member, and the plurality of openings 30 are formed in the second electrode 3.
In the apparatus of the eighth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the eighth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the openings 30 provided in the second embodiment 3, which allows the gas space to be formed at a part of the first electrode 4, which is located near the opening 30.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the part of the first electrode 4. Accordingly, at the part of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated by the gas 70 at the openings 30 provided in the second electrode 3.
Thus, according to the eighth embodiment, the first electrode 4 which is of the electric discharge portion is in the same state as the state in which the first electrode 4 is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the recalcitrant organic matter dissolved in the water can efficiently be decomposed by the radical.
(Ninth Embodiment)
In the apparatus of the ninth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the plate-shaped second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. The electrode unit is attached to the bottom portion of the treatment water tank 1 made of, for example, a corrosion resistant metal material such as stainless steel through the insulating portion 6.
The first electrode 4 includes the needle-shaped electrode member to which the high voltage necessary to the electric discharge is applied from the power supply 5, and the periphery of the electrode member is covered with the dielectric member 11 made of, for example, quartz glass. In the first electrode 4, a gas flow path 110 through which the gas 70 flows is formed between the dielectric member 11 and the needle-shaped electrode member.
In the apparatus of the ninth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the third embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the gas flow paths 110 provided in the first electrode 4, which allows the gas space to be formed at the leading edge (electric discharge portion 40) of the first electrode 4 opposite to the second electrode 3, and the leading edge is not in direct contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2. Therefore, the bubbles 10 are generated by the gas 70 near the leading edges of the first electrodes 4.
Thus, according to the ninth embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Tenth Embodiment)
In the structure of the electrode unit according to the tenth embodiment, the needle-shaped electrode member that is arranged in a through-hole 120 forms the first electrode 4. The through-hole 120 is made in a glass member 12 that is arranged parallel to the second electrode 3. The first electrode 4 has the structure, in which the space between the needle-shaped electrode members is eliminated and the treatment water 2 does not enter the space. The through-hole 120 corresponds to the gas flow path 110 shown in
The functional effect of the third embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the through-holes 120 provided in the glass member 12, which allows the gas space to be formed at the leading edge (electric discharge portion 40) of the first electrode 4 opposite to the second electrode 3, and the leading edge is not in direct contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in the through-hole 120 from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2. Therefore, the gas 70 near the leading edges of the first electrodes 4 generates the bubbles 10.
Thus, according to the tenth embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Eleventh Embodiment)
In the apparatus of the eleventh embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the plate-shaped second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. In the second electrode 3, the plurality of openings 30 are formed at the position opposite to the leading edges of the first electrodes 4 (electric discharge portions 40).
The first electrode 4 is formed by the needle-shaped electrode member to which the high voltage necessary to the electric discharge is applied from the power supply 5, and the periphery of the electrode member is covered with the dielectric member 11 made of, for example, quartz glass. In the first electrode 4, the gas flow path 110 through which the gas 70 flows is formed between the dielectric member 11 and the needle-shaped electrode member.
The electrode unit is attached to the bottom portion of the treatment water tank 1 made of, for example, stainless steel through the insulating portion 6. In the apparatus of the eleventh embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the eleventh embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to inflow pressure, the gas 70 passes through the gas flow path 110 provided in the first electrode 4, and the gas 70 is blown into the treatment water 2 from the openings 30 provided in the second electrode 3, which allows the gas space to be formed at the leading edge of the first electrode 4 (electric discharge portion 40) opposite to the second electrode 3, and the leading edge is not in direct contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in the gas flow path 110 from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the bubbles 10 are generated near the opening 30 by the gas 70.
Thus, according to the eleventh embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Twelfth Embodiment)
In the apparatus of the twelfth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the second electrode 3 having the metal mesh structure. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. The second electrode 3 is arranged at the position opposite to the leading edge of the first electrode 4 (electric discharge portion 40).
The first electrode 4 is formed by the needle-shaped electrode member to which the high voltage necessary to the electric discharge is applied from the power supply 5, and the periphery of the electrode member is covered with the dielectric member 11 made of, for example, quartz glass. In the first electrode 4, the gas flow path 110 through which the gas 70 flows is formed between the dielectric member 11 and the needle-shaped electrode member.
The electrode unit is attached to the bottom portion of the treatment water tank 1 made of, for example, stainless steel through the insulating portion 6. In the apparatus of the twelfth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the twelfth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to inflow pressure, the gas 70 passes through the gas flow path 110 provided in the first electrode 4, and the gas 70 is blown into the treatment water 2 from the mesh of the second electrode 3, which allows the gas space to be formed at the leading edge of the first electrode 4 (electric discharge portion 40) opposite to the second electrode 3, and the leading edge is not in direct contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in the gas flow path 110 from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the mesh of the second electrode 3. Therefore, the bubbles 10 are generated near the second electrode 3 by the gas 70.
Thus, according to the twelfth embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the recalcitrant organic matter dissolved in the water can efficiently be decomposed by the radical.
(Thirteenth Embodiment)
In the apparatus of the thirteenth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the plate-shaped second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. The electrode unit is attached to the bottom portion of the treatment water tank 1 made of, for example, stainless steel through the insulating portion 6.
