Method for generating ozone

Abstract

An ozone generator includes one or more electrode pairs each containing two electrodes arranged at a distance of a predetermined gap length and a power source for applying an alternating-current voltage between the two electrodes. In the ozone generator, ozone is produced when a source gas flows at least between the two electrodes and a discharge is generated between the two electrodes. The ozone generator has a discharge space formed between the two electrodes, and the ozone generator satisfies the condition of 0.5<V/f/L wherein V (m/s) represents a flow velocity of the source gas flowing through the discharge space, f (Hz) represents a frequency of the alternating-current voltage, and L (m) represents a length of the discharge space in the main flow direction of the source gas.

Claims

1. A method for generating ozone, comprising: flowing at least a portion of a source gas at least through a discharge space between a first electrode and a second electrode; and applying an alternating-current voltage between the first electrode and the second electrode, a value of V/f/L is greater than 0.5, wherein V (m/s) represents a flow velocity of the source gas flowing through the discharge space, f (Hz) represents a frequency of the alternating-current voltage, and L (m) represents a length of the discharge space in a main flow direction of the source gas.

2. A method as recited in claim 1, wherein the value of V/f/L is greater than 1.

3. A method as recited in claim 1, wherein the value of V/f/L is less than 50.

4. A method as recited in claim 1, wherein the value of V/f/L is less than 20.

5. A method as recited in claim 1, wherein the first and second electrodes are arranged at a gap length of a distance which is at least 0.2 mm and not greater than 0.5 mm.

6. A method as recited in claim 1, wherein the source gas is an atmospheric air.

7. A method as recited in claim 1, wherein each of the first and second electrodes comprises a tubular dielectric body having a hollow portion and a conductive body disposed in the hollow portion.

8. A method as recited in claim 1, wherein: the method comprises flowing the source gas through a plurality of pairs of electrodes arranged in parallel, in series, or in parallel and series, and some of the source gas passes through a non-discharge space on a gas passage plane, the gas passage plane having a normal direction parallel to the main flow direction of the source gas.

9. A method as recited in claim 1, wherein a flow rate of the source gas flowing through the discharge space is 380 L/min or less.

10. A method as recited in claim 5, wherein each of the first and second electrodes comprises a tubular dielectric body having a hollow portion and a conductive body disposed in the hollow portion.

11. A method as recited in claim 10, wherein the dielectric body of the first electrode faces the dielectric body of the second electrode.

12. A method as recited in claim 1, wherein each of the first and second electrodes comprises a conductive body and a dielectric body that covers an entire periphery of the conductive body.

13. A method as recited in claim 1, wherein the first and second electrodes are arranged at a gap length of a distance which is less than 1.0 mm.

14. A method as recited in claim 1, wherein the source gas has an absolute humidity in the range of from 0 g/m.sup.3 to about 50 g/m.sup.3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a longitudinal cross-sectional view of a principal part of an ozone generator according to an embodiment of the present invention;

(2) FIG. 2 is a cross-sectional view taken along the line II-II of FIG. 1;

(3) FIG. 3 is an explanatory view for specifically illustrating the flow velocity V (m/s) of a source gas flowing through a discharge space, the frequency f (Hz) of an alternating-current voltage v, and the length L (m) of the discharge space in the main flow direction of the source gas in the principal part of the ozone generator of the present embodiment;

(4) FIG. 4A is an explanatory view for illustrating a disadvantage of an ozone generator having an electrode pair with a larger gap length;

(5) FIG. 4B is explanatory view for illustrating an advantageous effect of the ozone generator of the present embodiment;

(6) FIG. 5 is a longitudinal cross-sectional view of a principal part of an ozone generator according to a first modification example;

(7) FIG. 6 is a longitudinal cross-sectional view of a principal part of an ozone generator according to a second modification example;

(8) FIG. 7 is a longitudinal cross-sectional view of a principal part of an ozone generator according to a third modification example;

(9) FIG. 8 is a graph showing the ozone concentration changes with changing V/f/L value in samples 1 to 3 using different source gas flow rates; and

(10) FIG. 9 is a graph showing the ozone production efficiency changes with absolute humidity in samples 11 to 16.

