JP2010089054A - Treating device and treating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating technology which efficiently removes decomposition-difficult compounds contained in a gas. <P>SOLUTION: A treating device for treating a gas which contains decomposition-difficult compounds is provided. The treating device includes: a lower part treating tank 22 into which a decomposition-difficult compound-containing PFC (perfluorocarbon) gas 81 is introduced; a nanobubble-containing water discharging part 54 which discharges nanobubble-containing water into the lower part treating tank 22; an upper part treating tank 21 into which a gas mixed with first decomposed substances produced in the lower part treating tank 22 is introduced; and a calcium-containing material which is arranged in the upper part treating tank 21. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a processing apparatus and a processing method for processing a gas containing a hardly decomposable compound.

  Dioxins, PCBs (polychlorinated biphenyls) and organic fluorine compounds (for example, perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA)) are chemically stable substances, Excellent chemical resistance (for example, acid resistance). Therefore, these hardly decomposable compounds are widely used as surfactants or industrial materials such as antireflection films in semiconductor production.

  However, the more widely used these hardly decomposable compounds are, the more likely they are released to nature.

  As described above, since a hardly decomposable compound is a chemically stable substance, once it is released into nature, it can cause serious environmental pollution. For example, the above-mentioned hardly decomposable compounds have been detected in the polar bears, seals, and whales, and environmental pollution due to the hardly decomposable compounds is becoming increasingly serious internationally.

  In recent years, for example, gases containing persistent compounds used in semiconductor factories or liquid crystal factories (for example, various PFC (perfluorocarbon) gases) have been regarded as one of the causes of global warming. It is thought to have a greenhouse effect several thousand times that of carbon dioxide. Since the bond between carbon and fluorine in the PFC gas is strong and stable, it is not decomposed in nature. Therefore, it is an important issue to reduce such decomposable compounds in the gas.

Conventionally, PFC gases such as CF ₄ , CHF ₃ , C ₃ F ₈ , SF ₆ , and NF ₃ used in semiconductor factories or liquid crystal factories have been conventionally decomposed at a high temperature of 750 ° C. to 1400 ° C. It is processed by an apparatus, a plasma decomposition apparatus, a combustion decomposition apparatus or the like. However, since PFC gas is hardly decomposable, it is necessary to investigate the setting of decomposition temperature conditions, the determination of the processing amount, the determination of the removal rate, the study of by-products, the study of running costs, and the like. Moreover, the conventional method of processing under high temperature conditions consumes a great deal of energy.

  By the way, in recent years, it has been clarified that bubbles having a small diameter have various functions and effects. Currently, research on techniques for producing such bubbles and their effects is being advanced. Attempts have also been made to decompose various organic substances using bubbles.

  The bubbles can be classified into microbubbles, micronanobubbles and nanobubbles according to their diameters. Specifically, the microbubble is a bubble having a diameter of 10 μm to several tens of μm at the time of its generation, the micro-nano bubble is a bubble having a diameter of several hundred nm to 10 μm at the time of its generation, and the nanobubble is Bubbles having a diameter of several hundred nm or less at the time of generation. Note that a part of the microbubble may be changed to a micro / nanobubble by the contraction movement after the generation. Nanobubbles have the property that they can exist in a liquid for a long period of time.

  For example, various nanobubble utilization methods and various devices utilizing nanobubbles have been conventionally known (see, for example, Patent Document 1). More specifically, in Patent Document 1, nanobubbles exhibit surface-active action and bactericidal action by reducing buoyancy, increasing surface area, increasing surface activity, generating a local high-pressure field, or realizing electrostatic polarization. It is described. Furthermore, Patent Document 1 describes a technique for cleaning various objects and a technique for purifying polluted water using the surface-active action and bactericidal action of nanobubbles. Furthermore, Patent Literature 1 describes a method for recovering fatigue of a living body using nanobubbles. In Patent Literature 1, nanobubbles are produced by electrolyzing water and applying ultrasonic vibration to the water.

  Conventionally, a method for producing nanobubbles using a liquid as a raw material is known (see, for example, Patent Document 2). In the liquid, the production method includes 1) a step of decomposing and gasifying part of the liquid, 2) a step of applying ultrasonic waves to the liquid, or 3) a step of decomposing and gasifying part of the liquid, and A step of applying ultrasonic waves to the liquid. It is described that an electrolysis method or a photolysis method can be used as a step of decomposing and gasifying a part of the liquid.

Conventionally, a waste liquid treatment apparatus using microbubbles (ozone microbubbles) made of ozone gas has been used (see, for example, Patent Document 3). In the waste liquid treatment apparatus, microbubbles made of ozone gas are produced by mixing the ozone gas produced by the ozone generator and the waste liquid using a pressure pump. And when the said microbubble reacts with the organic substance in a waste liquid, the organic substance in a waste liquid is oxidized and decomposed | disassembled.
JP 2004-121962 A (published April 22, 2004) JP 2003-334548 A (published on November 25, 2003) JP 2004-321959 A (published November 18, 2004)

  However, the conventional processing technique using bubbles has a problem in that the hardly decomposable compound contained in the gas cannot be removed.

  The present invention has been made in view of the above-mentioned problems, and its purpose is to provide a processing technique capable of efficiently and easily removing a hardly decomposable compound contained in a gas discharged from a factory or the like. It is to provide.

As a result of intensive studies in view of the above problems, the present inventors have found the following 1) to 5) and have completed the present invention. That means
1) It is possible to efficiently process a hardly decomposable compound by including nanobubble-containing water mist in a gas containing a hardly decomposable compound (PFC (perfluorocarbon), etc.) discharged from a factory,
2) By utilizing the synergistic effect of the oxidizing power of nanobubbles and the catalytic action of activated carbon, it is possible to efficiently decompose difficult-to-decompose compounds,
3) It is possible to efficiently generate a gas containing a large amount of nanobubble-containing water mist by introducing micro-nanobubbles containing the gas into nanobubble-containing water.
4) Introducing the micro-nano bubbles containing the gas into the liquid, and further shearing the liquid in the nano-bubble-containing water discharge unit to physically decompose the hardly decomposable compound,
5) When the gas containing the decomposition product of the hardly decomposable compound generated by treating the gas is brought into contact with the calcium-containing material, the decomposition product is efficiently removed.

  That is, the processing apparatus according to the present invention is a processing apparatus for processing a gas containing a hardly decomposable compound, the first processing unit into which the first gas containing the hardly decomposable compound is introduced, and the first Nanobubble-containing water discharge means for discharging nanobubble-containing water into one processing unit, a second processing unit into which a second gas generated in the first processing unit is introduced, and a calcium-containing material disposed in the second processing unit It is characterized by having things.

  With the above configuration, the hardly decomposable compound contained in the first gas, which can be contained in the second gas generated by treating the first gas containing the hardly decomposable compound with the nanobubble-containing water, and the decomposition thereof By bringing the substance into contact with the calcium-containing substance in the second processing section, it can be made harmless efficiently. Thereby, the first gas can be processed successfully.

  It is preferable that the main component of the calcium-containing material is calcium carbonate. Substances mainly composed of calcium carbonate such as limestone, marble, calcite and aragonite can be suitably used as the calcium-containing material.

  Moreover, it is preferable that the processing apparatus according to the present invention further includes micro / nano bubble generating means for generating the micro / nano bubbles containing the first gas in the nano bubble-containing water.

  With the above configuration, since the first gas is contained in the micro-nano bubbles in the first processing unit, it can be retained in the nano-bubble-containing water for a long time, and the hardly decomposable compound contained in the first gas is nano-bubbles. Can be decomposed more efficiently.

  Further, in the processing apparatus according to the present invention, the micro / nano bubble generating means includes a spiral channel through which the first gas passes and a mushroom-like projection in which the first gas that has passed through the channel collides. It is preferable to provide a thing.

  According to the above configuration, the first gas passes through the spiral flow path and is converted into a spiral flow, and then collides with a mushroom-like protrusion to become micro-nano bubbles. Thereby, the micro nano bubble which contains the 1st gas in nano bubble content water can be generated efficiently.

  In the treatment apparatus according to the present invention, the micro / nano bubble generating means preferably generates micro / nano bubbles having a diameter of 0.5 μm or more and 3 μm or less in the nanobubble-containing water.

  According to said structure, since the ultrafine micro nano bubble containing 1st gas is generated in nanobubble containing water, 1st gas and nanobubble containing water are fully mixed, and 1st gas is longer. By being retained in the nanobubble-containing water for a long time, the hardly decomposable compound contained in the first gas can be efficiently decomposed by the nanobubbles.

  In the processing apparatus according to the present invention, the first gas is introduced into the first processing section as micro-nano bubbles after being introduced into the micro-nano bubble generating means, and is introduced into the micro-nano bubble generating means. It is preferable to further include a first gas amount adjusting means for adjusting the amount of the first gas.

  According to said structure, adjusting the quantity of the 1st gas discharged in a 1st process part from a micro nano bubble generation means by adjusting the quantity of the 1st gas introduce | transduced into a micro nano bubble generation means. Can do. Therefore, for example, by increasing the amount of the first gas introduced into the micro / nano bubble generating means, the inside of the first processing unit can be strongly aerated, so that the inside of the first processing unit can be efficiently stirred and will be described later. Nanobubble-containing water mist can be generated efficiently. Moreover, the quantity of the micro nano bubble generated in the nano bubble containing water in a 1st process part can be adjusted by adjusting the quantity of the 1st gas discharged in a 1st process part from a micro nano bubble generation means.

  Furthermore, for example, when activated carbon described later is provided in the first processing section, activated carbon can be flowed better by the aeration, so that the catalytic action of activated carbon is effectively exhibited, and the decomposition efficiency is improved. obtain. In addition, for example, when granular activated carbon described later is provided, pulverized fine activated carbon can be produced from granular activated carbon by strongly aeration of the inside of the first processing unit, and thus the catalytic action of activated carbon can be adjusted. it can.

  Moreover, in the processing apparatus which concerns on this invention, it is preferable that activated carbon is contained in the said 1st process part.

  With the above configuration, the catalytic action of activated carbon has a synergistic effect with the oxidation action of the nanobubble radicals, contributing to efficient decomposition.

  In the treatment apparatus according to the present invention, the activated carbon is preferably granular activated carbon or crushed fine activated carbon. Thus, by using granular activated carbon that adsorbs a hardly decomposable compound, or crushed fine activated carbon that is finer and larger in surface area than granular activated carbon, the catalytic action in the treatment tank can be more effectively exhibited. it can. That is, due to the catalytic action of granular activated carbon or crushed fine activated carbon, the oxidizing action by nanobubbles is further synergistically enhanced, and the hardly decomposable compound can be efficiently decomposed.

The processing apparatus according to the present invention, the activated carbon is preferably provided with respect to the capacity of the treatment tank 0.2 ^{(cm 3} / cm 3) or more 0.4 ^{(cm 3} / cm 3) or less . According to said structure, the catalytic action of activated carbon can be improved more.

  Moreover, the processing apparatus according to the present invention is provided in the first processing unit, and the activated carbon is separated by the separation means for separating the activated carbon from the mixed solution of the nanobubble-containing water and the activated carbon, and the separation means. A storage tank for storing the mixed solution, and the nanobubble-containing water discharge means creates nanobubble-containing water using the mixed solution in the storage tank and discharges it into the first processing section. Preferably there is.