The first electrode 4 includes the electrode member having the hollow cylindrical structure, to which the high voltage necessary to the electric discharge is applied from the power supply 5, and the first electrode 4 has the gas flow path 41 formed by the hollow portion. In the first electrode 4, the periphery of the electrode member is covered with the dielectric member 11 made of, for example, quartz glass. The electric discharge portion 40 located at the leading edge of each first electrode 4 is arranged in the treatment water 2.
In the apparatus of the thirteenth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the thirteenth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 is blown into the treatment water 2 from the gas flow paths 41 provided in the first electrode 4, which allows the gas space to be formed at the leading edge of the first electrode 4 (electric discharge portion 40) opposite to the second electrode 3, and the leading edge is not in direct is contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in the gas flow paths 41 from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3. Therefore, the gas 70 near the leading edges of the first electrodes 4 generates the bubbles 10.
Thus, according to the thirteenth embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Fourteenth Embodiment)
In the apparatus of the fourteenth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the plate-shaped second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. In the second electrode 3, the plurality of openings 30 are formed at the positions opposite to the leading edges of the first electrode 4 (electric discharge portion 40). The electrode unit is attached to the bottom portion of the treatment water tank 1 made of, for example, stainless steel through the insulating portion 6.
The first electrode 4 includes the electrode member having the hollow cylindrical structure, to which the high voltage necessary to the electric discharge is applied from the power supply 5, and the first electrode 4 has the gas flow path 41 formed by the hollow portion. In the first electrode 4, the periphery of the electrode member is covered with the dielectric member 11 made of, for example, quartz glass. The electric discharge portion 40 located at the leading edge of each first electrode 4 is arranged in the treatment water 2.
In the apparatus of the fourteenth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the fourteenth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 passes through the gas flow paths 41 provided in the first electrode 4, and the gas 70 is blown into the treatment water 2 from the openings 30 of the second electrode 3, which allows the gas space to be formed at the leading edge of the first electrode 4 (electric discharge portion 40) opposite to the second electrode 3, and the leading edge is not in direct contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in the gas flow paths 41 from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the openings 30 provided in the second electrode 3 so as to impinge on the water. Therefore, the bubbles 10 are generated near the opening 30 by the gas 70.
Thus, according to the fourteenth embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the blown gas 70 and the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Fifteenth Embodiment)
In the apparatus of the fifteenth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the plurality of first electrodes 4 and the plate-shaped second electrode 3. The second electrode 3 constitutes the ground electrode, and is arranged in the treatment water 2. The second electrode 3 is formed by the electrode member having the metal mesh structure, and the second electrode 3 is arranged in parallel with the first electrode 4. The electrode unit is attached to the bottom portion of the treatment water tank 1 made of, for example, stainless steel through the insulating portion 6.
The first electrode 4 includes the electrode member having the hollow cylindrical structure, to which the high voltage necessary to the electric discharge is applied from the power supply 5, and the first electrode 4 has the gas flow path 41 formed by the hollow portion. In the first electrode 4, the periphery of the electrode member is covered with the dielectric member 11 made of, for example, quartz glass. The electric discharge portion 40 located at the leading edge of each first electrode 4 is arranged in the treatment water 2.
In the apparatus of the fifteenth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the fifteenth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 passes through the gas flow paths 41 provided in the first electrode 4, and the gas 70 is blown into the treatment water 2 from the mesh of the second electrode 3, which allows the gas space to be formed at the leading edge of the first electrode 4 (electric discharge portion 40) opposite to the second electrode 3, and the leading edge is not in direct contact with the treatment water 2.
In this state, when the high voltage is applied to the electrode unit from the power supply 5, the electric discharge is generated from the electric discharge portion 40 that is of the leading edge of the first electrode 4. Accordingly, at the leading edge of the first electrode 4, the radical is generated by the electric discharge from the gas 70 flowing in the gas flow paths 41 from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2 from the mesh of the second electrode 3 so as to impinge on the water. Therefore, the bubbles 10 are generated near the mesh by the gas 70.
Thus, according to the fifteenth embodiment, the leading edge of the first electrode 4 which is of the electric discharge portion 40 is in the same state as the state in which the leading edge is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Sixteenth Embodiment)
In the apparatus of the sixteenth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the dielectric member 11 made of the quartz glass, the first electrode 4, and the second electrode 3. The electrode unit has the structure in which the first electrode 4 and the second electrode 3 are oppositely arranged in the prism hollow portion (through-hole) 40 provided in the dielectric member 11.
As mentioned later, the hollow portion 40 forms the gas flow path. The gas 70 flows in through the gas flow path, and is blown into the treatment water 2 through the gas flow path. The first electrode 4 is one to which the high voltage is applied from the power supply 5. The second electrode 3 is the ground electrode. The hollow portion 40, in which the first and second electrodes 4 and 3 are arranged, corresponds to the electric discharge portion which discharges in the gas space. The gas space is formed in the hollow portion 40, and the hollow portion 40 is not in direct contact with the treatment water 2.
In the apparatus of the sixteenth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the sixteenth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 flows in from the hollow portion 40 of the electrode unit, and the gas 70 is blown into the treatment water 2 so as to impinge on the treatment water 2, which allows the gas space to be formed in the hollow portion 40.
