JP6598730B2 - Discharge ozonolysis equipment - Google Patents

Description

  The present invention relates to a discharge type ozone decomposing apparatus that generates a discharge phenomenon in an electrode space formed between first and second electrode portions and decomposes ozone in an ozone-containing gas in the electrode space.

  As prior art documents disclosing conventional ozonolysis techniques, for example, there are techniques disclosed in Patent Document 1, Patent Document 2, and the like.

  Patent Document 1 discloses a system in which exhaust ozone gas is heated to about 500 ° C. by heat exchange with high-temperature exhaust gas from a turbine by an exhaust ozone decomposer, and residual ozone in exhaust ozone gas is thermally decomposed. .

In Patent Document 2, as a waste ozone treatment device, a system that decomposes residual ozone by heating a catalyst agent cylinder provided with MnO ₂ therein to 60 to 90 ° C. with an electric heater is disclosed.

  In addition to the ozonolysis technology disclosed in Patent Document 1 and Patent Document 2, as a method for decomposing high-concentration ozonized gas (residual ozone gas), a cylinder equipped with activated carbon (activated carbon method), or a catalyst agent is used. An ozonolysis device for supplying ozonized gas to a provided cylinder (catalyst method) is generally used.

  On the other hand, Patent Document 3 and Patent Document 4 disclose high-concentration ozone generators that use electric discharge as an ozone generation technique opposite to ozonolysis.

  The techniques disclosed in Patent Literature 3 and Patent Literature 4 are opposite to the idea of mounting an ozonolysis agent in the ozonolysis device disclosed in Patent Literature 1 and Patent Literature 2, and the discharge surface in the ozone generator. By attaching the material, it is an invention as an ozone generator that can take out ozone generated by discharge without decomposing gas and without decomposing it.

  In Patent Document 3, an alkali metal, an alkaline earth metal, or a rare earth element is contained in the A position of a transition metal oxide having a crystal structure in which atoms do not exist at the A position of the perovskite structure on the discharge surface of the ozone generator. It is described that the presence of a transition metal makes it possible to extract high-concentration ozone without decomposing ozone generated in the ozone generator.

  Further, Patent Document 3 has been developed on the basis of an unknown theory in the current state of the art. In particular, regarding “transition metal oxide having a crystal structure in which no atom exists at position A of the perovskite structure”, “does not decompose ozone”. Therefore, it is stated that high-concentration ozone can be obtained. However, in Patent Document 3, only the extracted ozone concentration characteristics are described, and there is no description that sufficiently shows the data and the basis for proving that the generated ozone is not decomposed in the generator.

  In addition, the perovskite structure and the effect of suppressing ozonolysis are also described with poor chemical basis.

  Compared to the description of the invention technology of the ozonolysis principle in the ozonolysis device in the disclosure content of Patent Literature 1 and Patent Literature 2, the disclosure content of Patent Literature 3 is an explanation of the principle that high concentration ozone is generated in the ozone generator. It is clear from the text that the invention is not sufficient and the explanation of the grounds is poor.

  Further, Patent Document 4 similarly discloses an “ozone generator that bakes and fixes a functional substance that prevents a decrease in ozone concentration on the dielectric surface (the functional substance is contained in the ceramic)”. There is not enough theoretical explanation about the existence of substances and functions that can suppress decomposition of ozone gas. In other words, although it has been determined that the functional substance described in Patent Document 4 is a functional substance (catalyst substance) that prevents a decrease in ozone concentration, the disclosed data result of the result of obtaining high-concentration ozone is disclosed. However, it is an invention in a state where the reason is unknown whether the cause of obtaining high-concentration ozone is due to the material that prevents the decrease in ozone concentration.

  In general, the catalytic reaction is defined as “acceleration and ionization of ozone and oxygen molecules into atoms and ion atoms by discharge and catalytic function”. However, although the molecular catalytic decomposition technique using an ozonolysis agent shown in Patent Literature 1 and Patent Literature 2 is generally demonstrated, discharge generation as shown in Patent Literature 3 and Patent Literature 4 is performed. There is no ground explanation that there is a functional substance that has the function of suppressing the ozonolysis of high-density ozone molecules obtained by the vessel, and the invention description of the disclosure contents of Patent Literature 3 and Patent Literature 4 is insufficient. There is no document to prove as a reliable invention. Therefore, it is judged that the invention has been made with a technique capable of obtaining high-concentration ozone other than Patent Document 3 and Patent Document 4.

JP 2002-58960 A JP-A-9-315804 Japanese Patent No. 4948007 Japanese Patent No. 5052304

  In the activated carbon method, which is a conventional ozonolysis technique, ozone remains on the activated carbon due to the slow decomposition rate, and the risk of the activated carbon igniting suddenly due to the heat of ozone decomposition, or the activated carbon itself deteriorates over time and due to oxidation by ozone. However, there was a problem of becoming a consumable item.

  Moreover, in the thermal decomposition method disclosed in Patent Document 1 and the like, in which the residual ozone is thermally decomposed, it is necessary to heat the gas containing the residual ozone to a high temperature (about 500 ° C.), which increases the heating cost. There was a point.

  In the catalytic method, which is a conventional ozone decomposition technique, the catalyst provided in the ozone decomposition cylinder through which the gas containing residual ozone flows is oxidized by being exposed to ozone, and the catalyst is deteriorated (has a lifetime). There was a problem that occurred.

Furthermore, with the conventional ozone decomposition treatment technique described above, the residual ozone in a high concentration region (several tens of g / m ^{3 to} 500 g / m ³ ) and the high-range ozone amount at a gas flow rate of 1 SLM or more are immediately decomposed. It was unsuitable for processing. When installing an ozonolysis apparatus with the maximum ozonolysis capacity to decompose such high concentration and large flow ozone gas, there is a problem that the apparatus size of the ozonolysis apparatus becomes very large and the cost becomes high. there were.