  According to said structure, activated carbon is isolate | separated from the mixed solution of the nano bubble containing water and activated carbon in a 1st process part by a isolation | separation means, and the mixed solution from which the activated carbon was isolate | separated is transferred to the water tank from the 1st process part. . Thereafter, the nanobubble-containing water discharge means creates nanobubble-containing water using the mixed liquid in the water storage tank and discharges it into the first processing unit. By circulating the mixed solution introduced with the first gas between the first processing unit and the water storage tank, and further shearing the nanobubble-containing water containing the first gas to produce nanobubble-containing water, The hardly decomposable compound contained in the first gas can be efficiently decomposed. Furthermore, since the activated carbon in the first processing unit is separated by the separation means and stays in the first processing unit without being transferred to the water storage tank, it exhibits a catalytic action for a long time in the first processing unit and contributes to the decomposition process. be able to.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable to further provide the heating means which heats the said mixed solution in the said water tank. According to said structure, the decomposition efficiency of the hardly decomposable compound contained in the said mixed solution can be improved by heating the mixed solution in a water storage tank.

  Moreover, it is preferable that the processing apparatus which concerns on this invention is further equipped with the large sized activated carbon with a particle size larger than the said activated carbon in the said water tank. According to said structure, the hardly decomposable compound contained in the mixed solution in a water tank can be decompose | disassembled efficiently by the catalytic action and adsorption | suction action of large sized activated carbon. Further, since the large activated carbon has a large particle size, it is not taken into the nanobubble-containing water discharge means, and does not hinder the performance of the nanobubble-containing water discharge means.

  Moreover, it is preferable that the processing apparatus according to the present invention further includes gas processing means for processing the third gas generated in the second processing unit.

  According to said structure, the 3rd gas generated in the 2nd process part can be further processed. That is, the third gas containing the hardly decomposable compound remaining without being processed in the first processing unit and the second processing unit can be further decomposed in the gas processing means.

  Here, in the first processing unit, the second gas containing a large amount of nanobubble-containing water mist that is a mixture of microbubbles containing the first gas and nanobubble-containing water and is mist-like nanobubble-containing water, Occurs in the second processing unit. And among the hard-to-decompose compounds in the second gas, the hard-to-decompose compounds that remain without being processed in the second processing section become the third gas and are introduced into the gas processing means together with the nanobubble-containing water mist. And can be more efficiently decomposed by the nanobubbles contained in the nanobubble-containing water mist. Further, in the nanobubble-containing water in the first processing section, the second gas generated by decomposing the first gas to some extent by the nanobubbles and processing the first gas contains calcium in the second processing section. The energy cost required for the decomposition of the third gas in the gas processing means can be suppressed by bringing it into contact with an object and detoxifying it to some extent.

  In the treatment apparatus according to the present invention, the gas treatment means may include at least one selected from the group consisting of a thermal decomposition apparatus, a catalytic decomposition apparatus, a plasma decomposition apparatus, and a burner type combustion decomposition apparatus. preferable.

  If the gas treatment means includes a thermal decomposition apparatus, the hardly decomposable compound can be efficiently decomposed at a high temperature (eg, 1300 ° C.). In addition, if the gas treatment means includes a catalyst decomposing apparatus, it is possible to efficiently decompose the hardly decomposable compound by using a catalyst. Moreover, if the gas treatment means includes a plasma decomposition apparatus, it is possible to efficiently decompose the hardly decomposable compound by decomposing with plasma. Further, if the gas treatment means includes a burner type combustion decomposition apparatus, it can be burned and decomposed at a temperature from 1300 ° C. to 1400 ° C. using combustion gas.

  In the processing apparatus according to the present invention, the first gas is a gas discharged from an apparatus using the hardly decomposable compound, and the first gas is discharged from the apparatus using the hardly decomposable compound. It is preferable to further include a sequence control unit that operates the nanobubble-containing water discharge unit when the operation is performed.

  According to said structure, when the 1st gas is discharged | emitted by the sequence control means, in order to operate the nano bubble containing water discharge means in the processing apparatus which concerns on this invention, when the 1st gas is not discharged | emitted, This means can be activated only when necessary, and energy consumption can be suppressed.

In the processing apparatus according to the present invention, the first gas preferably contains perfluorocarbon. The first gas preferably includes at least one selected from the group consisting of CF ₄ , CHF ₃ , C ₃ F ₈ , SF ₆ , and NF ₃ . According to the above structure, processing apparatus according to the present invention, a strong bond between the oxidizing power by radical having the nano bubbles, perfluorocarbon, the atoms and fluorine such as carbon in a CHF _{3, SF} 6, NF 3, etc. Can be suitably used for treating the first gas.

Moreover, the processing apparatus which concerns on this invention WHEREIN: The said nano bubble containing water discharge means is the following 1) -4).
1) A first gas shearing unit that mixes and shears a supply liquid and a supply gas to produce microbubble-containing water. 2) A second gas shearing unit that further shears the microbubble-containing water to produce nanobubble-containing water. ) A third gas shearing section for further shearing the nanobubble-containing water to produce nanobubble-containing water containing a large amount of nanobubbles. 4) Further shearing the nanobubble-containing water discharged by the third gas shearing section to further increase the amount of nanobubbles. It is preferable to provide the 4th gas shearing part which produces nanobubble content water containing.

  If it is said structure, the nanobubble containing water containing a lot of nanobubbles can be generated efficiently. In addition, since the nanobubble-containing water discharge means includes at least four gas shearing portions, a larger amount of fine nanobubbles can be contained than in the case where the number of gas shearing portions is three or less. The oxidative degradation action can be strengthened.

  In addition, for example, when the first gas containing the hardly decomposable compound is taken into the nanobubble-containing water discharge means, the hardly decomposable compound is obtained by shearing the hardly decomposable compound with at least four shearing portions. Can be physically decomposed.

  Moreover, in the processing apparatus according to the present invention, the nanobubble-containing water discharge means includes the pump for mixing the supply liquid and the supply gas supplied to the first gas shearing section, and the supply to the first gas shearing section. It is preferable that the apparatus further includes a third pipe that supplies gas and a second gas amount adjusting unit that adjusts the amount of the supply gas supplied to the first gas shearing portion. According to said structure, the nanobubble containing water containing a lot of nanobubbles can be produced.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that a said 2nd gas quantity adjustment means supplies the said supply gas at 1.0 liter / min or less with respect to a said 1st gas shearing part. According to said structure, since the quantity of supply gas does not increase too much, generation | occurrence | production of a nano bubble is not prevented and a lot of nano bubbles can be generated.

  In the processing apparatus according to the present invention, it is preferable that the supply gas is taken into the first gas shearing section after the output of the pump reaches the maximum value. According to the above configuration, only the supply liquid is initially supplied and the supply gas is introduced after the pump output reaches the maximum value, so that cavitation does not occur and the pump is not damaged.

  In the processing apparatus according to the present invention, it is preferable that the supply gas is taken into the first gas shearing section after 60 seconds from the start of the operation of the pump. According to the above configuration, since the pump output reaches the maximum value after 60 seconds from the start of the operation of the pump, the above configuration does not cause cavitation and the pump is not damaged.

  In the processing apparatus according to the present invention, the third pipe may be connected to the first gas shearing portion so as to form an angle of 18 degrees with respect to the inner surface of the first gas shearing portion. preferable. With the above configuration, a large amount of microbubbles can be generated in the first gas shearing portion.

  Further, in the processing apparatus according to the present invention, the internal cross section of the first gas shearing portion is elliptical or perfectly circular, and two or more grooves are provided on the internal surface of the first gas shearing portion. It is preferable that According to said structure, it can control the swirling turbulent flow of the fluid in a 1st gas shear part by having a groove | channel.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: The depth of the said groove | channel is 0.3 mm-0.6 mm, and it is preferable that the width | variety of the said groove | channel is 0.8 mm or less. According to said structure, the swirling turbulent flow of the fluid in a 1st gas shear part can be controlled more effectively.

  Moreover, in the processing apparatus according to the present invention, the first gas shearing unit supplies the supply liquid via the first pipe and discharges the water containing microbubbles via the second pipe. The area of the cross section of the lumen of one pipe is preferably larger than the area of the cross section of the lumen of the second pipe. According to the above configuration, air can be sheared reasonably and stably, and a large amount of microbubbles can be produced.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the thickness of the partition of the said 1st gas shearing part is 6 mm-12 mm. If it is said structure, a microbubble can be stably generated in a 1st gas shear part.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: The said supply gas may contain ozone gas. According to said structure, the nanobubble containing water containing the nanobubble containing ozone can be produced, and a hardly decomposable compound can be oxidatively decomposed | disassembled strongly.

  The treatment method according to the present invention is a treatment method for treating a gas containing a hardly decomposable compound, and includes a nanobubble-containing water discharge step for discharging nanobubble-containing water into the first treatment part, and the nanobubble-containing water is difficult to be discharged. A first treatment step having a micro / nano bubble generation step for generating a micro / nano bubble containing a first gas containing a decomposable compound, and a second gas generated by treating the first gas, a calcium-containing material And a second processing step for introducing and processing the second processing unit. The processing method according to the present invention further includes a third processing step of introducing the third gas generated by processing the second gas in the second processing step into the gas processing means and processing the third gas. It is preferable.

  According to said structure, there can exist an effect equivalent to the processing apparatus which concerns on this invention.

  According to the treatment apparatus of the present invention, the first treatment part into which the first gas containing the hardly decomposable compound is introduced, the nanobubble-containing water ejection means for ejecting the nanobubble-containing water into the first treatment part, and the first Since it has the 2nd processing part in which the 2nd gas generated in 1 processing part is introduced, and the calcium content arranged in the 2nd above-mentioned processing part, it is efficient about the hardly decomposable compound contained in gas. It can be removed well and easily.

  Hereinafter, the present invention will be described in detail.

  In this specification, “weight” is treated as a synonym for “mass”, and “weight%” is treated as a synonym for “mass%”. Further, “A to B” indicating the range indicates that the range is A or more and B or less.

  Moreover, in this specification, the "main component" means containing 50 mass% or more.

[First Embodiment]
A first embodiment of a processing apparatus according to the present invention will be described below with reference to FIG. FIG. 1 is a schematic diagram showing a first embodiment of a processing apparatus 20 according to the present invention. The processing apparatus 20 according to the present embodiment is for processing a gas containing a hardly decomposable compound. As shown in FIG. 1, the processing tank 19 and a nanobubble-containing water discharge unit (nanobubble-containing water discharge means) 54 are provided. And a micro / nano bubble generating part (micro / nano bubble generating means) 79 and a tank (water tank) 5.

Here, although the hard-to-decompose compound processed by the processing apparatus 20 which concerns on this invention is not specifically limited, For example, an organic fluorine compound, a sulfur compound, nitrate, a chloride, etc. are contained. Examples of the organic fluorine compound include perfluorocarbon (PFC), and examples include PFC having 4 to 9 carbon atoms, PFC such as CF ₄ , CHF ₃ , C ₃ F ₈ , SF ₆ , and NF _3. can do.

  If the hardly decomposable compound processed by the processing apparatus 20 of the present invention is the above-mentioned compound, it can be processed efficiently. If the hardly decomposable compound is the above-described organic fluorine compound, a strong bond between an atom such as carbon and fluorine can be efficiently decomposed. In the present embodiment, an organic fluorine compound will be described as an example of the hardly decomposable compound.

In addition, the hardly decomposable compound processed in the processing apparatus 20 according to the present invention may be one used in a semiconductor manufacturing apparatus, one used in a liquid crystal manufacturing apparatus, or the like. For example, an etching apparatus in a semiconductor factory uses CF ₄ , CHF ₃ , C ₄ F ₈ or the like as an etching gas, and a chemical vapor deposition (CVD) apparatus uses C ₂ F as a cleaning gas for a product attached in the chamber. such as _6, NF ₃ is used. The hardly decomposable compound processed in the processing apparatus 20 according to the present invention may be, for example, PFC gas discharged from the above-described apparatus or the like. For example, PFC gas discharged at the time of fine pattern processing by dry etching in the semiconductor manufacturing process can be used.