DETAILED DESCRIPTION OF THE INVENTION

(11) An embodiment of the ozone generator of the present invention will be described below with reference to FIGS. 1 to 9. In this description, a numeric range of A to B includes both the numeric values A and B as the lower limit and upper limit values.

(12) As shown in FIGS. 1 and 2, an ozone generator 10 according to this embodiment has a housing 14 in which a source gas 12 flows, one or more electrode pairs 16 disposed in the housing 14, and an alternating-current power source 18. Each of the electrode pairs 16 contains two electrodes 20 (one electrode 20a and the other electrode 20b) arranged at a distance of a predetermined gap length Dg. The alternating-current power source 18 acts to apply an alternating-current voltage v (=A sin(2f)t) between the two electrodes 20.

(13) In the ozone generator 10, ozone is produced when the source gas 12 flows at least between the two electrodes 20 of the electrode pair 16 and a discharge is generated between the two electrodes 20. A space formed between the two electrodes 20, in which the discharge is generated, is defined as a discharge space 22.

(14) The ozone generator 10 has non-discharge spaces 26 on a gas passage plane 24 having a normal direction parallel to the main flow direction of the source gas 12. Specifically, the non-discharge spaces 26 include a space between the one electrode 20a and one inner wall 28a of the housing 14 (the inner wall closer to the one electrode 20a) and a space between the other electrode 20b and the other inner wall 28b of the housing 14 (the inner wall closer to the other electrode 20b) on the gas passage plane 24. The term the main flow direction of the source gas 12 means the flow direction of the oriented center of the source gas 12. Thus, the main flow direction excludes flow directions of non-oriented peripheral components of the source gas 12.

(15) Each of the electrodes 20 has a rod shape, contains a tubular dielectric body 32 having a hollow portion 30, and further contains a conductive body 34 disposed in the hollow portion 30 of the dielectric body 32. In an example of FIGS. 1 and 2, the dielectric body 32 has a cylindrical shape, and the hollow portion 30 formed therein has a circular cross-section. The conductive body 34 has a circular cross-section. Of course, the shapes of the components are not limited to the example. The dielectric body 32 may have a tubular shape with a polygonal cross-section such as a triangular, quadrangular, pentangular, hexangular, or octangular section. The conductive body 34 may have a columnar shape with a polygonal section such as a triangular, quadrangular, pentangular, hexangular, or octangular section corresponding to the shape of the dielectric body 32.

(16) In this embodiment, the source gas 12 is used for the purpose of producing ozone, and therefore may be an atmospheric air, an oxygen-containing gas, etc. In this case, the source gas 12 may be a non-dehumidified air.

(17) The dielectric body 32 may be composed of a single-oxide, composite-oxide, or composite-nitride material containing one or more substances selected from the group consisting of barium oxide, bismuth oxide, titanium oxide, zinc oxide, neodymium oxide, titanium nitride, aluminum nitride, silicon nitride, alumina, silica, and mullite.

(18) The conductive body 34 is preferably composed of a material containing a substance selected from the group consisting of molybdenum, tungsten, silver, copper, nickel, and alloys containing at least one thereof. Examples of such alloys include invar, kovar, inconel (registered trademark), and incoloy (registered trademark).

(19) The dielectric body 32 is preferably composed of a ceramic material such as LTCC (Low Temperature Co-fired Ceramics), which can be fired at a temperature lower than the melting point of the conductive body 34. Specifically, the dielectric body 32 is preferably composed of a single-oxide, composite-oxide, or composite-nitride material containing one or more substances selected from the group consisting of barium oxide, bismuth oxide, titanium oxide, zinc oxide, neodymium oxide, titanium nitride, aluminum nitride, silicon nitride, alumina, silica, and mullite.