  The present invention has been made to solve the above-described problems, and provides an ozone decomposing apparatus capable of accurately decomposing ozone in an ozone-containing gas by decomposing ozone in a gas containing ozone with a relatively simple apparatus configuration. With the goal.

The discharge-type ozonolysis apparatus according to claim 1 of the present invention is a discharge-type ozonolysis apparatus provided independently of an ozone generator and an ozone treatment apparatus, and is a first type output by the ozone generator. One of the ozone-containing gas and the second-type ozone-containing gas discharged by executing a predetermined ozone treatment step by the ozone treatment device with respect to the first-type ozone-containing gas is selected as the selected ozone-containing gas. an ozone-containing gas selection mechanism, and first and second electrode portions facing each other, the selection ozone containing containing ozone to the electrode portion space formed between the first and second electrode portions A gas is supplied, a metal compound layer is provided on the surface of the electrode part space side of at least one of the first and second electrode parts, and a discharge current is supplied to the first and second electrode parts. The first and second electrode parts generate a discharge phenomenon in the electrode part space when supplying the discharge power, and the metal compound layer acts as an ozone decomposition catalyst. to decompose ozone of the selection ozone-containing gas in the electrode portion space acts as an ozone decomposer obtaining ozonolysis gas used, ozonolysis ability to degrade the ozone of the selection ozone-containing gas by the ozone decomposer may have a power value and positive correlation of the discharge power, the metal compound material layer satisfies the following conditions (1) and condition (2), {condition (1) is not a conductor, condition (2 ) Activated (excited) by the discharge phenomenon}, the discharge type ozone decomposing apparatus comprises a concentration meter for detecting the ozone concentration of the selected ozone-containing gas, and the supply of the selected ozone-containing gas to the electrode space. Flow rate A flow rate detector for detecting the discharge power based on the ozone concentration and the supply flow rate so that the ozone content of the ozone-decomposed gas is not more than a set reference value. It is characterized by determining .

2. The discharge type ozonolysis apparatus according to claim 1, wherein the first and second electrode parts generate a discharge phenomenon in the electrode part space when supplying the discharge power, and the metal compound layer is supplied when the discharge power is supplied. by work as an ozone decomposition catalyst to decompose the ozone in the selection ozone-containing gas in the electrode portion in a space to function as an ozone decomposer obtaining ozonolysis gas used, the ozone selection ozone-containing gas by the ozone decomposer The ozonolysis capability of the catalyst on the discharge surface to be decomposed is characterized by having a positive correlation with the power value of the discharge power.

The discharge-type ozonolysis apparatus according to the first aspect of the present invention has the above-described characteristics, so that the first and second electrode portions function as an ozonolysis device, thereby allowing a selective ozone-containing gas to be formed with a relatively simple apparatus configuration. Ozone decomposition gas can be obtained by decomposing ozone inside. At this time, the ozonolysis capability can be variably set with high accuracy according to the power value of the discharge power.

It is explanatory drawing which shows typically the structure of the electrode part used as the principal part of the discharge type | formula ozonolysis apparatus which is embodiment of this invention, and a high frequency power supply. It is explanatory drawing which shows typically the usage example of the discharge type ozonolysis apparatus of embodiment. It is explanatory drawing which shows the internal structure of the discharge type | formula ozonolysis apparatus of this Embodiment, and its periphery. It is explanatory drawing which shows the performance specification example of the discharge type ozonolysis device in this Embodiment in a table form. It is explanatory drawing which shows the ozonolysis capability characteristic of the discharge type ozonolysis device in this Embodiment.

<Principle of the invention>
Apart from the techniques disclosed in Patent Document 3 and Patent Document 4, the catalytic reaction has only the ability to decompose molecular gas, and has the ability to generate ozone only by three-body collision of dissociated oxygen atoms during the non-discharge period. This principle can sufficiently explain the effect of the metal material applied to the discharge surface of the ozone generator.

  On the other hand, two opposing electrodes are formed by using a metal compound layer having a specific metal material compound activated by discharge light or thermal energy by reversely utilizing the decomposition effect of the molecular gas of the metal material applied to the discharge surface. An electrode structure with a specific metal may be considered, for example, by being applied to a discharge interface between the electrodes or the dielectric.

  The inventors use the electrode structure with a specific metal, apply a voltage between the electrodes, generate a discharge phenomenon in the electrode space formed between the electrodes, and generate ozone in the electrode space (discharge space). It was found for the first time that a function as a discharge-type ozone decomposing unit that obtains ozone-decomposed gas by decomposing ozone in the ozone-containing gas by flowing the contained gas (ozone-containing gas) was obtained. This discharge type ozonolysis device is an invention obtained by reversing the conventional ozone generation technology in which ozone is generated by a discharge phenomenon.

  Furthermore, the inventors adjust the power value (W) of the discharge power according to the amount of ozone contained in the ozone-containing gas, thereby increasing the photocatalytic ability by the discharge light energy of the two electrode surfaces facing each other. As a result, the inventors have devised to realize a discharge type ozone decomposer capable of decomposing a desired amount of ozone by variably setting the catalytic ozone decomposing capability in the discharge type ozone decomposing unit.

  As described above, the discharge-type ozonolysis device using the electrode structure with a specific metal activates (excites) the metal compound layer provided at the discharge interface by heat energy and light energy at the time of occurrence of the discharge phenomenon. Therefore, even if ozone gas has a high concentration and a large (supply) flow rate, it is easy to increase the catalytic decomposition capability in the electrode space (discharge space) of the ozone decomposer simply by injecting discharge power corresponding to the concentration. It has been found through experiments that it has the effect of accelerating the dissociation reaction of ozone molecules and immediately decomposing a high concentration ozonized gas to a low concentration.