  The processing tank 19 includes a lower processing tank (first processing unit) 22 and an upper processing tank (second processing unit) 21, and a first gas containing a hardly decomposable compound is introduced into the lower processing tank 22. The Details of the lower processing tank 22 and the upper processing tank 21 will be described later. The first gas is a gas including a hard-to-decompose compound such as the organic fluorine compound described above, and may include, for example, a gas discharged from a semiconductor manufacturing apparatus, a liquid crystal manufacturing apparatus, or the like. In the present embodiment, a PFC gas (first gas) 81 discharged from a semiconductor manufacturing apparatus (not shown) will be described as an example of the first gas.

  In this embodiment, the processing apparatus 20 is connected to the semiconductor manufacturing apparatus and the PFC gas discharge facility 31, and the PFC gas 81 discharged from the semiconductor manufacturing apparatus is introduced into the processing apparatus 20 through the PFC gas discharge facility 31. Processed. The processing apparatus 20 according to the present embodiment is installed in the vicinity of the semiconductor manufacturing apparatus. Thereby, for example, it becomes easy to operate the processing apparatus 20 based on a signal indicating the discharge condition or state of the PFC gas 81 from the semiconductor manufacturing apparatus. That is, the semiconductor manufacturing apparatus and the processing apparatus 20 can be easily linked by transmitting and receiving signals.

  Thus, it is preferable that the processing apparatus 20 which concerns on this invention is installed in the vicinity of the apparatus which discharge | releases a hardly decomposable compound. Furthermore, it is more preferable that the processing apparatus 20 according to the present invention and the apparatus for discharging the hardly decomposable compound are operated in cooperation.

  Although the installation place of the processing apparatus 20 according to the present invention is not particularly limited, for example, in a clean room, installed in the vicinity of a facility that discharges a hardly decomposable compound such as a semiconductor manufacturing apparatus, and the hardly decomposable compound generated in the clean room It is possible to treat gas containing. Moreover, it is also possible to connect and use it with the apparatus which discharges | emits the gas containing another hardly decomposable compound.

  The processing apparatus 20 and the semiconductor manufacturing apparatus according to the present embodiment are linked by a sequencer (sequence control means) 53 by transmitting and receiving signals through the signal line 44. The sequencer 53 is connected to the semiconductor manufacturing apparatus via the signal line 44 and recognizes that the PFC gas 81 is discharged from the semiconductor manufacturing apparatus by receiving a signal via the signal line 44.

  In the present embodiment, the sequencer 53 further includes a PFC gas discharge facility 31, each device described later provided in the present processing device, that is, a gas-liquid mixing circulation pump (pump) 7 in the nanobubble-containing water discharge unit 54, an inverter control blower (First gas amount adjusting means) 23, watering pump 45, exhaust fan 41, PFC gas decomposition apparatus (gas processing means) 33, and scrubber 34 are also connected via signal line 44. When the sequencer 53 receives a signal indicating that the PFC gas 81 is discharged from the semiconductor manufacturing apparatus, the sequencer 53 activates each apparatus. With the above configuration, each device can be operated when the PFC gas 81 is discharged, so that it can be operated only when necessary and energy consumption can be suppressed. Note that the timing for operating each device is not particularly limited to that described above, and may be operated according to a program incorporated in the sequencer 53, for example.

(Lower treatment tank 22)
Nanobubble-containing water is discharged from the nanobubble-containing water discharge unit 54 to the lower treatment tank 22. Further, a micro / nano bubble generating unit 79 is provided in the lower treatment tank 22, and the micro / nano bubbles 27 including the PFC gas 81 are generated in the nano bubble-containing water in the lower treatment tank 22. Thereby, in the lower treatment tank 22, the PFC gas 81 contained in the micro / nano bubbles 27 is decomposed by the nano bubbles in the nano bubble-containing water. Details of the nanobubble-containing water discharge unit 54 and the micro-nanobubble generation unit 79 will be described later.

  In the present embodiment, an example in which the PFC gas 81 is introduced into the lower processing tank 22 as the micro / nano bubbles 27 will be described. However, as the method of introducing the first gas into the processing apparatus according to the present invention, this is particularly true. It is not limited to.

  In the lower treatment tank 22, nanobubble-containing water including nanobubbles 49 is discharged from the nanobubble-containing water discharge unit 54 as a nanobubble flow 30. In this embodiment, the nanobubble containing water discharge part 54 produces nanobubble containing water using the liquid stored in the tank 5, and discharges the nanobubble containing water into the lower treatment tank 22.

  In this embodiment, the tank 5 is supplied with makeup water. Although it does not specifically limit as makeup water, For example, industrial water, tap water, etc. can be used. Further, the mixed solution is introduced into the tank 5 from the lower processing tank 22 as described later.

  The tank 5 is connected to a suction water pipe 43. The liquid in the tank 5 is sucked up by a watering pump 45 provided in the suction water pipe 43 and sprayed into the upper processing tank 21 through a watering water pipe 46 as will be described later.

  The micro / nano bubble generating unit 79 generates the micro / nano bubbles 27 containing the PFC gas 81 discharged from the PFC gas discharge facility 31 in the nano bubble-containing water in the lower treatment tank 22. Thereby, in the lower treatment tank 22, the nanobubble-containing water and the PFC gas 81 contained in the micro / nanobubble 27 can be decomposed by the oxidizing power of the nanobubble 49.

  Thus, radicals are generated by the nanobubbles 49 in the lower treatment tank 22, and the PFC gas 81 is oxidatively decomposed by the radicals. For example, it is known that the bond between carbon and fluorine in PFC is strong and stable. However, with the processing apparatus 20 according to the present invention, such a bond can also be oxidatively decomposed.

  Here, the radical means an atom, molecule, or ion having an unpaired electron, and may be referred to as a free radical. Since radicals are usually highly reactive, as soon as they are generated, they undergo oxidation-reduction reactions with other atoms and molecules to become stable molecules and ions. A radical exhibits a strong oxidizing power when it becomes a stable molecule or ion. Due to the oxidizing power of this radical, a strong bond between an atom such as carbon and fluorine in the organic fluorine compound is decomposed. The oxidizing power of the nanobubbles 49 produced in the nanobubble-containing water discharge unit 54 is much stronger than the oxidizing power of microbubbles or micronanobubbles.

  In the processing apparatus 20 according to the present invention, it is preferable that the granular activated carbon 26 flows in the lower processing tank 22. In the present embodiment, “Kuraray Coal (registered trademark)” (manufactured by Kuraray Chemical Co., Ltd.) is used as the granular activated carbon 26. The micro / nano bubbles 27 containing the PFC gas 81 are mixed with the granular activated carbon 26 in the lower treatment tank 22.

  By the way, as shown in Example 2 to be described later, the present inventors have compared the case where the organic fluorine compound is treated with the nanobubble 49 in the presence of activated carbon as compared with the case where the organic fluorine compound is treated only with the nanobubble 49. Found that the removal rate of the organic fluorine compound was high. That is, it has been found that when an organic fluorine compound is treated with nanobubbles in the presence of activated carbon, the decomposition of the organic fluorine compound proceeds efficiently due to the oxidizing power of nanobubbles and the adsorption and catalytic action of activated carbon.

Therefore, in the lower treatment tank 22, the organic fluorine compound in the PFC gas 81 is efficiently decomposed by the oxidation action of the nanobubbles and the adsorption action and catalytic action of the granular activated carbon 26. In particular, by increasing the concentration of the granular activated carbon 26 that flows into the lower treatment tank 22, the adsorption action and catalytic action of the granular activated carbon 26 are improved, so that the organic fluorine compound can be decomposed more efficiently. Therefore, it is preferable that the processing apparatus 20 according to the present invention contains activated carbon in an amount of 0.2 (cm ³ / cm ³ ) to 0.4 (cm ³ / cm ³ ) with respect to the capacity of the lower processing tank 22. .

  In addition, when the lower treatment tank 22 is aerated by the micro / nano bubbles discharged from the micro / nano bubble generation unit 79, the granular activated carbon 26 in the lower treatment tank 22 is agitated with strong aeration, and a part of the granular activated carbon 26 is crushed. The crushed fine activated carbon 62 is produced. Since the pulverized fine activated carbon 62 has a larger surface area than the granular activated carbon 26, the adsorbing action and the catalytic action are stronger than the granular activated carbon 26. Therefore, the synergistic effect with the oxidizing power of the nanobubbles 49 increases the decomposition efficiency of the hardly decomposable compound. Further improvement. The present inventors have found that the catalytic action of activated carbon further promotes the decomposition of hydrogen peroxide. Therefore, in the treatment apparatus 20 according to the present invention, the activated carbon acts catalytically and the nanobubbles 49 have. The oxidative degradation power can be enhanced.

  In the treatment apparatus 20 according to the present invention, the activated carbon contained in the lower treatment tank 22 may be granular activated carbon, crushed fine activated carbon, or both, and can enhance the oxidizing power of the nanobubbles 49 by catalytic action. If it exists, the activated carbon of another shape may be sufficient. The granular activated carbon 26 preferably has an average particle diameter of 1 mm, and the crushed fine activated carbon 62 preferably has an average particle diameter of 0.2 mm or less.

  In the lower treatment tank 22, the nanobubble-containing water is agitated by aeration by the micro / nano bubble generating unit 79 together with the micro / nano bubbles 27 including the PFC gas 81 remaining without being decomposed by the nano bubbles 49, the granular activated carbon 26 and the crushed fine activated carbon 62. Present as a mixed solution. In the present embodiment, a part of the mixed solution in the lower processing tank 22 is transferred to the tank 5 through the distribution pipe 14. A filter portion (separating means) 16 including a filter 17 and a screen 18 is provided in the vicinity of the mixed solution discharge port (not shown) in the lower processing tank 22 connected to the distribution pipe 14 in the lower processing tank 22. The granular activated carbon 26 and the crushed fine activated carbon 62 are separated from the mixed solution transferred from the lower processing tank 22 to the tank 5 through the distribution pipe 14 by the filter unit 16.

  The filter 17 is disposed near the mixed solution outlet, and the screen 18 is disposed on the liquid phase side of the filter 17 so as to cover the filter 17. A relatively large granular activated carbon 26 is separated by the screen 18, and a finer pulverized fine activated carbon 62 is separated by the filter 17. Thereby, in the filter part 16, the granular activated carbon 26 and the crushing fine activated carbon 62 are fully isolate | separated from a mixed solution, and the granular activated carbon 26 and the crushing fine activated carbon 62 do not flow out into the distribution | circulation piping 14 from the lower process tank 22. FIG. Yes.

  In the lower treatment tank 22, a part of the mixed solution that has been treated with the nanobubbles 49, the granular activated carbon 26 and the crushed fine activated carbon 62 and decomposed the organic fluorine compound is discharged through the primary treated water drain pipe 70. . In the vicinity of the mixed solution discharge port (not shown) in the lower treatment tank 22 connected to the primary treated water drain pipe 70 in the lower treatment tank 22, the granular activated carbon 26 contained in the mixed solution and the large crushed fine particles A screen 69 for separating the activated carbon 62 is provided.

  In the screen 69, the granular activated carbon 26 and the large crushed fine activated carbon 62 are sufficiently separated from the mixed solution, and the granular activated carbon 26 and the large crushed fine activated carbon 62 flow out from the lower treatment tank 22 to the primary treated water drain pipe 70. However, the crushed fine activated carbon 62 having a small size can flow out to the primary treated water drain pipe 70. The crushed fine activated carbon 62 that has flowed out is introduced into the waste water treatment device 35 to be described later and processed. Therefore, the pulverized fine activated carbon 62 that has been used for a long time and has a reduced size and reduced processing capability can be discharged from the lower treatment tank 22.

  In the present embodiment, a synthetic resin sponge is used as the filter 17, and a resin mesh sheet is used as the screens 18 and 69. However, the present invention is not limited to this. Further, take-out ports 63 and 67 are provided in the lower processing tank 22 for replacement, maintenance, and the like of the filter 17 and the screens 18 and 69.