In this state, when the high voltage is applied to the first electrode 4 from the power supply 5, the electric discharge is generated in the hollow portion 40. Accordingly, in the hollow portion 40, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2. Therefore, the bubbles 10 are generated by the gas 70 in the hollow portion 40.
Thus, according to the sixteenth embodiment, the electric discharge portion which is of the hollow portion 40 is in the same state as the state in which the electric discharge portion is arranged in the treatment water 2, so that the radical can efficiently be dissolved into the treatment water 2. Accordingly, the recalcitrant organic matter dissolved in the water can efficiently be decomposed by the radical.
(Seventeenth Embodiment)
In the apparatus of the seventeenth embodiment, the electrode unit is provided in the lower chamber of the treatment water tank 1. The electrode unit includes the dielectric member 11 made of the quartz glass or the like, the first electrode 4, and the second electrode 3. The electrode unit has the prism hollow portion (through-hole) 40 provided in the dielectric member 11. As mentioned later, the hollow portion 40 forms the gas flow path. The gas 70 flows in through the gas flow path, and is blown into the treatment water 2 through the gas flow path.
The first electrode 4 is one to which the high voltage is applied from the power supply 5. The second electrode 3 is the ground electrode. The first and second electrodes 4 and 3 are incorporated into the dielectric member 11, and the first and second electrodes 4 and 3 are arranged so as to oppose to each other through the hollow portion 40. Therefore, the hollow portion 40 functions as the electric discharge portion which discharges in the gas space. The gas space is formed in the hollow portion 40, and the hollow portion 40 is not in direct contact with the treatment water 2.
In the apparatus of the seventeenth embodiment, the lower chamber of the treatment water tank 1 in which the electrode unit is provided has the same structure as the gas tank 9 in which the gas inflow pipe 7 is provided.
The functional effect of the sixteenth embodiment will be described below.
The gas 70 such as air containing moisture is caused to flow in the lower chamber of the treatment water tank 1 through the gas inflow pipe 7. According to the inflow pressure, the gas 70 flows in from the hollow portion 40 of the electrode unit, and the gas 70 is blown into the treatment water 2 so as to impinge on the treatment water 2, which allows the gas space to be formed in the hollow portion 40.
In this state, when the high voltage is applied to the first electrode 4 from the power supply 5, the electric discharge is generated in the hollow portion 40. The electric discharge is generated as numerous micro-discharges in the gas space of the hollow portion 40.
Accordingly, in the hollow portion 40, the radical is generated by the electric discharge from the gas 70 flowing in from the gas inflow pipe 7. Both the radical and the gas 70 are blown into the treatment water 2. Therefore, the bubbles 10 are generated by the gas 70 in the hollow portion 40.
Thus, according to the seventeenth embodiment, the electric discharge portion that is of the hollow portion 40 is in the same state as the state in which the electric discharge portion is arranged in the treatment water 2, so that the radical such as the OH radical can efficiently be dissolved into the treatment water 2. Accordingly, the radical can efficiently decompose the recalcitrant organic matter dissolved in the water.
(Eighteenth Embodiment)
FIGS. 19 to 21 are graphs for explaining the functional effect of the water treatment apparatus according to an eighteenth embodiment. In the same configuration as the water treatment apparatus according to the first embodiment shown in
Referring to FIGS. 19 to 21, the functional effect of the eighteenth embodiment will be described. In
It is confirmed that a life of the OH radical generated in the gas phase is determined by density of the OH radical. An extinction reaction formula (13) of the OH radical is shown below.
OH+OH→H2O2 (13)
A reaction rate of the extinction reaction formula (13) can be expressed by the following chemical formula (14) using a rate constant k and OH radical density [OH].
As can be seen from the chemical formula (14), the OH radical is decreased in the density in proportion to the square of concentration of the OH radical. Namely, as the density of the OH radical is increased, the extinction rate of the OH radical is increased, and the life of the OH radical becomes shortened.
As shown in
As shown in
The difference between the dielectric barrier discharge and the corona discharge is the amount of generation of the OH radical. In the dielectric barrier discharge, the density of the OH radical is 1015/cm3 at the peak (see
In the apparatus of the eighteenth embodiment, it is assumed that a distance between the leading edge of the pin electrode and the water surface of the treatment water ranges from zero to tens of mm. Accordingly, when the life of the OH radical is about 10 ms, the OH radical generated by the electric discharge can sufficiently reach the treatment water by concentration diffusion, ionic wind, and gas flow. As a result, in the case where the density of the OH radical is 1014/cm3, the water treatment can efficiently be performed by the OH radical.
Further, referring to
The corona discharge is generated by the locally high electric field. When the locally high electric field reaches dielectric breakdown strength of the atmospheric gas, the corona discharge is formed. As shown in
However, when the voltage exceeds a certain value, the current value is rapidly increased (in this case, an inflection point is located around 60 A). Namely, the ratio of “dV/dI” is decreased. This is because the electron density in the electric discharge is rapidly increased and the electric discharge power becomes also high (electric discharge power region B shown in
In such the case, the life of the OH radical is remarkably shortened while the amount of generation of the OH radical is increased (see
(Nineteenth Embodiment)
Attention is directed toward the case in which the distance between the electrode and the treatment water surface is about 2.5 mm (position shown by thin line). When the electric discharge power per surface area 1 m2 of the treatment water is lowered below 7 kW, it is confirmed that the treatment efficiency (η) is increased. Specifically, because it is estimated that the treatment efficiency (η) of acetic acid is about 0.5 g/kWh in an ozone/ultraviolet ray method that is of the conventional OH radical generation method, the treatment efficiency (η) can relatively be improved.