  By using such a discharge-type ozonolysis device to decompose relatively high-concentration ozone to obtain relatively low-concentration ozone, the conventional low-concentration method using a thermal decomposition method or a catalyst method attached to the latter stage is used. The load of the ozone decomposing apparatus can be reduced, and the life of the latter ozone decomposing apparatus can be extended, the ozonolysis treatment speed can be improved, and the cost can be reduced.

  The above is the basic part of the principle of the present invention. Further, details of the principle of the invention such as the combination of the discharge phenomenon and the metal compound layer will be described in detail later.

  The above-described present invention achieves the above-described prior art by realizing a discharge-type ozonolysis device in which a catalytic decomposition function is added to a relatively simple configuration that is a combination structure of first and second electrodes facing each other. It is possible to solve the problems of Patent Document 1 and Patent Document 2, which are documents.

<Embodiment>
FIG. 1 is an explanatory view schematically showing the configuration of the electrode parts 1A and 1B and the high-frequency power source 13 which are the main parts of the discharge ozonolysis apparatus 22 according to the embodiment of the present invention.

  As shown in the figure, the discharge-type ozonolysis apparatus 22 includes an electrode part 1A and an electrode part 1B (first electrode part and second electrode part) facing each other, and includes an electrode part 1A and an electrode part 1B. A high-concentration residual ozone gas G2 (ozone-containing gas) containing ozone is supplied to the electrode space SP1 formed therebetween.

  The electrode portion 1A is formed by a laminated structure of a conductive electrode 10a, a dielectric 11a, and a metal compound layer 12a, and the metal compound layer 12a is provided on the electrode portion space SP1 side.

  The electrode portion 1B is formed by a laminated structure of a conductive electrode 10b, a dielectric 11b, and a metal compound layer 12b, and the metal compound layer 12b is provided on the electrode portion space SP1 side. Thus, both the metal compound layers 12a and 12b are provided on the discharge surface side.

  One of the metal compound layers 12a and 12b may be omitted. In other words, any metal compound layer may be provided on the surface of the electrode part space SP1 side of at least one of the electrode parts 1A and 1B.

  Thus, the electrode portions 1A and 1B described above have the electrode structure with a specific metal described in the principle of the invention.

  Further, in the discharge type ozone decomposing apparatus 22, a high frequency power source 13 is provided between the electrode 10a of the electrode portion 1A and the electrode 10b of the electrode portion 1B, and the high frequency power source 13 generates AC discharge power between the electrode portions 1A and 1B. Supply. As a result, a high frequency voltage can be applied between the electrode portions 1A and 1B.

  Then, when supplying the discharge power from the high-frequency power source 13 between the electrode portions 1A and 1B, that is, when applying a high-frequency discharge voltage, a dielectric barrier discharge, which is a discharge phenomenon, is generated in the electrode space SP1, and the metal compound layer A discharge-type ozone decomposing unit 221 that decomposes ozone in the high-concentration residual ozone gas G2 in the electrode space SP1 to obtain a low-concentration residual ozone gas G3 (ozone-decomposed gas) by using 12a and 12b as an ozone decomposition catalyst. As a result, the electrode portions 1A and 1B are made to function.

  The ozonolysis ability of decomposing ozone in the high-concentration residual ozone gas G2 in the ozonolysis device 221 realized by the electrode portions 1A and 1B depends on the catalyst decomposition ability formed on the electrode surface. 13 has a positive correlation with the power value (W) of the discharge power supplied from 13. That is, in principle, the ozonolysis capability of the ozonolysis device 221 increases or decreases according to the power value (discharge energy) of the discharge voltage applied to the electrode portions 1A and 1B. Furthermore, it is assumed that if the power frequency (output frequency) of the discharge power is increased to a high frequency discharge of 100 kHz or higher, discharge with a lower discharge load impedance can be realized and the ozone decomposition ability can be further enhanced.

  As described above, it was confirmed that the ozonolysis capability of the ozonolysis device 221 depends on the power value of the discharge power supplied from the high-frequency power source 13. Therefore, at least when the power frequency of the discharge power supplied from the high frequency power supply 13 is constant, the ozonolysis capability increases or decreases according to the power value of the discharge power.

  By using the property of the ozonolysis device 221 and setting the power value of the discharge power from the high frequency power source 13, the ozonolysis capability of the ozonolysis device can be set to an appropriate value. Specifically, the ozone decomposing capability of the ozone decomposing unit 221 can be set by setting the power value of the discharge power that becomes the discharge energy corresponding to the residual ozone amount and supply flow rate contained in the high concentration residual ozone gas G2. it can.

  As described above, the ozonolysis capability of the ozonolysis device 221 depends in principle on the power value of the discharge power, that is, has a positive correlation, while being provided on the electrode space SP1 side by coating or the like. It has been found that it depends greatly on the materials of 12a and 12b.

  That is, if the metal compound layers 12a and 12b having high ozone decomposing ability are selected, there is an effect that a relatively high residual ozone amount can be decomposed even with a discharge power having a relatively small power value.

  However, with respect to the supplied ozone concentration, relatively many substances have the ability to decompose ozone, but the ozone decomposition ability as disclosed in Patent Document 3 and Patent Document 4 is very high. There was no degradation inhibitor having the property of inhibiting at the level.

  If the decomposition inhibitory substance exists, even if the ozone gas flow rate to be supplied is increased or the gas temperature is increased to increase the number of collisions between the ozone gas and the decomposition inhibitory substance, the ozone concentration is extremely lowered. Not expected. However, if the power value (W) of the discharge power from the high-frequency power source 13 is increased in a situation that depends on the number of collisions due to an increase in the gas flow velocity or gas temperature of the high-concentration residual ozone gas G2, the ozone concentration decreases regularly, that is, It was confirmed that the ozonolysis ability increased regularly with increasing discharge power value. Therefore, the metal compound layer itself applied to the discharge interface on the electrode part space SP1 side acts as an ability to decompose ozone gas, but the decomposition ability of ozone gas is extremely suppressed by contact with the high-concentration residual ozone gas G2. It has been found that there is no substance with a special function that can.