  The distribution pipe 14 connecting the lower treatment tank 22 and the tank 5 is provided with flanges 13 and 15 that increase the degree of freedom in designing the distribution pipe 14, and the mixed solution in the lower treatment tank 22 is transferred to the tank 5. Transport. At this time, the mixed solution transferred from the lower treatment tank 22 to the tank 5 contains nanobubbles 49 and micro / nanobubbles 27 including the PFC gas 81 remaining without being decomposed by the nanobubbles 49. The mixed solution is transferred to the tank 5 and then taken into the nanobubble-containing water discharge section 54 through the first pipe 6 and returned to the lower treatment tank 22 as nanobubble-containing water. Since the granular activated carbon 26 and the crushed fine activated carbon 62 are removed from the mixed solution in the tank 5, a clogging phenomenon occurs when the mixed solution is taken into the nanobubble-containing water discharge unit 54 and discharged into the lower treatment tank 22. There is nothing.

  Thus, since the mixed solution in the lower processing tank 22 circulates between the lower processing tank 22 and the tank 5 and the nanobubble-containing water is repeatedly supplied, the oxidizing action by the nanobubbles 49 becomes stronger. Further, the granular activated carbon 26 and the crushed fine activated carbon 62 stay in the lower treatment tank 22 without flowing out into the tank 5, so that the resolution of the organic fluorine compound by these catalytic actions can be maintained.

  Further, since the mixed solution processed in the lower processing tank 22 includes the micro / nano bubbles 27 including the PFC gas 81 remaining in the lower processing tank 22 without being decomposed by the nanobubbles, the PFC gas 81 is also in the lower part. It circulates between the treatment tank 22 and the tank 5 and is taken into the nanobubble-containing water discharge part 54. The PFC gas 81 is repeatedly sheared by the nanobubble-containing water discharge unit 54, and the strong bond between carbon and fluorine in the PFC gas 81 is physically decomposed. Further, the nanobubble-containing water discharge unit 54 repeatedly creates nanobubble-containing water using a mixed solution containing the circulating PFC gas 81 and discharges the nanobubble-containing water into the lower treatment tank 22, thereby nanobubbles the PFC gas 81 in the nanobubble-containing water. It can be efficiently decomposed by the oxidizing power of 49. Part of the PFC gas 81 is decomposed by the decomposition by the oxidizing power of the nanobubbles 49 and the physical decomposition in the nanobubble-containing water discharge section 54, and the hydrogen fluoride (HF) gas 50 and the other decomposed gas 52 Become. The PFC gas 81 remaining without being decomposed in the lower treatment tank 22, and the hydrogen fluoride gas 50 and the decomposed gas 52 generated by the decomposition of the PFC gas 81 are a first decomposed gas mixture (second gas). ) And is generated from the lower processing tank 22 and diffuses into the upper processing tank 21.

  The specific shape of the lower processing tank 22 is not particularly limited, and a known water tank can be used as appropriate. In addition, it is preferable that the lower process tank 22 is provided with the inclination parts 25 and 55 which comprise the taper shape which tapers toward a bottom part. According to the said structure, the mixed solution in the lower process tank 22 is stirred more effectively by the discharge pressure of the micro nano bubble by the micro nano bubble generation part 79 and the discharge pressure of the nano bubble containing water by the nano bubble containing water discharge part 54. be able to. As a result, the oxidative decomposition reaction of the organic fluorine compound contained in the mixed solution in the lower treatment tank 22 can be further promoted. In addition, although the angle which the bottom face of the lower process tank 22 and the inclination part 25 make is not specifically limited, For example, it is preferable that it is 45 to 60 degree | times. Moreover, as said angle, it is preferable to select a preferable angle according to the kind and supplier of activated carbon to be used.

(Micro / Nano Bubble Generation Unit 79)
The micro / nano bubble generating unit 79 includes a spiral channel (channel) 32 and a current cutter (mushroom-shaped projection) 37. The micro / nano bubble generating unit 79 includes a spiral flow path 32 that converts the PFC gas 81 into a spiral flow, and a large number of mushroom-like protrusions (mushroom-like collision bodies) that finely crush the PFC gas 81 that has become a spiral flow. The current cutter 37 is provided. By converting the PFC gas 81 sent to the micro / nano bubble generating unit 79 into a spiral flow by passing through the spiral flow path 32, the PFC gas 81 is collided with the mushroom-like collision body of the current cutter 37, and repeatedly collides and shears. Then, the micro / nano bubbles 27 containing the PFC gas 81 are generated in the nano bubble-containing water in the lower treatment tank 22. By generating the micro / nano bubbles 27 containing the PFC gas 81 in the nano bubble-containing water in the lower treatment tank 22, the PFC gas 81 can be retained in the nano bubble-containing water for a longer time. Can be decomposed more efficiently.

  As used herein, “micronanobubble” refers to a group of bubbles in which microbubbles and nanobubbles are actually mixed, although it is a bubble having a diameter of about several hundred nm to 10 μm. “Microbubbles” are bubbles having a diameter of about 10 to 50 μm, and gradually shrink in water and finally disappear (completely dissolve). Further, “nano bubbles” are bubbles having a diameter of about 1 μm or less (about 100 to 200 nm), and can exist in water for a long time.

  The micro / nano bubble generating unit 79 preferably includes a gas refining mechanism for generating fine micro / nano bubbles 27 including the PFC gas 81 in the water containing nano bubbles. In particular, it is more preferable to generate micro-nano bubbles 27 having a PFC gas 81 of 0.5 μm or more and 3 μm or less in the nanobubble-containing water in the lower treatment tank 22. With the above configuration, the micro-nano bubbles 27 containing finer PFC gas 81 can be generated in the nano-bubble-containing water, so that the PFC gas 81 contained in the micro-nano bubbles 27 and the nano-bubble-containing water are sufficiently mixed. The PFC gas 81 is efficiently decomposed by the nanobubbles 49. Examples of the micro / nano bubble generating unit 79 used in the present invention include a line mixer.

  The processing apparatus 20 according to the present invention may include an inverter control blower 23 that adjusts the amount of PFC gas 81 introduced into the micro / nano bubble generating unit 79. In the present embodiment, the inverter control blower 23 is provided outside the processing tank 19, and is connected to a micro / nano bubble generating unit 79 provided in the lower processing tank 22 of the processing tank 19 through a gas pipe 24. The inverter control blower 23 sends the PFC gas 81 from the PFC gas discharge facility 31 to the micro / nano bubble generation unit 79 via the gas pipe 24 and adjusts the introduction amount by inverter control. That is, the discharge amount of the PFC gas 81 from the micro / nano bubble generating unit 79 to the lower processing tank 22 is adjusted by the inverter control blower 23. Thereby, the amount of the micro / nano bubbles 27 generated in the water containing nano bubbles in the lower treatment tank 22 is adjusted. In addition, the stirring state of the nanobubble-containing water in the lower processing tank 22 is adjusted by adjusting the discharge amount of the PFC gas 81 discharged into the lower processing tank 22.

  As the inverter control blower 23, it is preferable to employ a type that can perform inverter operation, that is, can control the rotation speed of the electric motor. The flow state of the granular activated carbon 26 and the crushed fine activated carbon 62 in the lower treatment tank 22 can be adjusted by adjusting the number of micro-nano bubbles 27 generated by controlling the rotation speed of the electric motor. The amount of aeration into the lower treatment tank 22 adjusted by the inverter control blower 23 is preferably at a level at which the granular activated carbon 26 does not settle.

Further, the amount of aeration into the lower processing tank 22 adjusted by the inverter control blower 23 is the PFC gas 81 in the liquid phase of the lower processing tank 22, the hydrogen fluoride gas 50 generated by the decomposition of the PFC gas, and the decomposition product. It is preferable that the amount of aeration is such that the gas 52 is sufficiently stirred, and these gases are raised to the liquid level in the lower processing tank 22 and released into the upper processing tank 21. In order to satisfy the above conditions, the aeration amount is preferably an aeration amount of 50 m ³ / hour / m ³ or more per volume of the lower treatment tank 22. In addition, by controlling the aeration amount with an inverter, the aeration amount can be adjusted so that the granular activated carbon 26 and the crushed fine activated carbon 62 do not accumulate on the screens 18 and 69 and the filter 17 described later, and the activated carbon has. The strength of the catalyst can be adjusted.

(Nanobubble-containing water discharge part 54)
Next, the nanobubble-containing water discharge unit 54 will be described. The nanobubble-containing water discharge part 54 includes a first pipe 6, a first gas shearing part 8 having a gas-liquid mixing circulation pump 7, a second pipe 9, a second gas shearing part 10, an electric needle valve (second gas amount adjusting means). ) 11, the third pipe 12, the third gas shearing portion 80, and the fourth gas shearing portion 29. In the present embodiment, the nanobubble-containing water discharge part 54 is provided between the tank 5 and the treatment tank 19, and the fourth gas shearing part 29 of the nanobubble-containing water discharge part 54 is in the lower treatment tank 22 of the treatment tank 19. The nanobubble-containing water is discharged into the lower treatment tank 22.

  A first pipe 6 and a second pipe 9 are connected to the first gas shearing portion 8. The first pipe 6 is connected to the tank 5, and the liquid (supply liquid) is supplied to the first gas shearing portion 8 through the first pipe 6 and the first gas is supplied through the third pipe 12. Gas (supply gas) is supplied to the shearing portion 8. And the said liquid and said gas are mixed and sheared in the 1st gas shearing part 8, As a result, microbubble containing water is produced.

  The liquid supplied to the first gas shearing unit 8 is makeup water stored in the tank 5 or a mixture of the makeup water and the mixed solution transferred from the lower treatment tank 22 to the tank 5. obtain. Thereby, the processing apparatus 20 can be designed small and space saving can be realized.

  Moreover, it does not specifically limit as gas supplied to the 1st gas shearing part 8, For example, air, ozone, oxygen, nitrogen, a carbon dioxide gas etc. are mentioned. The gas is preferably ozone or oxygen. If it is the said structure, since a large quantity of radicals can be generated rather than air, a hardly decomposable compound can be oxidatively decomposed more effectively. In this case, it is preferable to provide a tank capable of storing each gas at the end of the third pipe 12 on the electric needle valve 11 side. In addition, it does not specifically limit as a specific structure of the said tank, It is possible to use a well-known tank suitably.

  The liquid is supplied into the first gas shearing section 8 by operating the gas-liquid mixing circulation pump 7. Further, the supply of gas into the first gas shearing portion 8 and the adjustment of the supply amount of the gas can be adjusted by the opening / closing operation of the electric needle valve 11.

  The timing of the opening / closing operation of the electric needle valve 11 is not particularly limited. For example, first, by starting the operation of the gas-liquid mixing circulation pump 7, the liquid is introduced into the first gas shearing portion 8 and the liquid is stirred. Thereafter, it is preferable to open the electric needle valve 11 after the time when the output of the gas-liquid mixing circulation pump 7 reaches the maximum value, thereby supplying the gas into the first gas shearing portion 8. It is more preferable to open the electric needle valve 11 after 60 seconds from the start of the operation of the gas-liquid mixing circulation pump 7, thereby supplying gas into the first gas shearing portion 8.

  Although it is possible to open the electric needle valve 11 at the start of the operation of the gas-liquid mixing circulation pump 7, in this case, the gas-liquid mixing circulation pump 7 causes a cavitation phenomenon, and as a result, the gas-liquid mixing circulation pump 7 is damaged. There is a fear. However, if it is the said structure, it can prevent that the gas-liquid mixing circulation pump 7 raise | generates a cavitation phenomenon, As a result, it can prevent that the gas-liquid mixing circulation pump 7 is damaged.