Namely, in the nineteenth embodiment, the electric discharge control is performed so that the upper limit of the electric discharge power per surface area 1 m2 of the treatment water becomes about 7 kW, which allows the high treatment efficiency to be realized. When the electric discharge power is relatively decreased, the concentration of the OH radical is decreased. Therefore, it is presumed that the life of the OH radical is relatively lengthened. Accordingly, it is presumed that the OH radical exists for a relatively longer time and the OH radical affects the treatment of acetic acid that is of the treatment water.
(Twentieth Embodiment)
When the positive pulse voltage is applied as the high-voltage pulse, the conditional expression of “V<2.4×d+5, and d>0” satisfies the part shown by oblique lines of
Namely, in the twentieth embodiment, the provision of the high-voltage pulse is controlled so that the conditional expression is satisfied, which allows the high treatment efficiency to be realized.
(Twenty-First Embodiment)
Light having the wavelength of 309 nm means the density of the OH radical in the excited state (A2Σ).
As shown in
When the density of the OH radical continues to increase, the extinction by the reaction between the OH radicals is generated, which results in the decrease in treatment efficiency. Therefore, in the twenty-first embodiment, as shown in
(Twenty-Second Embodiment)
Attention is directed toward the case in which the distance between the electrode and the treatment water surface is about 2.5 mm (position shown by the thin line). When the amount of electric discharge power per one pin electrode is lowered below 100 μWs, it is confirmed that the treatment efficiency (η) is increased. Specifically, because it is estimated that the treatment efficiency (η) of acetic acid is about 0.5 g/kWh in the ozone/ultraviolet ray method that is of the conventional OH radical generation method, the treatment efficiency (η) can relatively be improved.
Namely, in the twenty-second embodiment, the electric discharge control is performed so that the upper limit of the amount of electric discharge power per one pine electrode becomes about 100 μWs, which allows the high treatment efficiency to be realized. When the amount of electric discharge power is relatively decreased, the concentration of the OH radical is decreased. Therefore, it is presumed that the life of the OH radical is relatively lengthened. Accordingly, it is presumed that the OH radical exists in the valid state for a relatively longer time and the OH radical affects the treatment of acetic acid which is of the treatment water.
The twenty-second embodiment can also be applied to the wire electric discharge using the wire electrode in the apparatus corresponding to the eighth embodiment described referring to
(Twenty-Third Embodiment)
In the same configuration as the water treatment apparatus according to the first embodiment shown in
In the twenty-third embodiment, the provision of the high-voltage pulse is controlled so that the average current passing through per 1 m2 of the treatment water becomes not more than 30 A when the electric discharge is generated by applying the high voltage to the electrode from the power supply.
Specifically, the electric discharge power region A can be realized when the ground electrode is not more than 30 A/m2.
(Twenty-Fourth Embodiment)
As shown in
Inflow ports 21 in which the treatment water 2 flows and an outflow port 22 from which the treatment water 2 is drained are provided in the water tank 1. The water 2 is continuously treated as it flows in the water tank 1 from the inflow port 21 to the outflow port 22. Nonetheless, the water 2 may be treated in the tank 1 in any other manner. In this case, the water tank 1 need not have the ports 21 and 22. A gas introduction port 23 that introduces the gas 70 containing the air or oxygen is also provided in the water tank 1.
The first electrode member 400 has a structure in which a plurality of projection members 410 for generating the electric discharge is provided on a main body 411. A gas exhaust port 12, which exhausts a part of the gas 70 introduced from the gas introduction port 23, is provided in the first electrode member 400.
The radical treatment apparatus has the high-voltage power supply 5 that applies the high voltage between the main body 411 of the first electrode member 400 and the second electrode member (ground electrode) 3 arranged in the water tank 1. In the first electrode member 400, according to the application of the high voltage, the electric discharge is generated from the leading edge of each projection member 410. The ground electrode 3 is formed by a disk-shaped metal plate.
The gas 70 is supplied from a gas supply device 24 shown in
It is preferable that the gas 70 is introduced from the gas supply device 24 to the gas introduction port 23 through a water tank 25. The water tank 25 is one in which the water used for causing air or oxygen to contain the moisture is stored. It is confirmed that the gas 70 containing the water molecule is the gas that is easy to generate the OH radical by the later-mentioned electric discharge.
As shown in
(Structure of Electrode)
The first electrode 400 has the plurality of projection members 410 which is formed by cutting one metal plate 500. Each projection member 410 is configured in a pyramid shape so that the leading edge where the electric discharge is generated becomes an acute angle. It is also possible that each projection member 410 is configured in a conical shape or the needle shape.