The discharge in the thermal equilibrium state generally has the ability to easily decompose and dissociate oxygen molecules and ozone molecules by electron collision of the discharge, but it is several hundred g / m ³ (tens of thousands ppm) or more and is large. It does not have the ozone decomposing ability to decompose ozone at a flow rate to ozone with a low concentration (1000 ppm or less) only with electrons generated by discharge plasma.

  In other words, only normal discharge plasma has an ozone decomposing ability that immediately decomposes a large amount of residual ozone by simply passing the high-concentration residual ozone gas G2 through the electrode space SP1 that is a limited discharge space. Therefore, it has been extremely difficult to achieve the ozone decomposing capability required by the present application with a discharge-type ozone decomposing device using only discharge plasma.

  Therefore, when a metal compound layer composed of a compound of a specific metal material is provided on the electrode portion space SP1 side of the electrode portions 1A and 1B by a process such as coating at the discharge interface, a discharge phenomenon occurs in the electrode portion space SP1. The applied metal compound layer can be easily activated (excited) by the heat energy and light energy. The activated state of these metal compound layers is always maintained in the continuous discharge operation state, and the discharge is extremely high in ozonolysis by the catalytic catalytic reaction between the activated metal compound layer and the ozonized gas. It was found that an ozonolysis device 221 of the formula could be realized.

  That is, the discharge type ozonolysis device 221 is realized by combining the discharge phenomenon generated in the electrode portion space SP1 and the metal compound layer applied to the electrode portion space SP1 side of the electrode portions 1A and 1B, that is, the discharge surface side. By doing so, it was found that the ozonolysis ability can be greatly improved.

In this way, a high concentration residual ozone amount of several hundred g / m ³ (tens of thousands ppm) or more is supplied from the high frequency power supply 13 with a discharge power having a power value of several hundred to several kW. In addition, by variably setting the power value (W) of the discharge power, the ozone decomposing ability that immediately decomposes high concentration ozone of several g / m ³ to several hundred g / m ³ to low concentration (less than 1000 ppm) ozone. It was found that the ozonolysis device 221 can be exhibited. And this embodiment implement | achieved the discharge type | formula ozone decomposition apparatus 22 which added the catalytic decomposition function which makes the basic composition the combination of electrode part 1A and 1B and the high frequency power supply 13. FIG.

  As the metal compound layers 12a and 12b, any metal material compound that can be easily activated (excited) by thermal energy or light energy at the time of occurrence of a discharge phenomenon in the electrode space SP1 and becomes a substance having semiconductor properties, Basically, it has the ability to decompose high concentration ozone gas. However, some of the metal material compounds have the ability to not only catalyze the decomposition of ozone molecules but also the decomposition of oxygen molecules. Therefore, only the ozone molecules cannot be selectively dissociated. There is also a metallic material compound that cannot generate ozone gas by collision of atoms and oxygen molecules (three-body collision), and as a result, can decompose high-concentration ozonized gas to sufficiently low concentration ozone.

From the above, as a result of experimental verification, the metal compound layers 12a and 12b having specific substances particularly suitable for ozonolysis are particularly Ni (nickel), Mn (manganese), Co (cobalt), and Cu. It became clear that the metal compound of (copper) is a substance having high decomposition ability. Specific examples of the above-described specific metal compound material of the specific substance include substances such as MnO ₃ , Co ₂ O ₃ , Cu ₂ O, and Ag ₂ O.

  These metal compounds are easily activated (excited) simply by receiving heat energy at a relatively low temperature from the outside, become a substance having semiconductor properties, and are active molecular gases such as ozone. Although it exhibits a catalytic reaction, it is a substance that hardly exhibits a catalytic reaction with respect to oxygen molecules having an activity ability lower than that of ozone.

  Therefore, it can be said that the metal compound containing Ni, Mn, Co, and Cu is a substance suitable for the ability to selectively decompose only ozone molecular gas. Also, in materials other than metal compounds including Ni, Mn, Co, and Cu, metal compounds activated by a discharge phenomenon or the like to be in an excited state are almost very high in catalytic decomposition reaction with ozone gas. It is a substance that can be an ozonolysis catalyst substance. Furthermore, these metal compounds having an ozone catalytic decomposition action generate heat due to the heat of ozonolysis by being brought into contact with ozone gas, the excited state of these metal compounds is further promoted, and the ozonolysis catalytic reaction is further promoted. The ozonolysis ability can be increased.

  Further, when the power value of the discharge power of the high frequency power supply 13 is increased, the discharge power density per unit discharge area in the electrode space SP1 increases, and the metal compound material applied to the discharge surface side in proportion to the discharge power density. The discharge energy (discharge power) injected into the layers 12a and 12b increases, and the catalytic ozonolysis ability by the activated metal compound layers 12a and 12b increases proportionally. The discharge area means an overlapping area in plan view between the electrode parts 1A and 1B that form the electrode part space SP1.

  In addition, in the action of the ozone decomposing ability, it is desirable to realize an equilibrium high-temperature plasma rather than a non-equilibrium discharge plasma because the ozone decomposing ability is improved. Further, the relationship between the discharge power and the gas flow rate of the high-concentration residual ozone gas G2 to be supplied is shown. When the gas flow rate of the high-concentration residual ozone gas G2 to be supplied is reduced or the discharge area is increased, the electrode that becomes the discharge space Since the time for passing through the partial space SP1 becomes longer and the gas temperature due to the discharge heat energy also becomes higher, the effect of increasing the ozone decomposing ability is produced, which is desirable for increasing the ozone decomposing ability.

  The discharge-type ozonolysis device 221 of the above-described embodiment has the electrode portions 1A and 1B as a basic configuration, and the discharge form in the discharge phenomenon generated in the electrode portion space SP1 is a dielectric barrier discharge. Even if a discharge phenomenon caused by arc discharge, glow discharge or creeping discharge is generated, the same effect can be obtained. When the above-described other discharge forms are employed, the dielectric 11a and the dielectric 11b are not necessary in the electrode portions 1A and 1B.