(20) As shown in FIG. 3, the ozone generator 10 of the above embodiment preferably satisfies the following inequality (1) where V (m/s) represents the flow velocity of the source gas 12 flowing through the discharge space 22, f (Hz) represents the frequency of the alternating-current voltage v, and L (m) represents the length of the discharge space 22 in the main flow direction of the source gas 12.
0.5<V/f/L(1)

(21) The value of V/f/L indicates how many times as long the movement distance of the source gas 12 per period of the alternating-current voltage is as the length L.

(22) When the ozone generator 10 satisfies the inequality (1), the ozone molecules produced by the discharge are hardly exposed to the discharge again. Therefore, the ozone molecules are hardly decomposed via a reaction with an O atom, a water molecule, or an OH group. Thus, the ozone production amount reduction can be prevented.

(23) When the ozone generator 10 satisfies the following inequality (2), a smaller amount of the produced ozone molecules are exposed to the discharge again, as compared with the inequality (1). Therefore, the ozone molecules are hardly decomposed via a reaction with the O atom, the water molecule, or the OH group. Thus, the ozone production amount reduction can be further prevented.
1<V/f/L(2)

(24) When the ozone generator 10 satisfies the following inequality (3), the amount of the unreacted source gas 12 can be reduced, so that the ozone production amount reduction can be prevented.
50>V/f/L(3)

(25) When the ozone generator 10 satisfies the following inequality (4), the residual amount of the unreacted source gas 12 can be further reduced, so that the ozone production amount reduction can be further prevented.
20>V/f/L(4)

(26) In the ozone generator 10 of this embodiment, the flow rate of the source gas 12 flowing through the discharge space 22 is preferably 380 L/min or less. The flow rate is more preferably 300 L/min or less, further preferably 150 L/min or less.

(27) In this case, the distribution of the source gas 12 can be narrowed in the discharge space 22, the ozone molecules can be uniformly produced in the discharge space 22, and the source gas 12 can be used up for the ozone production. Therefore, the ozone production amount reduction due to the ozone decomposition can be prevented, and the amount of the unreacted source gas 12 flowing through the discharge space 22, can be reduced. Consequently, the ozone generator 10 can exhibit a high ozone production efficiency.

(28) As shown in FIG. 1, the upper limit of the gap length Dg between the two electrodes 20 is preferably less than 1.0 mm. The gap length Dg denotes the shortest distance between the dielectric body 32 of the one electrode 20a and the dielectric body 32 of the other electrode 20b.

(29) In this embodiment, each electrode 20 contains the tubular dielectric body 32 having the hollow portion 30 and the conductive body 34 disposed in the hollow portion 30. Therefore, the distance between the electrodes 20 can be easily adjusted. Thus, the gap length Dg between the electrodes 20 can be easily reduced to less than 1.0 mm as compared with the creeping discharge-type structure disclosed in Japanese Laid-Open Patent Publication No. 10-324504.

(30) In a high-humidity environment, water molecules and OH groups may negatively affect the ozone production of the ozone generator 10. Therefore, it is preferable to adsorb as many water molecules and OH groups as possible to the dielectric bodies 32 of the electrodes 20. In this case, the amounts of the water molecules and the OH groups remaining in a central portion 22a of the discharge space 22 can be reduced to decrease the negative effect on the ozone production. However, when the gap length Dg is 1.0 mm or more as shown in FIG. 4A, the distance between the dielectric bodies 32 is increased, whereby a smaller amount of the water molecules and the OH groups are adsorbed to the dielectric bodies 32, and a larger amount of the water molecules and the OH groups remain around the dielectric bodies 32 or in the central portion 22a of the discharge space 22. Therefore, in the high-humidity environment, the ozone production is inhibited, the ozone production efficiency is reduced, or the ozone production is stopped, by the increased water molecules and OH groups which are contained in the source gas 12 and remain around the dielectric bodies 32 or in the central portion 22a of the discharge space 22.