It is preferable that the projection member 410 is made of corrosion resistant metal. When the electric discharge is generated near the water surface of the treatment water 2, corrosion of the projection member 410 is easy to occur by vapor from the treatment water 2. Therefore, when the projection member 410 is made of corrosion resistant metal, the corrosion can be suppressed to lengthen a component life. Accordingly, running costs can be reduced. Specifically examples of the corrosion resistant metal include the stainless steel.
(Function and Effect)
Referring to
The treatment water 2 flows into the water tank 1 from the inflow port 21. Then, the gas 70 that is of, e.g. the air is introduced from the gas introduction port 23. The gas 70 is supplied so that the periphery of each projection member 410 of the first electrode 400 is filled with the gas 70.
In the atmosphere of the filled gas 70, when the high voltage is applied from the power supply 5 between the main body 411 of the first electrode 400 and the ground electrode 3 arranged in the water tank 1, the electric discharge is generated from the leading edge of each projection member 410.
The electric discharge is generated between the leading edge of each projection member 410 and the water surface of the treatment water 2 in the atmosphere of the gas 70. A mode of the electric discharge is changed according to a level of the applied voltage from the high-voltage power supply 5. When the applied voltage remains at a relatively low level, the electric discharge becomes the corona discharge that is generated near the leading edge of each projection member 410. When the applied voltage reaches a relatively high level, the electric discharge becomes a streamer discharge that is generated across the water surface of the treatment water 2 from the leading edge of each projection member 410.
As described above, in the case where the corona discharge having the low electric power necessary to the electric discharge is generated by the applied voltage of the relatively low level, it is confirmed that the density of the OH radical becomes low and the life of the OH radical is lengthened. Accordingly, in the radical treatment apparatus, the corona discharge is generated from each projection member 410 of the first electrode 400 by applying the low-level applied voltage from the high-voltage power supply 5. The Oh radical and ozone (O3) are generated by the corona discharge to decompose the organic matter contained in the treatment water 2. A reaction process of the organic decomposition by the electric discharge will be described below.
The corona discharge generated from each projection member 410 of the first electrode 400 reacts with the water molecule (H2O) generated by saturated vapor pressure of the treatment water 2 and oxygen (O2) in the gas 70. Specifically, in the corona discharge, the OH radical (OH), the oxygen atom O(3P) in the ground state, and the oxygen atom O(1D) in the excited state are generated by the collision between the electron e and the gas molecule.
The reaction process is shown by the following chemical formulas (21) to (31):
e+H2O→.OH+H+e (21)
e+O2→O(1D)+O(3P) (22)
At this point, O(1D) reacts with the water molecule to generate the OH radical as shown in the following chemical formula (23):
O(1D)+H2O→2.OH (23)
The OH radical forms hydrogen peroxide by recombination of the OH radicals as shown in the following chemical formula (24):
.OH+.OH→H2O2 (24)
When hydrogen peroxide is dissolved in the water, hydrogen peroxide is dissociated to form HO2− and the hydrogen ion H+ as shown in the following chemical formula (25):
H2O2HO2−+H+ (25)
At this point, the generated HO2− reacts with O3 to form O3− and the HO2 radical as shown in the following chemical formula (26):
HO2−+O3→O3−+HO2. (26)
At this point, the generated HO2. is dissociated to form O2− and H+ as shown in the following chemical formula (27):
HO2.O2−+H+ (27)
At this point, the generated O2− reacts with ozone to form O3− as shown in the following chemical formula (28):
O2−+O3→O3−+O2 (28)
O3− reacts with H+ to form HO3 as shown in the following chemical formula (29):
O3−+H+→HO3 (29)
HO3 is dissociated to form the OH radical as shown in the following chemical formula (30):
HO3+→.OH+O2 (30)
Thus, HO2− dissociated from hydrogen peroxide H2O2 reacts with ozone to generate the HO2 radical, and the OH radical is formed in the water to react with an organic matter R contained in the treatment water 2. At this point, as shown in the following chemical formula (31), the OH radical resolves the organic matter R into the water, carbon dioxide gas, and hydrogen peroxide.
.OH+R→H2O+CO2+H2O2 (31)
Namely, the recalcitrant organic matter (R) dissolved in the treatment water 2 is decomposed and treated by the corona discharge which reacts with the gas 70.
As described above, according to the radical treatment apparatus of the twenty-fourth embodiment, the corona discharge is generated from each projection member 410 of the first electrode 400 by applying the low-level applied voltage from the high-voltage power supply 5. The OH radical and ozone (O3) are generated by the corona discharge to decompose the organic matter contained in the treatment water 2. In this case of the corona discharge in which the applied voltage is at the relatively low level and the electric power necessary to the electric discharge is low, the density of the OH radical becomes low and the life of the OH radical becomes lengthened, so that the high treatment efficiency can be realized.
In the first electrode 400 of the twenty-fourth embodiment, each pyramid-shaped projection member 410 is formed by cutting the one metal plate 500 so that the leading edge of each projection portion where the electric discharge is generated becomes an acute angle. Accordingly, because the electric discharge electrode where the corona discharge is generated can be produced at relatively low cost, the practical radical treatment apparatus can easily be provided.