  Further, if the power frequency of the AC discharge voltage applied from the high frequency power supply 13 is increased and the discharge phenomenon generated in the electrode space SP1 is a high frequency discharge plasma, the discharge plasma is likely to become a thermal equilibrium plasma and becomes a discharge space. The gas temperature in electrode part space SP1 rises and it can improve an ozone decomposition processing capacity more. That is, as described above, the ozonolysis ability of the ozonolysis device can be expected to be increased by increasing the power frequency and setting it to a high frequency. In addition, 100 kHz or more is assumed as a high frequency electric power frequency.

  As described above, a relatively small discharge-type ozonolysis device 221 having the electrode portions 1A and 1B as a basic configuration is used, and the discharge phenomenon in the electrode portion space SP1 is utilized to achieve a high concentration and a high flow rate. The ozone in the residual concentration ozone gas G2 can be decomposed to obtain an ozone-decomposed gas.

  Further, the discharge type ozone decomposing apparatus 22 of the present embodiment has a long life as an apparatus, and does not require replacement of a decomposing agent using a large amount of an ozone decomposing agent, unlike the conventional ozone decomposing apparatus. Therefore, it is desirable to use the discharge-type ozonolysis apparatus 22 of the present embodiment in combination with the conventional ozonolysis apparatus having a low ozonolysis capability. By using the discharge-type ozonolysis apparatus 22 together, the conventional ozonolysis apparatus is used. This contributes to the reduction of ozone decomposing ability and long life of the equipment.

  In the discharge-type ozonolysis apparatus 22 of the present embodiment described above, the electrode portions 1A and 1B (first and second electrode portions) cause a discharge phenomenon in the electrode space SP1 when the discharge power is supplied from the high frequency power supply 13. By generating and using the metal compound layers 12a and 12b as an ozone decomposition catalyst, the ozone in the high concentration residual ozone gas G2 (ozone-containing gas) in the electrode space SP1 is decomposed and the low concentration residual ozone gas G3 (ozone decomposition completed) The first feature that functions as an ozonolysis device 221 for obtaining a gas).

  Further, the discharge type ozone decomposing apparatus 22 has an ozone decomposing ability for decomposing ozone in the high concentration residual ozone gas G2 in the ozone decomposing unit 221 (electrode portions 1A and 1B) as a power value of discharge power supplied from the high frequency power source 13. There is a second feature that it has a positive correlation with (W).

  As described above, the discharge-type ozonolysis apparatus of the present embodiment has the first feature, so that the electrode portions 1A and 1B that receive the supply of discharge power from the high-frequency power supply 13 function as the ozonolysis device 221. Thus, there is an effect that the ozone in the high concentration residual ozone gas G2 can be decomposed to obtain the low concentration residual ozone gas G3 with a relatively simple apparatus configuration.

  Furthermore, the discharge-type ozonolysis apparatus 2 according to the present embodiment has the second feature described above, so that the ozonolysis capability can be variably set with high accuracy according to the power value of the discharge power supplied from the high-frequency power supply 13. .

  In addition, as shown in FIG. 1, the discharge type ozonolysis apparatus 22 of the present embodiment can be applied to the discharge interface of the dielectric 11a and the dielectric 11b of the electrode portions 1A and 1B that function as the ozonolysis unit 221. The metal compound layers 12a and 12b are provided by the treatment.

  On the other hand, if only the normal discharge phenomenon is caused by the electrode portions 1A and 1B without the metal compound layers 12a and 12b, the power value of the discharge power supplied from the high frequency power supply 13 is set to several hundred watts to several K watts. However, the ozonolysis ability is at most about a few (mg / h) to several (g / h), and a residual ozone amount (g / h) of several hundred (mg / h) to several thousand (g / h) is supplied. Even so, it has only an ozonolysis capability of about 0.01 to 0.001 times.

  However, as described above, the ozonolysis device 221 in the discharge ozonolysis device 22 is activated by applying discharge heat or discharge light energy to the discharge interface on the electrode portion space SP1 side of the electrode portions 1A and 1B. Metal compound layers 12a and 12b that can be (excited) are provided by coating or the like. For this reason, the discharge type ozonolysis apparatus 22 activates (excites) the metal compound layers 12a and 12b of the electrode portions 1A and 1B by the discharge power of the high-frequency power source 13, and exhibits a photocatalytic chemical reaction. The ability to decompose ozone gas that passes through the space SP1 has been dramatically improved, and the ability to decompose ozone is several hundred to several thousand times that of a discharge-type ozone decomposer that is not coated with the metal compound layers 12a and 12b. The discharge-type ozonolysis device 221 can be realized.

  As the metal compound layers 12a and 12b, in particular, when a metal compound of Ni, Mn, Co, and Cu is used, it is several thousand times that of a discharge-type ozonolyzer that does not have the metal compound layers 12a and 12b applied. Among them, the discharge type ozonolysis device with Ni metal compound material applied has the highest ozonolysis capability, and the predetermined power decomposition (W) of the injected discharge power is small. It turns out to have the ability.

  Further, even if it is a metal compound other than the metal compounds of Ni, Mn, Co, and Cu, {(1) not a conductor but (2) activated (excited) by a discharge phenomenon in the electrode space SP1} The metal compound layers 12a and 12b have a decomposition ability that is several tens to several hundreds times that of a discharge-type ozonolysis device that is not coated with the metal compound layers 12a and 12b. The effect of decomposing ozone can be expected.