  The amount of gas supplied into the first gas shearing portion 8 by opening the electric needle valve 11 is not particularly limited. For example, the gas is preferably supplied to the first gas shearing portion 8 at 1.0 liter / min or less. If it is the said structure, a lot of nanobubble containing water can be produced efficiently.

  As shown in FIG. 1, gas is supplied to the first gas shearing portion 8 via the third pipe 12. When connecting the 3rd piping 12 to the 1st gas shearing part 8, the connection position of the 3rd piping 12 on the 1st gas shearing part 8, the connection angle of the 3rd piping 12 with respect to the 1st gas shearing part 8, etc. are especially. It is not limited.

  For example, the third pipe 12 is connected to the side surface of the first gas shearing portion 8 and is approximately 18 degrees with respect to the inner side surface of the first gas shearing portion 8 (that is, tangent to the inner surface of the first gas shearing portion 8). It is preferable that they are connected so as to form an angle of. In other words, when considering the local area at the connection location of the third pipe 12, the first gas shearing section 8 is configured so that the third pipe 12 forms an angle of 18 degrees with respect to the moving direction of the mixture of gas and liquid. It is preferable to be connected to the inner surface of the.

  In order to efficiently produce microbubbles, it is necessary to efficiently shear gas. At this time, the liquid is rotated at an extremely high speed to form a negative pressure portion, and a gas is introduced into the negative pressure portion. The gas is efficiently sheared by the difference in rotational speed between the gas and the liquid. In this case, when the incident angle is 18 degrees, the shearing efficiency of the gas is the highest, so that the largest number of microbubbles can be produced.

  In the present embodiment, the nanobubble-containing water discharge unit 54 having four gas shearing portions has been described. However, the present invention is not limited to four, and one having more gas shearing portions may be used. The present inventors have found that the decomposition efficiency of various hardly decomposable compounds is further improved by using a nanobubble-containing water discharge part having four or more gas shearing parts. For example, when PFC gas is converted into micro / nano bubbles and introduced into a nanobubble-containing water discharge part having four or more gas shearing parts and physically sheared, it is found that a part of the PFC gas is decomposed into hydrogen fluoride or the like. It was. Therefore, by using a nanobubble-containing water discharge part having four or more gas shearing parts, it is possible to cope with the decomposition treatment of various hardly decomposable compounds.

  Next, the process of producing nanobubble-containing water by the nanobubble-containing water discharge unit 54 will be described in more detail. In general, the nanobubble-containing water is produced through two steps (a first gas shearing step and a second gas shearing step). Below, a 1st gas shear process and a 2nd gas shear process are demonstrated.

<First gas shearing process>
In the first gas shearing step, microbubble-containing water is produced from the gas and the liquid.

  In the first gas shearing process, in the first gas shearing section 8, the pressure of the mixture of gas and liquid is controlled hydrodynamically using the gas-liquid mixing circulation pump 7, and the gas is supplied to the negative pressure section. Inhaled. The “negative pressure part” means a region where the pressure is smaller than that of the surroundings in the mixture of gas and liquid. Then, fine microbubbles are generated by shearing the gas while moving the mixture at high speed to form a negative pressure portion. That is, the liquid and the gas are effectively self-sufficiently mixed and pumped. Thereby, microbubble-containing water containing finer microbubbles can be formed.

Although it does not specifically limit as the gas-liquid mixing circulation pump 7, It is preferable that it is a pump with a high head of 40 m or more (pressure of 4 kg / cm < ² >). The gas-liquid mixing circulation pump 7 is preferably a two-pole pump having a stable torque. According to the said structure, it is possible to apply a desired pressure with respect to the microbubble containing water in the 1st gas shearing part 8, As a result, the microbubble contained in microbubble containing water is sheared more finely be able to.

  Moreover, in the gas-liquid mixing circulation pump 7, it is preferable that the pressure of the pump is controlled. For example, it is preferable that the rotation speed of the gas-liquid mixing circulation pump 7 is controlled by a rotation control unit (not shown) such as an inverter. The rotation control unit can be further controlled by a sequencer (not shown). According to the said structure, it becomes possible to apply a desired pressure with respect to the microbubble containing water in the said 1st gas shearing part 8, As a result, the microbubble contained in microbubble containing water is made into a desired size. Can be aligned.

  Although the material of the 1st gas shearing part 8 is not specifically limited, It is preferable that they are stainless steel, a plastics, or resin. Of the above materials, stainless steel is most preferred. According to the said structure, while being able to prevent an impurity from mixing in microbubble containing water, it can prevent that the 1st gas shearing part 8 vibrates.

  Moreover, the thickness (thickness of the partition wall) of the first gas shearing portion 8 is not particularly limited, but is preferably 6 mm to 12 mm. Generally, if the thickness of the first gas shearing portion 8 is thin, the first gas shearing portion 8 vibrates due to the movement of the water containing microbubbles in the first gas shearing portion 8. That is, since the kinetic energy of the microbubble-containing water propagates to the outside as vibration and is lost, the high-speed fluid motion of the microbubble-containing water decreases, and as a result, the shear energy decreases. However, according to the said structure, since the vibration of the 1st gas shearing part 8 can be prevented, a microbubble can be produced efficiently.

  Next, the mechanism by which the first gas shearing part 8 having the gas-liquid mixing circulation pump 7 generates microbubbles will be described in more detail.

  First, in the 1st gas shearing part 8, the mixed phase swirl | flow which consists of the liquid and gas which are the structural components of microbubble containing water is generated. Specifically, a wing called an impeller is rotated at an ultra high speed to generate a mixed phase swirl composed of a liquid and a gas. At this time, a gas cavity that swirls at a high speed is formed at the center of the first gas shearing portion 8.

  Next, the gas cavity is narrowed in a tornado shape by pressure to generate a rotating shear flow that swirls at a higher speed. At this time, gas is automatically supplied to the gas cavity using the negative pressure of the gas cavity. Then, the mixed phase swirl is rotated while further cutting and crushing the microbubbles. Note that the cutting and pulverization are caused by the difference in the rotational speed of the gas-liquid two-phase fluid inside and outside the outlet of the first gas shearing portion 8. The difference in rotational speed is preferably 500 to 600 revolutions / second.

  That is, in the first gas shearing portion 8, the gas-liquid mixing circulation pump 7 moves the microbubble-containing water at high speed fluid motion to form a negative pressure portion and hydrodynamically control the pressure of the microbubble-containing water. The gas is supplied to the negative pressure part. As a result, in the first gas shearing part 8, microbubbles can be generated. In other words, the microbubble-containing water can be produced by using the gas-liquid mixing / circulation pump 7 to pump the liquid and the gas while effectively self-supplying and mixing them.

  The shape of the cross section of the lumen of the first gas shearing portion 8 is not particularly limited, but is preferably an ellipse, and most preferably a true circle. Moreover, it is preferable that the lumen | bore surface of the 1st gas shearing part 8 is formed by mirror surface finishing. According to the said structure, since the friction of the internal surface of the 1st gas shearing part 8 is small, while being able to rotate the mixture of gas and a liquid at high speed, gas can be sheared efficiently. As a result, many fine microbubbles can be generated, and finally many nanobubbles can be generated.

  Moreover, it is preferable that a groove is provided on the inner surface (lumen surface) of the first gas shearing portion 8. Further, the number of the grooves is not particularly limited, but two or more grooves are preferably provided. Moreover, the said groove | channel should just have a concave shape formed on the internal surface of the 1st gas shearing part 8, The shape is not specifically limited. For example, the groove preferably has a depth of approximately 0.3 mm to 0.6 mm and a width of approximately 0.8 mm or less. According to the above configuration, since the generation of the swirling turbulent flow of the mixture of the liquid and gas in the first gas shearing portion 8 can be controlled, many fine microbubbles can be generated and finally Many nanobubbles can be generated.

  Further, liquid is supplied to the first gas shearing portion 8 through the first pipe 6, and microbubble-containing water is discharged through the second pipe 9. At this time, the area of the cross section of the lumen of the first pipe 6 for supplying the liquid is preferably larger than the area of the cross section of the lumen of the second pipe 9 for discharging the microbubble-containing water. According to the said structure, since the discharge pressure of microbubble containing water can be raised, a microbubble can be generated stably.

<Second gas shearing process>
In the second gas shearing step, nanobubble-containing water is produced from the microbubble-containing water produced in the first gas shearing step. More specifically, the microbubble-containing water produced by the first gas shearing portion 8 is further sheared by the second gas shearing portion 10, thereby producing nanobubble-containing water.

  In addition, the 3rd gas shearing part 80 can further be provided as needed. If the 3rd gas shearing part 80 is provided, while the magnitude | size of the nanobubble produced by the 2nd gas shearing part 10 can be made still smaller, the quantity of nanobubble can be increased.

  Moreover, the 4th gas shearing part 29 can further be further provided as needed. The fourth gas shearing part 29 can further reduce the size of the nanobubbles produced by the third gas shearing part 80 and can increase the amount of nanobubbles.

  Microbubble-containing water is pumped from the first gas shearing section 8 to the second gas shearing section 10, further to the third gas shearing section 80, and further to the fourth gas shearing section 29 by the gas-liquid mixing circulation pump 7. When the microbubble-containing water is pumped from the first gas shearing portion 8 to the second gas shearing portion 10, further to the third gas shearing portion 80, and further to the fourth gas shearing portion 29 via a pipe, It is preferable that the diameter of the pipe be reduced gradually or stepwise in the direction in which the contained water is pumped. According to the above configuration, the microbubble-containing water can be thinned like a tornado while performing fluid motion at a higher speed. In other words, it is possible to generate a rotating shear flow that swirls at a higher speed. As a result, nanobubbles can be efficiently generated from microbubbles, and an ultra-high temperature extreme reaction field can be formed in nanobubble-containing water.

  When the above-mentioned extreme reaction field is formed, the water containing nanobubbles locally becomes a high-temperature and high-pressure state, and unstable free radicals are generated locally, and at the same time, heat is generated. A free radical is an atom or molecule having an unpaired electron, and tries to stabilize by taking an electron from another atom or molecule. Therefore, nanobubble-containing water containing free radicals exhibits a strong oxidizing power. Therefore, according to the said structure, organic substance etc. can be oxidatively decomposed | disassembled by the effect | action of a free radical.

  Moreover, it is preferable that the 2nd gas shearing part 10, the 3rd gas shearing part 80, and the 4th gas shearing part 29 are formed with stainless steel, a plastics, or resin.

  Further, the shape of the cross section of the lumen of the second gas shearing portion 10, the third gas shearing portion 80, and the fourth gas shearing portion 29 is preferably an elliptical shape, and most preferably a perfect circle. According to the said structure, since the resistance (friction) of the internal surface of the 2nd gas shear part 10, the 3rd gas shear part 80, and the 4th gas shear part 29 is small, while being able to rotate microbubble containing water at high speed The microbubble-containing water can be efficiently sheared, and as a result, many nanobubbles can be generated.

  Moreover, it is preferable that a small hole is opened in the second gas shearing portion 10, the third gas shearing portion 80, and the fourth gas shearing portion 29. The diameter of the opening of the small hole is not particularly limited, but is preferably 4 mm to 9 mm. According to the above configuration, the swirling motion of the bubble-containing water inside the second gas shearing unit 10, the third gas shearing unit 80, and the fourth gas shearing unit 29 can be controlled. That is, according to the above configuration, it is possible to control the generation of swirling turbulent flow inside the second gas shearing unit 10, the third gas shearing unit 80, and the fourth gas shearing unit 29. As a result, nanobubbles can be stably generated by the second gas shearing unit 10, the third gas shearing unit 80, and the fourth gas shearing unit 29. The specific size of the small hole can also be determined by the pump maximum suction value, the motor output value, and the pump discharge pressure value.