(Twenty-Fifth Embodiment)
The first electrode 400 of the twenty-fifth embodiment has the plurality of projection members 410 which are formed by press working of one metal plate 700. Each projection member 410 is formed in the pyramid shape so that the leading edge where the electric discharge is generated becomes an acute angle. In each projection member 410, concave portions 710 punched by the press working are formed in the surface that is connected to the side of the main body 411.
In the structure of the first electrode 400 according to the twenty-fifth embodiment, as with the twenty-fourth embodiment, because the electric discharge electrode where the corona discharge is generated can also be produced at relatively low cost, the practical radical treatment apparatus can easily be provided.
(Twenty-Sixth Embodiment)
The first electrode 400 of the twenty-sixth embodiment has the plurality of projection members 410 having two-layer structures. Each projection member 410 includes a metal projection portion 800 and a dielectric body 810, and the periphery of the projection portion 800 is covered with the dielectric body 810. Each projection member 410 is formed in the conical shape or the pyramid shape so that the leading edge where the electric discharge is generated becomes an acute angle.
According to the first electrode 400 having the structure of the twenty-sixth embodiment, the corona discharge can stably and evenly be generated from each projection member 410 toward the water surface of the treatment water 2 by ballast effect of the dielectric body 810. As with the first embodiment, because the electric discharge electrode where the corona discharge is generated can be produced at relatively low cost, the practical radical treatment apparatus can easily be provided.
(Twenty-Seventh Embodiment)
As shown in
According to the ground electrode 80 of the twenty-seventh embodiment, because the treatment water 2 passes through the hole 81 of the ground electrode 80 to circulate upward and downward, the treatment water 2 is easily stirred. Accordingly, when the decomposition treatment of the organic matter is performed to the treatment water 2 by the corona discharge, the efficiency of the decomposition treatment can be improved to achieve reduction of treatment time.
In the radical treatment apparatus of the twenty-seventh embodiment, as with the twenty-fourth embodiment, because the electric discharge electrode where the corona discharge is generated can be produced at relatively low cost, the practical radical treatment apparatus can easily be provided.
(Twenty-Eighth Embodiment)
The ground electrode 90 of the twenty-eighth embodiment includes a circular frame 91 made of, for example, stainless steel and a metal mesh 92 provided in the frame 91.
According to the ground electrode 90 of the twenty-eighth embodiment, because the treatment water 2 passes through gaps of the metal mesh 92 to circulate upward and downward, the treatment water 2 is easily stirred. Accordingly, when the decomposition treatment of the organic matter is performed to the treatment water 2 by the corona discharge, the efficiency of the decomposition treatment can be improved to achieve the reduction of the treatment time.
(Twenty-Ninth Embodiment)
The ground electrode 90 of the twenty-ninth embodiment includes the circular frame 91 made of, for example, stainless steel and a plurality of metal wires 93. The metal wires 93 are arrayed in the lengthwise direction and crosswise direction. It is also possible that metal rods be used instead of the metal wires 93.
According to the ground electrode 90 of the twenty-ninth embodiment, because the treatment water 2 passes through gaps of the metal wires 93 to circulate upward and downward, the treatment water 2 is easily stirred. Accordingly, when the decomposition treatment of the organic matter is performed to the treatment water 2 by the corona discharge, the efficiency of the decomposition treatment can be improved to achieve the reduction of the treatment time.
(Modification)
The projection member 410 shown in
(Application Example)
The radical treatment apparatus having the first electrode 400 that generates the electric discharge to the treatment water 2 containing the organic matter is described in the twenty-fourth embodiment. However, the first electrode 400 can be applied not only to the radical treatment apparatus used for the treatment water 2 but also to the radical treatment apparatus used for other treatment objects.
Specifically, the radical treatment apparatus that performs surface treatment of a solid body made of glass and the like as the treatment object can be cited as an example. In the radical treatment apparatus, the ground electrode 3 is arranged in, e.g. a machine on which the solid body is loaded, and the high voltage for the electric discharge is applied between the ground electrode 3 and the first electrode 400.
(Thirtieth Embodiment)
In
The high voltage is applied to the electrode 4 from the high-voltage power supply 5. When the high voltage is applied to the electrode 4, the electrode 4 generates an electric discharge 150.
A part of the electrode 4 is formed in the needle shape or the rod shape, which allows the electric field to concentrate on the part formed in the needle shape or the rod shape. Therefore, the electric discharge can be generated at a low voltage, i.e. the radical can be generated using less energy.
In order to decompose the recalcitrant organic matter dissolved in the treatment water by the OH radical generated from the electric discharge, it is necessary that the radical generated by the electric discharge is dissolved into the water. However, because the radical is very reactive substance, the radical reacts with other particles in a very short time. Therefore, it is necessary that the radical be dissolved into the water immediately after the generation of the radical.