In the ozonolysis device 221 used in the discharge-type ozonolysis apparatus 22 of the present embodiment, the discharge power is supplied from the high frequency power source 13 to generate a discharge phenomenon in the ozonized gas (ozone molecule group) in the electrode space SP1. By doing so, an efficient discharge type ozone decomposing apparatus with excellent ozonolysis ability was shown. The ozonolysis device 221 also forms a metal compound layer on the discharge surface even in other molecular exhaust gases, activates the metal compound layer applied by the discharge phenomenon, and activates the activated substance. Utilizing the catalytic action, it can be used as a decomposer of a predetermined component such as nitrogen oxide (NO _x ) in the exhaust gas.

  FIG. 2 is an explanatory view schematically showing an example of use of the discharge type ozone decomposing apparatus of the embodiment. The ozone generator 21 generates the high-concentration ozone gas G1, and the existing ozone processing apparatus executes an ozone processing step P20 that performs a specific process using the high-concentration ozone gas G1. Examples of the ozone treatment process P20 include a semiconductor manufacturing process and a water and sewage purification process that require a large volume of high-concentration ozone gas G1 such as a high concentration and a large flow rate.

  And unnecessary ozone gas is discharged | emitted as high concentration residual ozone gas G2 at the time of execution of ozone treatment process P20. The discharged high-concentration residual ozone gas G2 contains relatively high-concentration ozone.

  The discharge-type ozone decomposing apparatus 22 of the present embodiment receives the high-concentration residual ozone gas G2, and decomposes ozone in the high-concentration residual ozone gas G2 by the ozone decomposer 221 realized by the electrode portions 1A and 1B described above. A low-concentration residual ozone gas G3 is obtained. This low concentration residual ozone gas G3 is supplied to the low concentration ozone decomposition apparatus 23 in the next stage.

  The low-concentration ozone decomposition device 23 discharges the low-concentration residual ozone gas G3 to the outside air as a harmless gas G4 whose main component is oxygen decomposed to an extremely low concentration of allowable ozone concentration or less. As the low-concentration ozonolysis apparatus 23, an ozonolysis apparatus using an existing technique such as an activated carbon method, a catalyst method, or a thermal decomposition method is assumed.

  As described above, the high-concentration residual ozone gas G2 is reduced to the low-concentration residual ozone gas G2 through the discharge ozone decomposition apparatus 22 of the present embodiment in the ozonized gas decomposition treatment flow for the high-concentration residual ozone gas G2 discharged by the ozone treatment process P20. Ozone decomposition treatment can be performed to make the residual ozone gas G3. Furthermore, the burden of the existing low concentration ozone decomposition device 23 disposed downstream of the discharge type ozone decomposition device 22 is greatly reduced, and the life of the low concentration ozone decomposition device 23 is extended. It can also contribute to cost reduction.

  FIG. 3 is an explanatory diagram showing the internal configuration of the discharge-type ozonolysis apparatus 22 of the present embodiment and its periphery. The discharge type ozonolysis apparatus 22 of the present embodiment has a densitometer 223 and a flow rate detector 224 in addition to the discharge type ozonolysis apparatus 221 and the high frequency power supply 13 shown in FIG. In addition, the ozonolysis device 221 is implement | achieved by the combined structure of the electrode parts 1A and 1B shown in FIG.

  Referring to the figure, high-concentration ozone gas G1 is supplied from ozone generator 21 through valve 21a to ozone treatment apparatus 20, and ozone treatment apparatus 20 executes ozone treatment process P20 described above to perform high-concentration residual ozone gas G2. Is discharged.

  In general, the high-concentration ozone gas G1 may be supplied to the ozone treatment apparatus 20 or may be discarded directly as the high-concentration residual ozone gas G2 without going through the ozone treatment apparatus 20, and the valves 21a and 21b are connected to the ozone treatment apparatus 20. This is a switching valve for bypassing the supply and the ozone treatment device 20 to escape as high-concentration residual ozone gas G2.

  That is, when the valve 21a is “open” and the valve 21b is “closed”, the high-concentration residual ozone gas G2 after the execution of the ozone treatment process P20 by the ozone treatment device 20 is discharged to the discharge ozone decomposition device 22, and the valve 21a Is “closed” and the valve 21b is “open”, the high-concentration ozone gas G1 from the ozone generator 21 is supplied as it is to the discharge ozone decomposition apparatus 22 as the high-concentration residual ozone gas G2.

The discharge type ozone decomposition apparatus 22 receives the high concentration residual ozone gas G2. At this time, the concentration meter 223 detects the ozone concentration DC2 (g / m ³ ) of the high-concentration residual ozone gas G2, and further supplies the high-concentration residual ozone gas G2 to the ozone decomposer 221 by the flow rate detector 224 in the next stage. An ozone flow rate DQ2 (L / min) that is a flow rate is detected. The flow rate detector 224 may be installed on the line of the low concentration residual ozone gas G3 or the harmless gas G4.

As the ozone concentration DC2, a high concentration of about several g / m ³ (several thousand ppm) to several hundred g / m ³ (several hundred thousand ppm) is assumed, and the ozone flow rate DQ2 is 1 (L / min) to A large flow rate of about 100 (L / min) is assumed. That is, as the residual ozone amount H2 of the high-concentration residual ozone gas G2, a large amount of residual ozone amount of several hundreds (mg / h) to several thousand (g / h) is assumed in calculation.

  The ozone concentration DC2 and the ozone flow rate DQ2 detected by the densitometer 223 and the flow rate detector 224 are applied to the high frequency power source 13. The high-frequency power source 13 recognizes the residual ozone amount H2 (g / h) of the high-concentration residual ozone gas G2 from the ozone concentration DC2 and the ozone flow rate DQ2, and the residual ozone amount prescribed value SH (residual ozone) that the residual ozone amount H2 becomes the set reference value. Discharge power control is performed to set the power value (W) of the discharge power supplied to the ozonolysis device 221 so as to decrease below the concentration regulation value C2).