(31) In contrast, in this embodiment, the upper limit of the gap length Dg is less than 1.0 mm. Therefore, as shown in FIG. 4B, even in the high-humidity environment, the water molecules and the OH groups, which may negatively affect the ozone production, are mostly adsorbed to the surfaces of the dielectric bodies 32, and the amounts of the water molecules and the OH groups remaining around the dielectric bodies 32 and in the central portion 22a of the discharge space 22 are reduced. Consequently, the ozone production inhibition can be prevented, and the ozone production amount reduction can be prevented. Furthermore, an area in which the water molecules and the OH groups remain around the dielectric bodies 32 and in the central portion 22a of the discharge space 22, can be narrowed. Thus, an area in which the ozone production is inhibited, can be narrowed, and the ozone production amount reduction can be prevented.

(32) As a result, the ozone production performance is changed only slightly even under a high humidity, and therefore the ozone generator 10 can act to stably produce ozone in a wide range of humidity environments (with an absolute humidity of 0 to 50 g/m.sup.3).

(33) The upper limit of the gap length Dg is further preferably 0.5 mm or less. In this case, a further larger amount of the water molecules and the OH groups, which may inhibit the ozone production, can be adsorbed to the dielectric bodies 32, whereas the water molecules and the OH groups remaining around the dielectric bodies 32 and in the central portion 22a of the discharge space 22 can be accordingly further reduced. Therefore, the ozone production amount reduction can be further prevented.

(34) On the other hand, when the gap length Dg is excessively reduced, the discharge space 22 may be short-circuited by the water molecules and the OH groups adsorbed to the dielectric bodies 32. More specifically, the dielectric bodies 32 may be connected to each other by the water molecules and the OH groups. This case is similar to the situation where a larger amount of the water molecules and the OH groups remain in the central portion 22a of the discharge space 22. Thus, by the presence of water molecules and OH groups, the ozone production is inhibited, the ozone production efficiency is reduced, or the ozone production is stopped. The lower limit of the gap length Dg is preferably 0.1 mm or more, further preferably 0.2 mm or more. In this case, the short circuit of the discharge space 22 due to the water molecules and the OH groups can be prevented to suppress the ozone production amount reduction.

(35) The electrode 20 may be produced by the following method. Thus, for example, a tubular compact (or green body) is preliminarily fired to prepare a preliminarily fired body having a hollow portion, and thereafter the conductive body 34 is inserted into the hollow portion of the preliminarily fired body. Then, the preliminarily fired body and the conductive body 34 are fired at a temperature higher than the preliminary firing temperature to produce the electrode 20 containing the dielectric body 32 and the conductive body 34 directly integrated with each other, the conductive body 34 being inserted into the hollow portion 30 of the dielectric body 32.

(36) Alternatively, the electrode 20 may be produced by a gel casting method. In the gel casting method, the conductive body 34 is placed in a mold, a slurry containing a ceramic powder, a dispersion medium, and a gelling agent is cast into the mold, the slurry is gelled under a temperature condition or by adding a cross-linker, whereby the slurry is solidified and molded, and the resultant is fired to produce the electrode 20.

(37) Though one electrode pair 16 is described in the above example, also structures according to first to third modification examples shown in FIGS. 5 to 7 can be preferably used in the present invention.

(38) As shown in FIG. 5, an ozone generator 10a according to the first modification example is different from the ozone generator 10 (shown in FIGS. 1 and 2) in that a plurality of the electrode pairs 16 are arranged in parallel. The alternating-current power source 18 acts to apply the alternating-current voltage v between the one electrode 20a and the other electrode 20b in each of the electrode pairs 16.

(39) Also the ozone generator 10a has the non-discharge spaces 26 on the gas passage plane 24. Specifically, the non-discharge spaces 26 include spaces between the electrode pairs 16, a space between the one electrode 20a (adjacent to the one inner wall 28a of the housing 14) and the one inner wall 28a, and a space between the other electrode 20b (adjacent to the other inner wall 28b of the housing 14) and the other inner wall 28b on the gas passage plane 24.