The OH radical is generated from the electric discharge by the following chemical formula. When the electric discharge 150 in the atmosphere containing water vapor and oxygen, in the electric discharge 150, the oxygen atom O(3P) in the ground state and the oxygen atom O(1D) in the excited state are generated by the collision between the electron e and the gas molecule:
e+O2→O(1D)+O(3P) (41)
O(1D) reacts with the water molecule to generate the OH radical:
O(1D)+H2O→2.OH (42)
O(3P) generates ozone (O3) by the triple collision of O(3P), O2, and the neutral molecule M:
O(3P)+O2+M→O3+M (43)
The hydrogen atom and the OH radical are also generated by the direct collision of the water molecule and the electron:
e+H2O→H+OH. (44)
Thus, the generated OH radical has a traveling rate depending on the temperature and the pressure, and the OH. is dissolved into the treatment water. However, the OH radical has high oxidation power, and the OH radical reacts with other particles in a short time. Namely, in order to use the OH radical for the water treatment, it is necessary that the OH radical is dissolved into the treatment water before the OH radical reacts with other particles.
Assuming that the time from the generation of the OH radical to the reaction with other particles is the life, temperature dependence of the life of the OH radical is shown in
As shown in chemical formulas (42) and (44), when the electric discharge is ignited in the vapor atmosphere, the OH radical is generated. In the case where the vapor is generated with a steam boiler, although based on conditions, the temperature is limited to about one thousand and several hundreds degrees Celsius.
In the case where the further higher temperature is generated, the temperature can be increased up to thousand degrees Celsius by generating arc discharge, and temperature control can be performed by adjusting injection electric power to the arc discharge. However, since it is thought that the treatment water is boiled, the increase in temperature is limited to a certain value. Namely, in the case where the radical treatment of the water is industrially performed, it is said that the temperature of the radical treatment ranges from room temperature to one thousand and several hundreds degrees Celsius.
As described above, the OH radical is generated when the electric discharge is ignited in the high-humidity atmosphere. In the case where the humidity is 100%, a ratio of the water molecule that occupies the space is about 1% in the atmospheric pressure.
When all the molecules except for the water molecule are removed from the gas having the humidity of 100% in the atmospheric pressure, the gas contains only the water molecule in the pressure of 0.01 atmospheres. Therefore, in consideration of industrial application, it is desirable that the lower limit of the pressure range is up to about 0.01 atmospheres.
Thus, it is understood that the life of the OH radical is lengthened as the temperature is increased or as the pressure is decreased. In order to perform the water treatment by the OH radical, it is necessary that the OH radical be dissolved into the treatment water during the time when the OH radical exists.
The OH radical generated from the electric discharge reaches the surface of the treatment water by the diffusion. Traveling distance 8 of the OH radical by the diffusion can be expressed by the following equation using a diffusion constant D, a traveling time t, a temperature T, and a pressure P:
δ=(2Dt)1/2 (45)
D=5.4×10−4×T3/2/P (46)
Namely,
t=P×d2/(T3/2×1.08×10−3) (47)
As can be seen from
P×d2<(T5/4×10−6) (48)
In the expression (48), the temperature T is the room temperature, the pressure P is 50 torr (0.065 atmosphere), and the distance d between the electrodes is not more than 1.3 cm. It is possible that the temperature T is 1500° C., the pressure P is the atmospheric pressure, and the distance d between the electrodes is not more than 1 mm. Preferably the temperature T is set to 1500° C., the pressure P is set to 50 torr, and the distance d between the electrodes is set to a value not more than 3.78 cm. Therefore, the OH radical can treat the treatment water.
In the radical treatment apparatus having the distance d between the surface of the treatment water and the electrode discovered by the expression (48), the OH radical generated from the electric discharge is dissolved into the treatment water, and the OH radical reacts with the recalcitrant organic matter to be resolved into the water H2O, carbon dioxide CO2, and hydrogen peroxide:
OH.+R→H2O+CO2+H2O2 (49)
Unlike the conventional ozone treatment, the radical treatment can decompose the recalcitrant organic matter into inorganic matter.
It is possible that any one of an alternating-current power supply, a direct-current power supply, and the pulse power supply is used as the high-voltage power supply 5. When the alternating-current power supply is used as the power supply 5, the electric power can efficiently be injected to the electric discharge through a water layer, so that the decomposition efficiency of the recalcitrant organic matter can be improved. When the direct-current power supply is used as the power supply 5, the electric discharge can efficiently be ignited in the gas phase, so that the decomposition efficiency of the recalcitrant organic matter can be improved.
When the pulse power supply used as the power supply 5, the high energy can be injected to the electric discharge in a short time, so that the radical generation efficiency can be improved. Further, since the discharge time per pulse is short, the injection energy to the electric discharge is not used for the increase in temperature caused by Joule heating of the discharge space but the injection energy is substantially used for the generation of the radical. Therefore, the decomposition efficiency of the recalcitrant organic matter can be improved.
(First Modification)
The gas generated from a gas flow apparatus 160 is blown to the electric discharge from a gas-blowing device 170 through a gas guide 180. The gas-blowing device 170 is arranged so that the radical generated from the electrode 4 is guided to the treatment water 2, and the gas-blowing device 170 is formed by, e.g. a nozzle. The gas generated from the gas flow apparatus 160 is one that contains oxygen. For example, the gas generated from the gas flow apparatus 160 is the water vapor.