  Although it does not specifically limit as specific structures, such as the gas-liquid mixing circulation pump 7, the 1st gas shearing part 8, the 2nd gas shearing part 10, the 3rd gas shearing part 80, and the 4th gas shearing part 29 mentioned above, Commercially available products can be used. For example, it is possible to use a Bavidas HYK type manufactured by Kyowa Kikai Co., Ltd., but is not limited to this.

(Upper treatment tank 21)
In the present embodiment, the upper treatment tank 21 includes an upper calcium carbonate layer 1, an intermediate calcium carbonate layer 3, and a lower calcium carbonate layer 56 that contain calcium carbonate (calcium-containing material). Further, an upper support net 2, an intermediate support net 4, and a lower support net 57 are provided to support these calcium carbonates.

  The upper support net 2, the intermediate support net 4, and the lower support net 57 are formed and fixed so as to divide the upper processing tank 21 horizontally, and have a structure that supports calcium carbonate. It is preferable that the size of the mesh of these supporting nets is such that calcium carbonate does not fall and gas, liquid, calcium carbonate floc or slime, which will be described later, can pass through.

A large amount of calcium carbonate is provided on the upper support net 2, the intermediate support net 4, and the lower support net 57 to the extent that gas, liquid, etc. can pass through to form a calcium carbonate layer. It is preferable to provide calcium carbonate at 0.5 g or less per 1 m ³ on the support net. If it is such an amount, it can be avoided that the support network is blocked by a reaction product formed by the reaction of calcium carbonate with a hardly decomposable compound or the like. Moreover, it is preferable that calcium carbonate is a magnitude | size which does not fall from the mesh | network of each support net | network, For example, a granular thing with a diameter of 2 mm or more and 10 mm or less is more preferable. If it is such a magnitude | size, the reaction efficiency with the gas containing a hardly decomposable compound is good, and since it is easy to convey, handling becomes easy.

  In addition, as calcium carbonate, it is preferable that a main component is calcium carbonate, for example, limestone, crystalline limestone (marble), calcite (calcite), aragonite, etc. are mentioned. Moreover, it can replace with calcium carbonate and can also use what contains calcium (calcium containing material), such as a calcium compound, a calcium agent, ore containing calcium. Examples of the calcium agent include slaked lime. Since the calcium-containing material contains calcium, it can neutralize, for example, acid gas. Examples of the acid gas include hydrogen fluoride gas, hydrogen sulfide gas, nitric acid gas, and hydrogen chloride gas. Therefore, if the hardly decomposable compound to be processed in the processing apparatus according to the present invention is an organic fluorine compound, sulfur compound, nitrate, chloride, etc., these are decomposed in the lower processing tank 22 to generate hydrogen fluoride gas, sulfide Hydrogen gas, nitric acid gas, hydrogen chloride gas, etc. can be further neutralized and removed by the calcium-containing material.

  In the present embodiment, the gas as described above automatically reacts with calcium carbonate and is rendered harmless by contacting the surface of the calcium carbonate when passing through the calcium carbonate layer.

For example, hydrogen fluoride gas reacts with calcium carbonate and reacts as follows to become calcium fluoride and detoxified.
2HF + CaCO ₃ → CaF ₂ + H ₂ O + CO ₂
Such a reaction automatically proceeds when hydrogen fluoride gas contacts the surface of calcium carbonate.

  In the lower treatment tank 22, the PFC gas 81 contained in the micro / nano bubbles 27 is decomposed by the nano bubbles 49, the granular activated carbon 26 and the crushed fine activated carbon 62. Here, the PFC gas 81 is decomposed to generate hydrogen fluoride gas 50 and other decomposed gas 52, and the PFC gas 81 remaining in the lower processing tank 22 without being decomposed rises in the lower processing tank 22, It is discharged into the upper processing tank 21 as the first decomposition product mixed gas. At this time, the first decomposition product mixed gas released into the upper treatment tank 21 contains a large amount of nanobubble-containing water mist 76.

  The nanobubble-containing water mist 76 is mist-like nanobubble-containing water. When generating the micro / nano bubbles from the micro / nano bubble generating unit 79 in the nano bubble-containing water in the lower treatment tank 22, the discharge amount of the PFC gas 81 to the nano bubble-containing water is adjusted by the inverter control blower 23, whereby the nano bubble-containing water mist 76. Can be generated. For example, it is preferable to adjust the inverter control blower 23 so that the oxygen dissolution becomes 6% or more.

  The 1st decomposition product mixed gas discharge | released in the upper process tank 21 passes through each indication net | network and each calcium carbonate layer, and raises the inside of the upper process tank 21. FIG. At this time, the hydrogen fluoride gas 50 and the above-described acidic gas contained in the first decomposition product mixed gas react with calcium carbonate and are processed. The hydrogen fluoride gas 50 will be described as an example. The hydrogen fluoride gas 50 reacts with calcium carbonate to become calcium fluoride. The calcium fluoride forms floc and slime and adheres to the surface of the calcium carbonate or the supporting net or falls to the lower treatment tank 22 through the mesh of the supporting net. “Flock” generally means a chemically reacted aggregate, and “slime” means a thin film formed on a solid surface.

  The water sprinkling water pipe 46 described above is installed above each support net and the calcium carbonate layer in the upper treatment tank 21. The watering water pipe 46 is provided with a flange 47 and a watering nozzle 48. The flange 47 is a fastener that is formed so as to close the end of the watering water pipe 46, and the watering nozzle 48 is a nozzle that is installed in the watering water pipe 46 at a predetermined interval.

  In the sprinkling water pipe 46, the replenishing water supplied into the tank 5 and the mixed solution introduced into the tank 5 from the lower treatment tank 22 are introduced from the tank 5 through the suction water pipe 43 by the watering pump 45. . Then, the liquid flowing through the watering water pipe 46 is sprinkled into the upper processing tank 21 from the watering nozzle 48 and falls to the lower processing tank 22 through each calcium carbonate layer and each indicating net. At this time, since the surface of the calcium carbonate in each calcium carbonate layer and each indicating net are washed by the liquid, the floc and slime such as calcium fluoride adhering to the lower treatment tank together with the liquid Drops to 22. The flocs such as calcium fluoride and slime that have fallen into the lower treatment tank 22 are then transferred together with the mixed solution in the lower treatment tank 22 through the primary treated water drain pipe 70 to the wastewater treatment apparatus 35 described later.

  Further, the liquid sprayed into the upper treatment tank 21 dissolves a part of the gas having solubility such as the hydrogen fluoride gas 50 contained in the first decomposition product mixed gas in the upper treatment tank 21. To drop into the lower treatment tank 22. The dissolved hydrogen fluoride or the like becomes fluorine ions or the like and falls into the lower treatment tank 22.

  The mixed solution in the lower treatment tank 22 may partially contain hydrogen fluoride or the like generated by the decomposition of the PFC gas 81 in the lower treatment tank 22 as fluorine ions. Fluorine ions and the like contained in the lower treatment tank 22 can be introduced into the watering water pipe 46 through the tank 5 and sprinkled into the upper treatment tank 21. Fluorine ions or the like sprinkled in the upper treatment tank 21 can be made harmless by contacting with calcium carbonate to form calcium fluoride. Thus, the decomposition product etc. in which the hardly decomposable compound is decomposed and dissolved in the lower treatment tank 22 can be further processed.

  The first decomposed gas mixture diffused from the lower processing tank 22 into the upper processing tank 21 rises in the upper processing tank 21 and passes through each indicating net and each calcium carbonate layer. An exhaust duct 40 provided in the upper part of the upper treatment tank 21 is treated with calcium carbonate, hydrogen fluoride gas 50, acid gas, and the like contained in the mixed gas to form a second decomposition product mixed gas (third gas). To reach. That is, the second decomposition product mixed gas includes the PFC gas 81 remaining without being decomposed in the lower treatment tank 22, and the hydrogen fluoride gas 50 and the decomposition product gas 52 generated by the decomposition of the PFC gas 81. , Including residual gas not treated with calcium carbonate. The second decomposition product mixed gas further includes a large amount of nanobubble-containing water mist 76. The second decomposition product mixed gas is introduced into the PFC gas decomposition apparatus 33 and further decomposed.

  In the present embodiment, by treating a part of the hardly decomposable compound contained in the first decomposed mixture gas with calcium carbonate, the hardly decomposable compound contained in the second decomposed mixture gas can be reduced. . Therefore, energy consumption in the PFC gas decomposition apparatus 33 described later can be reduced.

(PFC gas decomposition unit 33)
The PFC gas decomposition apparatus 33 is provided outside the processing tank 19, and is connected to an exhaust duct 40 provided in the upper part of the upper processing tank 21 via a PFC gas pipe 36. The second decomposition product mixed gas that has reached the exhaust duct 40 is introduced into the PFC gas decomposition apparatus 33 via the PFC gas pipe 36 via the exhaust fan 41 provided in the exhaust duct 40 and decomposed.

By the way, in order to decompose the PFC gas 81, the following reaction formula CF ₄ + 2H ₂ O → 4HF + CO ₂
C ₂ F ₆ + 3H ₂ O → 6HF + CO ₂ + CO
NF ₃ + (3/2) H ₂ O → 3HF + (1/2) NO + (1/2) NO ₂
SF ₆ + 3H ₂ O → 6HF + SO ₃
As shown in FIG. 4, water (H ₂ O) is required for the decomposition reaction.

Therefore, in order to decompose the PFC gas 81 in the PFC gas decomposition apparatus 33, it is usually necessary to supply water (H ₂ O), but the second decomposition product mixed gas in the present embodiment has a large amount. A nanobubble-containing water mist 76 is included. That is, since the nanobubble containing water mist 76 containing water is introduced into the PFC gas decomposition apparatus 33 together with the gas, it is not necessary to supply water separately. Moreover, since the nanobubble containing water mist has the radical which is rich in reactivity, it is excellent in reactivity, and acts effectively in decomposition | disassembly of PFC gas.

  Here, the nanobubble-containing water mist 76 introduced into the PFC gas decomposing apparatus 33 works particularly effectively when, for example, the temperature in the PFC gas decomposing apparatus 33 is high. That is, when the inside of the PFC gas decomposition apparatus 33 in which the nanobubble-containing water mist 76 exists is at a high temperature, the decomposition reaction of the PFC gas 81 is promoted, and therefore the PFC gas 81 can be easily decomposed. As such temperature, it is preferable that it is 850 to 1400 degreeC, for example.

  As the PFC gas decomposition apparatus 33, for example, a conventionally used gas processing apparatus or the like can be used. The PFC gas decomposition apparatus 33 may include, for example, at least one of a PFC gas thermal decomposition apparatus, a PFC gas catalytic decomposition apparatus, a PFC gas plasma decomposition apparatus, and a PFC gas combustion decomposition apparatus, but is not limited thereto. Not. Each of the above devices will be described later. What is necessary is just to determine the apparatus used for the PFC gas decomposition | disassembly apparatus 33 with the density | concentration, component, etc. of the gas containing the hardly decomposable compound used as a process target.

  The hardly decomposable compound such as PFC gas decomposed in the PFC gas decomposition apparatus 33 is decomposed into, for example, hydrogen fluoride, carbon monoxide, carbon dioxide, and nitrogen oxide. Among these, since hydrogen fluoride has toxicity, it is necessary to detoxify before discharging the gas containing hydrogen fluoride into the atmosphere. Therefore, in the present embodiment, the processing apparatus 20 includes a scrubber 34 as an impurity removing unit for detoxifying the hydrogen fluoride-containing gas.

  The scrubber 34 is connected to the PFC gas decomposition apparatus 33 by a post-PFC gas decomposition pipe 38, and the hydrogen fluoride-containing gas generated in the PFC gas decomposition apparatus 33 is introduced through the post-PFC gas decomposition pipe 38. As the scrubber 34, for example, a water scrubber in which the cleaning water is water, an alkaline scrubber in which the cleaning water exhibits alkalinity, or the like can be used, but the scrubber 34 is not limited thereto. Specific examples of the scrubber 34 include a wet packed tower scrubber TRS type (manufactured by Seiko Chemical Industries, Ltd.). In the scrubber 34, hydrogen fluoride in the gas is brought into gas-liquid contact with the cleaning water and dissolved as fluorine ions in the cleaning water, thereby removing fluorine from the gas and detoxifying it.