  The high-frequency power source 13 supplies a power value (W of discharge power supplied to the ozone decomposer 221 with respect to the high-concentration residual ozone gas G2 having a large amount of residual ozone of several hundreds (mg / h) to thousands (g / h). ) Is variably set to several hundred watts to several kilowatts. In the example shown in FIG. 4 to be described in detail later, the power value of the discharge power supplied from the high frequency power supply 13 can be variably set at 0.1 to 5 (kW). The power frequency of the discharge power supplied from the high frequency power supply 13 is fixed at about 10 to 100 kHz.

  For example, when the basic ozone decomposing ability is set to the ozonolysis device 221 with a power value of discharge power per kW (about 120 g / h (33 mg / s)), by supplying a discharge power of a maximum of 5 kW from the high frequency power supply 13 The ozonolysis capacity of the ozonolysis device 221 can be increased to about 600 g / h ((120 g / h) × 5).

  As a result, the ozone decomposer 221 can reduce the ozone amount in the high-concentration residual ozone gas G2 to be equal to or less than the residual ozone amount prescribed value SH (residual ozone concentration prescribed value C2), which is a set reference value. The low-concentration residual ozone gas G3 that has been made SH or less is output to the low-concentration ozone decomposition device 23 in the next stage.

  As described above, the high-frequency power supply 13 supplies discharge power having an appropriately set power value to the ozonolysis device 221 so as to cause the discharge type ozonolysis device 221 to generate a discharge phenomenon. Depending on the power value of the discharge power, the ozone decomposition ability by the ozone decomposer 221 is determined.

  Therefore, by detecting the ozone concentration DC2 indicating the residual ozone gas concentration C and the ozone flow rate DQ2 indicating the gas flow rate Q, the residual ozone amount of the high-concentration residual ozone gas G2 is obtained. Discharge power control for setting the power value (W) of the discharge power supplied from the high-frequency power supply 13 can be performed so that the ozonolysis can be appropriately performed so as to fall below the specified amount SH. As a result, most of the residual ozone of the high-concentration residual ozone gas G <b> 2 that is discharged can be ozonolyzed by the discharge-type ozone decomposing device 22 having the ozonolysis device 221.

  The low-concentration ozone decomposition device 23 further decomposes the low-concentration residual ozone gas G3 into ozone, and discharges it as a harmless gas G4 (oxygen gas) decomposed to a very small amount of ozone of 0.01 ppm or less.

  As described above, the discharge-type ozone decomposing apparatus 22 of the present embodiment also has a power value (W) of discharge power supplied from the high-frequency power supply 13 to the high-concentration residual ozone gas G2 having a large amount of residual ozone. By setting appropriately, it is possible to obtain the low concentration residual ozone gas G3 that is surely equal to or less than the residual ozone amount prescribed value SH (residual ozone concentration prescribed value C2).

  That is, the ozone decomposing ability can be easily variably set by variably setting the power value (W) of the discharge power supplied from the high frequency power supply 13 in accordance with the residual ozone amount of the high concentration residual ozone gas G2.

  As a result, the discharge type ozone decomposition apparatus 22 of the present embodiment is a relatively simple discharge in which the power value (W) of the discharge power of the high-frequency power source 13 is set based on the remaining ozone amount of the high-concentration residual ozone gas G2. The ozone decomposition ability can be variably set so as to obtain the low-concentration residual ozone gas G3 by power control. For this reason, the discharge type ozone decomposing apparatus 22 of the present embodiment is an apparatus suitable for constructing an ozone decomposing apparatus in the field using high-concentration ozone gas.

  In the discharge power control example of the high-frequency power source 13 described above, the power value (W) of the discharge power injected into the discharge type ozone decomposer 221 according to the ozone concentration of the residual ozone gas of the high concentration residual ozone gas G2 and the supply flow rate. An example of control for adjusting is shown. Instead of this control example, the ozone concentration or gas flow rate of the high-concentration ozone gas G1 supplied from the ozone generator 21 is detected, and the power value of the discharge power supplied to the discharge-type ozone decomposer 221 is adjusted or preset. The power value of the discharge power may be adjusted based on the set gas flow rate and the residual ozone concentration assumed in advance.

  As described above, the high-frequency power supply 13 of the discharge-type ozone decomposing apparatus 22 of the present embodiment is based on the ozone concentration DC2 and the ozone flow rate DQ2 detected by the concentration meter 223 and the flow rate detector 224, and the low concentration residual ozone gas G3 (ozone It is characterized in that the power value (W) of the discharge power is determined so that the ozone content of the (decomposed gas) is equal to or less than the residual ozone amount prescribed value SH (residual ozone concentration prescribed value C2) which is a set reference value. .

  The discharge type ozone decomposing apparatus 22 according to the embodiment has the above characteristics, so that the ozone content is the set reference value even for the high-concentration residual ozone gas G2 (ozone-containing gas) in which the ozone concentration and the supply flow rate change. The low-concentration residual ozone gas G3 that is equal to or less than the residual ozone amount prescribed value SH (residual ozone concentration prescribed value C2) can be stably obtained.

FIG. 4 is an explanatory view showing a performance specification example of the discharge-type ozonolysis device 221 in a table format. As shown in FIG. 5 (a), the power value of the discharge power supplied from the high frequency power source 13 as an inverter power source is set to 100 W to 5 kW, and the ozone decomposable ozone concentration is 2 to 498 g / m with respect to the ozone decomposing ability. ³ and the maximum amount of ozone gas that can be decomposed by ozone is 600 g / h. The power frequency of the discharge power is fixed at about 10 to 100 kHz.

Then, as shown in FIG. 4B, the assumed ozone gas flow rate (supply flow rate) of the high concentration residual ozone gas G2 is in the range of 1 to 100 L / min, and the assumed ozone gas concentration of the high concentration residual ozone gas G2. As a range of 5 to 500 g / m ³ . In this case, the ozone gas amount of the high-concentration residual ozone gas G2 to be decomposed is empirically assumed to be 0.5 g / h to 600 g / h. Therefore, the decomposed ozone concentration (2 to 498 g / m ³ ) shown in FIG. 2A can be exerted without any trouble as long as the ozone gas flow rate of the high concentration residual ozone gas G2 is at least 100 L / min.