As described above, the life of the OH radical is short, and the traveling distance by the diffusion is short. In order to solve the problem, the gas blown from the gas flow apparatus 160 forcedly moves the O radical and OH radical that is generated by the electric discharge to the surface of the treatment water. At this point, in a gas flow rate V, in consideration of the OH radical extinction time obtained from
In
(Second Modification)
The electrode 4 is formed in a hollow shape, the electrode 4 and the gas flow apparatus 160 are connected to each other through the gas guide 180. The gas containing oxygen, which generated from the gas flow apparatus 160, flows in the inside of the electrode 4 through the gas guide 180. The gas flows in the inside of the electrode 4, which allows the O radical and the OH radical which are generated from the electric discharge 150 to forcedly be moved to the surface of the treatment water. In the case where the gas is the water vapor, when the gas flows in the inside of the electrode 4, the amount of generation of the OH radical is remarkably increased, which allows the decomposition treatment of the recalcitrant organic matter to be performed.
Thus, according to the modification of the thirtieth embodiment, the electrode 4 has the hollow shape, when the gas flows in the inside of the electrode 4, the discharge energy can be substantially injected into the gas. The OH radical generation efficiency is increased by causing the gas which is easily generates the OH radical to flow the inside of the electrode 4, which allows the decomposition efficiency of the recalcitrant organic matter to be improved.
(Third Modification)
As shown in
In order to obtain heat insulation effect from the outside of the electrode, an outer pipe 421 is provided around the inner pipe 420, so that delivered has temperature can become constant. As a result, the life of the radical is lengthened, and the water treatment can effectively be performed.
(Fourth Modification)
As shown in
The electric discharge can be generated in the wide range by providing the linear electrode 4 which is arranged opposite to the treatment water, so that the decomposition efficiency of the organic matter can be improved.
(Fifth Modification)
The feature of the fifth modification is that the electrode 4 is formed in the plate shape and the electrode 4 is arranged parallel to the treatment water 2. The electric discharge can be generated in the wide area with respect to the surface of the treatment water 2 by forming the electrode 4 in the plate shape, so that the generation efficiency of the O radical and the OH radical is improved and the high water treatment efficiency is obtained.
(Sixth Modification)
The feature of the sixth modification is that the periphery of the electrode 4 is covered with the dielectric body.
When the electrode 4 is covered with the dielectric body, not only secondary contamination of the treatment water caused by dissolving the electrode material by the electric discharge is prevented, but also numerous micro-discharges are generated when the alternating-current voltage is applied, so that the micro-discharge can stably and evenly be obtained in the electric discharge space. As a result, the generation efficiency of the O radical and the OH radical can be improved, and the decomposition efficiency of the organic matter can be improved.
(Seventh Modification)
In
In
According to the humidifier having the above-described structure, since the reaction vessel 300 is also used as the humidifier, the radical treatment apparatus can be miniaturized.
(Eighth Modification)
In
(Ninth Modification)
In
When the arc discharge is generated in the reaction vessel 300, the temperature is increased in the electric discharge portion by the heat generation effect of the arc discharge, which allows the diffusion rate of the O radical and the OH radical generated from the electric discharge 150 to be increased. Further, the oxygen atom is generated from the arc discharge in the atmosphere containing oxygen. Therefore, the generation efficiency of the O radical and the OH radical is improved, and the decomposition efficiency of the recalcitrant organic matter is improved.
(Tenth Modification)
In
(Eleventh Modification)
In
A part of the electrode 4 is arranged in the treatment water 2, bubbles 150 are generated into the water by blowing the gas from the electrode 4. The diameter of the generated bubble is controlled so that d/V is not more than 1 ms, where d (m) is the distance between the water surface of the treatment water s and the electrode 4 and V (m/s) is the gas flow rate. It is possible that the gas is blown to the leading edge of the electrode 4 from the outside with the gas-blowing device. Therefore, the treatment of the recalcitrant organic matter is enabled.
(Twelfth Modification)
The electric discharge can be generated in the wide area by providing the gas-blowing device 1600, and the shape of the electrode is easily changed, so that the shape of the electrode can be fitted to the shape of the reaction vessel. The O radical and the OH radical generated from the electric discharge are dissolved into the treatment water by the gas blown with the gas blowing device 1600, so that the treatment of the recalcitrant organic matter is enabled.
(Thirteenth Modification)
The electric discharge can be generated in the wide area by providing the blowing device 170, and the shape of the electrode is easily changed, so that the shape of the electrode can be fitted to the shape of the reaction vessel. The O radical and the OH radical generated from the electric discharge are dissolved into the treatment water by the gas blown with the blowing device 170, so that the treatment of the recalcitrant organic matter is enabled.
(Fourteenth Modification)
The vapor is delivered into the reaction vessel 300 in order to increase the humidity in the reaction vessel 300. At this point, both the vapor and the gas containing oxygen gas are delivered from the gas flow apparatus 160, which allows the generation efficiency of the OH radical and the O radical to be improved. Therefore, the decomposition efficiency of the recalcitrant organic matter is improved.
(Fifteenth Modification)
As shown in
Therefore, the same effect as the fourteenth modification can be obtained.
(Sixteenth Modification)
As shown in
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Number | Date | Country | Kind |
---|---|---|---|
2004-026615 | Feb 2004 | JP | national |
2004-075043 | Mar 2004 | JP | national |
2004-121996 | Apr 2004 | JP | national |
2005-002932 | Jan 2005 | JP | national |