  In the present embodiment, hydrogen fluoride in the hydrogen fluoride-containing gas is removed by the scrubber 34 and discharged as waste liquid together with the cleaning water, and is transferred to the wastewater treatment device 35 described later by the drainage pipe 42. The gas detoxified by removing hydrogen fluoride in the scrubber 34 is discharged out of the processing apparatus 20 as a processing gas 39.

  The treatment apparatus 20 according to the present invention may further include a waste water treatment apparatus 35 for treating the waste liquid discharged from the scrubber 34 and the lower treatment tank 22. The waste water treatment apparatus 35 according to this embodiment is connected to a scrubber 34 by a drain pipe 42, and waste liquid containing fluorine ions and the like discharged from the scrubber 34 is introduced. Further, the waste water treatment device 35 is connected to the lower treatment tank 22 by a primary treated water drain pipe 70, and waste liquid discharged from the lower treatment tank 22 is introduced. The waste liquid discharged from the lower treatment tank 22 may include decomposition products such as fluoride ions, small crushed fine activated carbon 62, calcium fluoride flocs and slime.

  The waste water treatment apparatus 35 according to this embodiment includes slaked lime (calcium hydroxide) as an inorganic flocculant, and includes a polymer flocculant as an organic flocculant. As such a polymer flocculant, for example, a polyacrylamide organic flocculant (Cliff Rock manufactured by Kurita Kogyo Co., Ltd.) can be used. Moreover, the waste water treatment apparatus 35 may be provided with the coagulation tank provided with slaked lime and a polymer flocculant, and the sedimentation tank for precipitating the calcium fluoride floc (aggregate | aggregate), for example.

  The fluorine ions in the waste liquid transferred from the scrubber 34 and the lower treatment tank 22 to the waste water treatment device 35 react with calcium in the slaked lime to form calcium fluoride and precipitate. Further, when the waste liquid discharged from the lower treatment tank 22 contains sulfate ions generated when the organic fluorine compound is decomposed, the sulfate ions react with calcium in slaked lime to form calcium sulfate, Detoxified. Further, flocs such as calcium fluoride and slime contained in the waste liquid discharged from the lower treatment tank 22 are subjected to precipitation after aggregation. The precipitates described above, the crushed fine activated carbon 62 discharged from the lower treatment tank 22 and the like are separated from the water to be treated in the waste water treatment device 35.

  The waste liquid rendered harmless in this way is discharged as treated water from the secondary treated water drain pipe 71.

  As described above, according to the processing apparatus 20 according to the present invention, a gas containing a hardly decomposable compound such as PFC gas is processed, and carbon in the PFC gas is oxidized by the oxidation action of nanobubbles and the catalytic action of activated carbon. Breaks down the strong bond between atoms and fluorine. The resulting decomposition gas, such as hydrogen fluoride gas, is made harmless by reacting with the calcium-containing material. Further, undecomposed PFC gas and decomposition product gas are decomposed in the PFC gas decomposition apparatus 33. Thereby, the hardly decomposable compound in the gas discharged from the semiconductor manufacturing apparatus or the like can be efficiently decomposed.

  According to the processing apparatus 20 according to the present invention, before introducing a gas containing a hardly decomposable compound to be processed in, for example, a conventional gas processing apparatus that processes at high temperatures, It can be decomposed and treated at room temperature by an oxidizing action, a catalytic action of activated carbon, and a neutralizing action of calcium-containing materials. Therefore, energy consumption can be significantly suppressed as compared with processing using only the gas processing apparatus.

[Second Embodiment]
A second embodiment of the processing apparatus 20 according to the present invention will be described below with reference to FIG. FIG. 2 is a schematic diagram showing a second embodiment of the processing apparatus 20 according to the present invention. The second embodiment is different from the first embodiment in that a PFC gas thermal decomposition apparatus 72 is used as the PFC gas decomposition apparatus, and the other configuration is the same as that of the first embodiment. . Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  In the present embodiment, the PFC gas pyrolysis device 72 includes a ceramic heater (not shown). In general, since the decomposition of the hardly decomposable compound is promoted when the temperature at the time of reaction is increased, the decomposition efficiency of the hardly decomposable compound is increased by raising the temperature in the PFC gas thermal decomposition apparatus 72 with a ceramic heater in this embodiment. To improve. As a heating means in the PFC gas thermal decomposition apparatus 72, an electric heater or the like can be used in addition to the ceramic heater.

  The PFC gas pyrolysis device 72 may be any type of device, and examples thereof include a device including a heating reaction section that includes a cylindrical casing, a cleaning gas introduction pipe, and a heater. In the above apparatus, for example, the inner peripheral surface of the housing and the outer peripheral surface of the heater are made of ceramics, and a pyrolytic treatment is performed by introducing a hardly decomposable compound such as PFC gas into the heating reaction part.

  The temperature in the PFC gas thermal decomposition apparatus 72 varies depending on various conditions such as the kind of the hardly decomposable compound to be introduced or the amount of the gas to be introduced, but it is preferable to increase the temperature to 1,300 ° C., for example. Thereby, the hardly decomposable compound in gas can be decomposed | disassembled efficiently.

[Third Embodiment]
A third embodiment of the processing apparatus 20 according to the present invention will be described below with reference to FIG. FIG. 3 is a schematic view showing a third embodiment of the processing apparatus 20 according to the present invention. The third embodiment is different from the first embodiment in that a PFC gas catalyst decomposition device 74 is used as the PFC gas decomposition device, and the other configuration is the same as that of the first embodiment. . Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  In this embodiment, the PFC gas catalytic decomposition apparatus 74 processes the gas containing the hardly decomposable compound introduced into the apparatus by electrical heating using a catalyst. As the catalyst, for example, a Ni · Al catalyst or a Pd / Ni / Al catalyst can be used. Moreover, as an electric heating means, an electric furnace can be used, for example. In the PFC gas catalyst decomposing apparatus 74, a hardly decomposable compound such as PFC gas in the exhaust gas is electrically heated in an electric furnace and further brought into contact with the catalyst to decompose the hardly decomposable compound at about 750 ° C. it can. That is, the PFC gas catalytic decomposition device 74 can decompose at a lower temperature than the PFC gas thermal decomposition device in the second embodiment. Moreover, it is preferable that the PFC gas catalytic cracking apparatus 74 includes a high-performance catalyst including a component that immediately absorbs the generated hydrogen fluoride.

[Fourth Embodiment]
A fourth embodiment of the processing apparatus according to the present invention will be described below with reference to FIG. FIG. 4 is a schematic diagram showing a fourth embodiment of the processing apparatus 20 according to the present invention. The fourth embodiment is different from the first embodiment in that a PFC gas plasma decomposition apparatus 75 is used as the PFC gas decomposition apparatus, and the other configuration is the same as that of the first embodiment. . Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  The PFC gas plasma decomposition apparatus 75 decomposes a hardly decomposable compound such as PFC gas in the exhaust gas with plasma, and adds water and oxygen to the gas, thereby preventing recombination of the decomposed gas and making it a processable gas. It is a device to convert. As a result, the hardly decomposable compound in the gas can be efficiently decomposed.

  The PFC gas plasma decomposition apparatus 75 may be, for example, a cavity resonator type apparatus using a microwave, which includes a pretreatment unit, a plasma generation unit, a reaction unit, and a gas cooler.

[Fifth Embodiment]
A fifth embodiment of the processing apparatus according to the present invention will be described below with reference to FIG. FIG. 5 is a schematic view showing a fifth embodiment of the processing apparatus according to the present invention. The fifth embodiment is different from the first embodiment in that a PFC gas combustion decomposition apparatus 77 is used as the PFC gas decomposition apparatus, and the other configuration is the same as that of the first embodiment. . Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  In the present embodiment, the PFC gas combustion decomposition apparatus 77 includes a burner as combustion means (not shown). As described above, since the decomposition of the hardly decomposable compound is promoted when the temperature during the reaction is increased, the decomposition efficiency of the hardly decomposable compound is improved by increasing the temperature in the PFC gas combustion decomposition apparatus 77.

  In the PFC gas combustion decomposition apparatus 77, a hardly decomposable compound such as PFC gas is introduced into the fuel furnace, and the fuel and oxygen gas are blown into the burner to burn and decompose. For example, the PFC gas is decomposed to hydrogen fluoride.

  The temperature to be raised by the burner varies depending on various conditions such as the kind of the hardly decomposable compound to be introduced or the amount of gas to be introduced, but is preferably raised to 1,300 ° C., for example. Thereby, the hardly decomposable compound in gas can be decomposed | disassembled efficiently.

[Sixth Embodiment]
A sixth embodiment of the processing apparatus 20 according to the present invention will be described below with reference to FIG. FIG. 6 is a schematic diagram showing a sixth embodiment of the processing apparatus 20 according to the present invention. The sixth embodiment is different from the first embodiment only in that a heater 64 is provided in the tank 5, and the other configuration is the same as that of the first embodiment. Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  In this embodiment, since the heater 64 is provided in the tank 5, the temperature of the liquid containing the hardly decomposable compound in the tank 5 can be adjusted. In general, since the decomposition of the compound is promoted when the temperature of the liquid rises, the liquid whose temperature has risen is transferred to the lower treatment tank 22 and treated with nanobubbles and activated carbon in the lower treatment tank 22, thereby causing a hardly decomposable compound. The decomposition efficiency of is improved. However, the temperature of the liquid is set from the kind of the hardly decomposable compound contained in the liquid, the specification of the nanobubble-containing water discharge unit 54, the amount of the granular activated carbon 26 in the lower treatment tank 22, and the micro / nano bubble generation unit 79. It may be determined from a comprehensive viewpoint (energy saving, cost, decomposition performance, etc.) based on experimental data obtained in advance.

[Seventh Embodiment]
A seventh embodiment of the processing apparatus according to the present invention will be described below with reference to FIG. FIG. 7 is a schematic view showing a seventh embodiment of the processing apparatus according to the present invention. The seventh embodiment is different from the first embodiment in that a large-sized activated carbon container 66 filled with a large-sized activated carbon 65 is provided in the tank 5, and the others are the same as in the first embodiment. It is configured. Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  In the present embodiment, the tank 5 is provided with a large activated carbon container 66 filled with a large activated carbon 65 larger than the granular activated carbon 26 contained in the lower treatment tank 22.

  Here, the activated carbon that acts as a catalyst usually has pores. The large activated carbon 65 is similarly open and has a large size, so that the amount and surface area of the activated carbon contained in the tank 5 increases, so the large activated carbon 65 contained in the tank 5 has a strong catalytic action. The tank 5 contains the nanobubbles 49 transferred from the lower treatment tank 22, and therefore the catalytic action of the large-sized activated carbon 65 can be further enhanced in the tank 5 by the oxidation action by the nanobubbles, and is thus included in the liquid. A hardly decomposable compound can be efficiently decomposed. Further, since the large activated carbon 65 also has an adsorption action, it can be decomposed by the oxidizing power of the nanobubbles after adsorbing the hardly decomposable compound.

  In addition, it is preferable to perform maintenance regularly, such as replacing | exchanging the large sized activated carbon 65 for a new large sized activated carbon after using for a fixed time. By replacing the large-sized activated carbon 65 whose performance has been reduced by adsorbing the hardly decomposable compound with a new one, the hardly decomposable compound can be decomposed more efficiently.