(40) As shown in FIG. 6, an ozone generator 10b according to the second modification example is different from the ozone generator 10 (shown in FIGS. 1 and 2) in that a plurality of the electrode pairs 16 are arranged in series. The alternating-current power source 18 acts to apply the alternating-current voltage v between the one electrode 20a and the other electrode 20b in each of the electrode pairs 16.

(41) Also the ozone generator 10b has the non-discharge spaces 26 on the gas passage planes 24. Specifically, the non-discharge spaces 26 include a space between the one electrode 20a in each of the electrode pairs 16 and the one inner wall 28a of the housing 14, and a space between the other electrode 20b in each of the electrode pairs 16 and the other inner wall 28b of the housing 14.

(42) As shown in FIG. 7, an ozone generator 10c according to the third modification example is different from the ozone generator 10 (shown in FIGS. 1 and 2) in that a plurality of the electrode pairs 16 are arranged in parallel and series. The alternating-current power source 18 acts to apply the alternating-current voltage v between the one electrode 20a and the other electrode 20b in each of the electrode pairs 16.

(43) Also the ozone generator 10c has the non-discharge spaces 26 on the gas passage planes 24.

First Example

(44) Ozone concentration changes with changing V/f/L value were evaluated in samples 1 to 3 using respective different flow rates of the source gas 12.

(45) An air was used as the source gas 12. The alternating-current power source 18 was used as a discharge power source for applying the alternating-current voltage v with a voltage (amplitude A) of 4 kV and a frequency f of 20 kHz.

(46) Under the above conditions, the ozone concentration of the exhaust gas was measured using an ozone concentration meter EG-3000D (available from Ebara Jitsugyo Co., Ltd.).

(47) As shown in FIG. 3, L represents the length (m) of the discharge space 22 in the main flow direction of the source gas 12, V represents the flow velocity (m/s) of the source gas 12 flowing through the discharge space 22, and f represents the frequency (Hz) of the alternating-current voltage v from the alternating-current power source 18.

(48) The details of the samples 1 to 3 were as follows.

(49) Sample 1

(50) The sample 1 had the structure shown in FIGS. 1 to 3 with the gap length Dg of 0.30 mm in the electrode pair 16, and the source gas 12 was supplied thereto under a flow rate of 350 L/min.

(51) Sample 2

(52) The sample 2 had the same structure as the sample 1 except that the source gas 12 was supplied thereto under a flow rate of 275 L/min.

(53) Sample 3

(54) The sample 3 had the same structure as the sample 1 except that the source gas 12 was supplied thereto under a flow rate of 145 L/min.

(55) Evaluation Result

(56) The evaluation results of the samples 1 to 3 are shown in FIG. 8. In FIG. 8, the horizontal axis of the graph representing V/f/L has a logarithmic scale.

(57) As is clear from FIG. 8, in the sample 1, the ozone concentration of 0.7 ppm or more was maintained within the range of 0.5<V/f/L10, and the ozone concentration of about 0.72 ppm was maintained within the range of 1<V/f/L<10. Furthermore, the ozone concentration of 0.6 to 0.7 ppm was maintained within the range of 10<V/f/L30, and the ozone concentration of 0.55 to 0.6 ppm was maintained within the range of 30<V/f/L<50.

(58) In the sample 2, the ozone concentration of 0.7 ppm or more was maintained within the range of 0.5<V/f/L20, and the ozone concentration of about 0.75 ppm was maintained within the range of 1<V/f/L<10. Furthermore, the ozone concentration of 0.6 to 0.7 ppm was maintained within the range of 20<V/f/L<50.

(59) In the sample 3, the ozone concentration of 0.8 ppm or more was maintained within the range of 0.5<V/f/L10, and the ozone concentration of about 0.82 ppm was maintained within the range of 1<V/f/L<10. Furthermore, the ozone concentration of 0.7 to 0.8 ppm was maintained within the range of 10<V/f/L35, and the ozone concentration of 0.65 to 0.7 ppm was maintained within the range of 35<V/f/L<50.