With respect to the high-concentration residual ozone gas G2 under the above assumption, a discharge-type discharge system having an ozone decomposing ability capable of setting the residual ozone concentration of the low-concentration residual ozone gas G3 to 2 g / m ³ or less and the residual ozone amount to 12 g / h or less. It becomes the performance specification of the ozonolysis device 221. As described above, FIG. 4 shows the performance of the ozonolysis device 221 having an ozonolysis capability for decomposing an ozone amount of 120 g / h (33 mg / s) per 1 kW of discharge power.

  FIG. 5 is an explanatory diagram showing the characteristics of the ozonolysis capability of the ozonolysis device 221 having the decomposition performance shown in FIG.

In FIG. 5, the horizontal axis indicates the exhaust gas flow rate Q (L / min) of the high-concentration residual ozone gas G2, which is the supply flow rate to the ozone decomposer 221, and the vertical axis indicates the exhaust ozone concentration C (g) of the high-concentration residual ozone gas G2. / M ³ ). The target ozone decomposition concentration maximum value C1 indicated by a one-dot chain line indicates the maximum value (500 g / m ³ ) of the target ozone decomposition concentration of the discharge-type ozone decomposer 221 of the present embodiment. A residual ozone concentration regulation value C2 indicated by a one-dot chain line indicates a residual ozone concentration regulation value (2 g / m ³ ) in the low-concentration residual ozone gas G3 after decomposition.

  Ozone decomposition characteristics L21 to L24 indicate characteristics that are a constant ozone amount Y (g / h) to be decomposed, which is obtained from the exhaust gas flow rate Q and the exhaust ozone concentration C. The ozonolysis characteristic L21 indicates a characteristic that provides a constant ozone amount of 600 g / h, which is the maximum decomposing ability of the ozonolysis device 221. The ozone decomposition characteristics L22, L23, and L24 indicate characteristics that give constant ozone amounts of 400 g / h, 100 g / h, and 10 g / h.

  The points PA, PB, and PC are detected by the flow rate detector 224 with the exhaust gas flow rates QA, QB, and QC as the ozone flow rate DQ2, and detected by the densitometer 223 with the exhaust ozone concentrations CA, CB, and CC as the ozone concentration DC2. It is a point obtained by doing. That is, the points PA, PB, and PC are (QA, CA), (QB, CB), and (QC, CC).

  The high frequency power source 13 calculates the ozone decomposition amount Y (broken line characteristics such as the ozone decomposition characteristics L21 to L24 in FIG. 5) based on the ozone flow rate DQ2 and the ozone concentration DC2, and the discharge type is calculated according to the obtained ozone decomposition amount Y. The discharge power control of the high frequency power supply 13 can be executed so as to control the power value (W) of the discharge power injected into the ozonolysis device 221.

Therefore, if the combination of the ozone flow rate DQ2 and the ozone concentration DC2 is within the characteristic range of the ozone decomposition characteristic L21 or less, there is no problem and the residual ozone concentration prescribed value C2 of 2 (g / m ³ ) and the residual ozone amount prescribed value SH The ozone decomposing ability that satisfies the setting reference value of 12 (g / h) or less can be exhibited.

  In the present invention, the embodiments can be appropriately modified and omitted within the scope of the invention.

DESCRIPTION OF SYMBOLS 1A, 1B Electrode part 10a, 10b Electrode 11a, 11b Dielectric body 12a, 12b Metal compound layer 13 High frequency power supply 21 Ozone generator 20 Ozone treatment device 22 Discharge type ozone decomposition device 23 Low concentration ozone decomposition device 221 Ozone decomposition device 223 Concentration Total 224 Flow detector G1 High concentration ozone gas G2 High concentration residual ozone gas G3 Low concentration residual ozone gas G4 Harmless gas

Claims (2)

A discharge-type ozone decomposition apparatus provided independently of an ozone generator and an ozone treatment apparatus,
The first-type ozone-containing gas output by the ozone generator, and the second-type ozone-containing gas discharged by executing a predetermined ozone treatment step by the ozone treatment device for the first-type ozone-containing gas. Among them, an ozone-containing gas selection mechanism that selects one as the selected ozone-containing gas,
The selective ozone-containing gas containing ozone is supplied to an electrode part space formed between the first and second electrode parts , the first and second electrode parts facing each other, and the first A metal compound layer is provided on the surface of the electrode part space side of at least one of the first and second electrode parts;
A power source for supplying discharge power to the first and second electrode portions;
The first and second electrode parts generate a discharge phenomenon in the electrode part space when the discharge power is supplied, and the metal compound layer acts as an ozone decomposition catalyst, thereby selecting the selection in the electrode part space. Functions as an ozonolysis device that decomposes ozone in ozone-containing gas to obtain ozone-decomposed gas,
The ozonolysis ability to degrade the ozone of the selection ozone-containing gas by an ozone decomposer, have a power value and positive correlation of the discharge power,
The metal compound layer satisfies the following conditions (1) and (2),
(1) Not a conductor
(2) activated (excited) by the discharge phenomenon,
The discharge type ozonolysis apparatus is:
A concentration meter for detecting an ozone concentration of the selected ozone-containing gas;
A flow rate detector for detecting a supply flow rate of the selected ozone-containing gas to the electrode space,
The power source is configured to determine a power value of the discharge power based on the ozone concentration and the supply flow rate so that an ozone content of the ozone-decomposed gas is equal to or lower than a set reference value .
Discharge type ozonolysis device. A discharge type ozone decomposing apparatus according to claim 1 Symbol placement,
The metal compound layer includes at least one metal oxide of nickel, manganese, cobalt, and copper.
Discharge type ozonolysis device.

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