(60) Consequently, it is clear that the ozone generator preferably satisfies the condition of 0.5<V/f/L, and further preferably satisfies the condition of 1<V/f/L. When the ozone generator satisfies these conditions, the ozone molecules produced by the discharge are hardly exposed to the discharge again. Therefore, the ozone molecules are hardly decomposed via a reaction with an O atom, a water molecule, or an OH group under the re-discharge. Consequently, the ozone production amount reduction can be prevented.

(61) In addition, it is clear that the ozone generator preferably satisfies the condition of 50>V/f/L, and further preferably satisfies the condition of 20>V/f/L. When the ozone generator satisfies these conditions, the amount of the unreacted source gas 12 can be reduced, so that the ozone production amount reduction can be prevented.

(62) Furthermore, as is clear from the results of the samples 1 to 0.3, the flow rate of the source gas 12 flowing through the discharge space 22 is preferably 380 L/min or less. The flow rate is more preferably 300 L/min or less, further preferably 150 L/min or less. When the ozone generator satisfies these conditions, the distribution of the source gas 12 can be narrowed in the discharge space 22, the ozone molecules can be uniformly produced in the discharge space 22, and the source gas 12 can be used up for the ozone production. Therefore, the amount of the residual source gas 12 that has flowed through the discharge space 22 without the production reaction, can be reduced. Consequently, the ozone generator can exhibit a high ozone production efficiency.

Second Example

(63) Ozone production efficiency changes with absolute humidity were evaluated in samples 11 to 16. The ozone production efficiency corresponds to the ozone concentration of an exhaust gas under a constant applied electric power and a constant gas flow rate.

(64) Method for Measuring Ozone Production Efficiency

(65) In the measurement of the ozone production efficiency, an air was used as the source gas 12 under a gag flow rate of 350 L/min and a gas pressure of 0.10 MPa.

(66) As in the first embodiment, the alternating-current power source 18 was used as a discharge power source for applying the alternating-current voltage v with a voltage (amplitude A) of 4 kV and a frequency f of 20 kHz.

(67) Under the above conditions, the ozone concentration of the exhaust gas was measured using an ozone concentration meter EG-3000D (available from Ebara Jitsugyo Co., Ltd.).

(68) The details of electrode structures in ozone generators of the samples 11 to 16 were as follows.

(69) Sample 11

(70) The sample 11 had the structure shown in FIGS. 1 and 2 with the gap length Dg of 0.60 mm in the electrode pair 16.

(71) Samples 12 to 15

(72) The samples 12, 13, 14, and 15 had the same structure as the sample 11 except that the gap lengths Dg were 0.45, 0.30, 0.15, and 0.05 mm in the electrode pairs 16 respectively.

(73) Sample 16

(74) The sample 16 had the same structure as the sample 11 except that the gap length Dg was 1.00 mm in the electrode pair 16.

(75) Evaluation Result

(76) The evaluation results of the samples 11 to 16 are shown in FIG. 9.

(77) As is clear from FIG. 9, in the sample 16, ozone was produced within the absolute humidity range of 0 to 15 g/m.sup.3.

(78) In contrast, in the samples 11 to 15, ozone was produced within the absolute humidity range of 0 to 50 g/m.sup.3. In the samples 12 to 14, the ozone production efficiencies of 15 g/kWh or more were maintained within the absolute humidity range of 0 to 50 g/m.sup.3, and thus the ozone production processes were stably performed in a wide range of humidity environments. Particularly in the samples 12 and 13, the ozone production efficiencies of 25 g/kWh or more were maintained within the absolute humidity range of 0 to 50 g/m.sup.3.

(79) Consequently, it is clear that the upper limit of the gap length Dg in the electrode pair 16 is preferably less than 1.0 mm, further preferably 0.5 mm or less. In addition, it is clear that the lower limit of the gap length Dg is preferably 0.1 mm or more, further preferably 0.2 mm or more.

(80) It is to be understood that the ozone generator of the present invention is not limited to the above embodiment, and various changes and modifications may be made therein without departing from the scope of the invention.