[Eighth Embodiment]
An eighth embodiment of the processing apparatus according to the present invention will be described below with reference to FIG. FIG. 8 is a schematic view showing an eighth embodiment of the processing apparatus according to the present invention. The eighth embodiment is different from the first embodiment only in that the gas introduced to produce nanobubbles in the nanobubble-containing water discharge portion 54 is specified as ozone gas, and the other is the first embodiment. The configuration is the same as in the embodiment. Therefore, in this embodiment, only points different from the first embodiment will be described, and members having the same configuration are denoted by the same member numbers, and description thereof is omitted.

  In this embodiment, since the gas introduced in order to produce a nanobubble is limited to ozone gas, the produced nanobubble turns into an ozone nanobubble. Therefore, since nanobubbles having a stronger oxidizing power than nanobubbles produced by a gas other than ozone can be produced, it is possible to more strongly oxidize and decompose hardly decomposable compounds in a liquid.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope indicated in the claims. In other words, embodiments obtained by appropriately combining technical contents disclosed in different embodiments are also included in the technical scope of the present invention.

[Example 1]
Based on FIG. 2, the processing apparatus 20 which processes PFC gas was produced.

In the processing apparatus 20 used in this example, the capacity of the tank 5 is 0.5 m ³ , the capacity of the upper processing tank 21 of the processing tank 19 is about 0.8 m ³ , and the capacity of the lower processing tank 22 is about 1.2 m ^3. The capacity of the PFC gas pyrolyzer 72 was about 1.5 m ³ and the capacity of the scrubber 34 was about 2.2 m ³ .

  As the nanobubble containing water discharge part 54, the HYK type | mold made by Kyowa Kikai Co., Ltd. provided with the gas-liquid mixing circulation pump 7 comprised with the electric motor which has an output of 3.7 kw was used. Further, activated carbon for water treatment “Kuraray Coal GW (for liquid phase) (registered trademark)” (manufactured by Kuraray Chemical Co., Ltd.) was introduced into the lower treatment tank 22.

A gas containing PFC discharged from a semiconductor factory was introduced into the micro / nano bubble generation unit 79. The discharge amount of the PFC gas discharged from the micro / nano bubble generating unit 79 to the lower processing tank 22 adjusted by the inverter control blower 23 was set to 0.1 m ³ / hour / m ³ per volume of the lower processing tank 22.

  In the tank 5, tap water was introduced as makeup water, and a series of facilities related to the treatment facility were operated. Six days after the start of operation, the total fluorine amount in the liquid obtained from the tank 5 and from the primary treated water drain pipe 70 was measured. The total fluorine amount was measured by combustion ion chromatography. The results are shown in Table 1. However, the tap water introduced into the tank 5 contained a trace amount of fluorine from the beginning.

  In addition, six days after the start of operation, PFC in the processing gas 39 discharged from the scrubber 34 was detected using a gas chromatograph-mass spectrometer method. The results are shown in Table 2.

From the results shown in Tables 1 and 2, the following a) and b) became clear.
a) Compared with the total fluorine amount in the liquid in the tank 5, the total fluorine amount in the liquid obtained from the primary treated water drain pipe 70 was remarkably high, so that the PFC contained in the PFC gas is lower in the lower treatment tank. It became clear that it was decomposed | disassembled in 22 into hydrogen fluoride (HF) etc., and melt | dissolved in the liquid as a fluorine ion.
b) Since no decomposition products such as PFC were detected in the processing gas 39 discharged from the scrubber 34, it was revealed that the decomposition products were reliably decomposed.

[Example 2]
In order to investigate the effect of further combining activated carbon with oxidative decomposition by nanobubbles, the following experiment was performed using the same apparatus as that used in Example 1.

In this embodiment, 20 liters of a liquid containing an organic fluorine compound such as PFOS (perfluorooctane sulfonic acid) discharged from a semiconductor factory is introduced into the lower treatment tank 22 and treated according to the following conditions 1) to 3). The device 20 was activated.
1) The inside of the lower processing tank 22 is aerated by the micro / nano bubble generating part.
2) The inside of the lower treatment tank 22 is aerated by the micro / nano bubble generating unit, and nano bubble-containing water is discharged.
3) The inside of the lower treatment tank 22 is aerated by the micro / nano bubble generating unit, nanobubble-containing water is discharged, and crushed fine activated carbon is added.

  In this example, HYK type manufactured by Kyowa Kikai Co., Ltd. was used as the nanobubble-containing water discharge section, and activated carbon for water treatment “Kuraray Coal GW (for liquid phase) (registered trademark)” ( Kuraray Chemical Co., Ltd.) was used.

  After operating the processing apparatus 20 for 6 days, the PFOS concentration, the total organic carbon (TOC) concentration, and the chemical oxygen demand (COD) in the liquid in the lower processing tank 22 were measured. The PFOS concentration was measured by the LC / MS / MS method (liquid chromatograph-tandem mass spectrometer method), the total organic carbon concentration was measured by the combustion catalytic oxidation method, and the chemical oxygen demand was measured by the potassium permanganate consumption method. The results are shown in Table 3.

  From the results shown in Table 3, the PFOS concentration, the total organic carbon content, and the chemical oxygen demand were greatly reduced by discharging the nanobubble-containing water and adding the crushed fine activated carbon. It was revealed that the oxidative degradation power by nanobubbles was enhanced.

Example 3
In order to investigate the effect when the upper treatment tank 21 is provided with a calcium-containing material, two sets of apparatuses similar to the apparatus used in Example 1 were produced and used as a processing apparatus A and a processing apparatus B. However, the upper processing tank 21 in the processing apparatus A was provided with a calcium carbonate mineral, and the processing apparatus B was not provided with a calcium carbonate mineral. As a mineral of calcium carbonate, 5000 g of calcite having a diameter of 0.6 mm that is commercially available was used per apparatus.

  Using the processing apparatus A and the processing apparatus B, an experiment was performed in the same manner as in Example 1. Six days after the start of operation, the concentration of hydrogen fluoride contained in the gas in the PFC gas pipe 36 was measured using a lanthanum-alizarin complexone absorptiometry. The results are shown in Table 4.

  As shown in Table 4, the concentration of hydrogen fluoride contained in the gas in the PFC gas pipe 36 of the processing apparatus A provided with the calcium-containing material in the upper processing tank 21 is higher than that of the processing apparatus B not provided with the calcium-containing material. Was also significantly lower. From the results of this example, it was revealed that hydrogen fluoride can be reliably treated by providing the upper treatment tank 21 with a calcium-containing material.

  Therefore, in the processing apparatus according to the present invention, hydrogen fluoride can be processed by providing the upper processing tank 21 with a calcium-containing material, so that the number of hardly decomposable compounds introduced into the subsequent PFC gas decomposition apparatus is reduced. Energy consumption in the PFC gas decomposition apparatus can be further suppressed.

  The present invention can be used in the field of manufacturing a gas processing apparatus for processing gas discharged from a factory or the like.

It is a mimetic diagram showing a 1st embodiment of a processing device concerning the present invention. It is a schematic diagram which shows 2nd Embodiment of the processing apparatus which concerns on this invention. It is a schematic diagram which shows 3rd Embodiment of the processing apparatus which concerns on this invention. It is a schematic diagram which shows 4th Embodiment of the processing apparatus which concerns on this invention. It is a schematic diagram which shows 5th Embodiment of the processing apparatus which concerns on this invention. It is a schematic diagram which shows 6th Embodiment of the processing apparatus which concerns on this invention. It is a schematic diagram which shows 7th Embodiment of the processing apparatus which concerns on this invention. It is a schematic diagram which shows 8th Embodiment of the processing apparatus which concerns on this invention.

Explanation of symbols

1 Upper calcium carbonate layer 2 Upper support net 3 Intermediate calcium carbonate layer 4 Intermediate support net 5 Tank (water tank)
6 1st piping 7 Gas-liquid mixing circulation pump (pump)
8 First gas shearing part 9 Second piping 10 Second gas shearing part 11 Electric needle valve (second gas amount adjusting means)
12 3rd piping 13 Flange 14 Distribution piping 15 Flange 16 Filter part (separation means)
17 Filter 18 Screen 19 Processing tank 20 Processing device 21 Upper processing tank (2nd processing part)
22 Lower treatment tank (first treatment part)
23 Inverter control blower (first gas amount adjusting means)
24 Gas piping 25 Inclined part 26 Granular activated carbon 27 Micro-nano bubble 29 4th gas shear part 30 Nano bubble flow 31 PFC gas discharge equipment 32 Spiral flow path (flow path)
33 PFC gas decomposition equipment (gas treatment means)
34 Scrubber 35 Wastewater treatment device 36 PFC gas piping 37 Current cutter (mushroom-shaped projection)
38 Pipe after PFC gas decomposition 39 Process gas 40 Exhaust duct 41 Exhaust fan 42 Drain pipe 43 Suction water pipe 44 Signal line 45 Sprinkling pump 46 Sprinkling water pipe 47 Flange 48 Sprinkling nozzle 49 Nano bubble 50 Hydrogen fluoride gas 52 Decomposed gas 53 Sequencer 54 Nano bubble-containing water discharge part (nano bubble-containing water discharge means)
55 Inclined part 56 Lower calcium carbonate layer 57 Lower support net 62 Crushing fine activated carbon 63 Outlet 64 Heater 65 Large activated carbon 66 Large activated carbon container 67 Outlet 69 Screen 70 Primary treated water drain pipe 71 Secondary treated water drain pipe 72 PFC Gas Pyrolysis Unit 74 PFC Gas Catalytic Decomposition Unit 75 PFC Gas Plasma Decomposition Unit 76 Nano Bubble Containing Water Mist 77 PFC Gas Combustion Decomposition Unit 79 Micro / Nano Bubble Generation Unit (Micro / Nano Bubble Generation Unit)
80 Third gas shearing part 81 PFC gas (first gas)

Claims (30)

A first processing unit into which a first gas containing a hardly decomposable compound is introduced;
Nanobubble-containing water discharging means for discharging nanobubble-containing water into the first processing section;
A second processing unit into which the second gas generated in the first processing unit is introduced;
The processing apparatus for processing the gas containing the hardly decomposable compound characterized by including the calcium containing material arrange | positioned in the said 2nd process part.   The processing apparatus according to claim 1, wherein the calcium-containing material contains calcium carbonate as a main component.   The processing apparatus according to claim 1, further comprising micro-nano bubble generating means for generating micro-nano bubbles containing the first gas in the nano-bubble-containing water. The micro-nano bubble generating means is
A spiral channel through which the first gas passes;
The processing apparatus according to claim 3, further comprising: a mushroom-like protrusion that the first gas that has passed through the flow path collides with the first gas.   The processing apparatus according to claim 3 or 4, wherein the micro-nano bubble generating means generates micro-nano bubbles having a diameter of 0.5 µm to 3 µm in the nanobubble-containing water. The first gas is discharged into the first processing unit as micro-nano bubbles after being introduced into the micro-nano bubble generating means,
The process according to any one of claims 3 to 5, further comprising first gas amount adjusting means for adjusting the amount of the first gas introduced into the micro / nano bubble generating means. apparatus.   The activated carbon is contained in the said 1st process part, The processing apparatus of any one of Claims 1-6 characterized by the above-mentioned.   The processing apparatus according to claim 7, wherein the activated carbon is granular activated carbon or crushed fine activated carbon. The activated carbon is provided with 0.2 (cm ³ / cm ³ ) or more and 0.4 (cm ³ / cm ³ ) or less with respect to the capacity of the first processing unit. The processing apparatus as described. Separation means provided in the first processing section, for separating the activated carbon from a mixed solution of the nanobubble-containing water and the activated carbon,
A water storage tank for storing the mixed solution from which the activated carbon has been separated by the separation means,
The said nano bubble containing water discharge means produces nano bubble containing water using the said mixed solution in the said water storage tank, and discharges it in the said 1st process part, The any one of Claims 7-9 characterized by the above-mentioned. The processing apparatus according to item 1.   The processing apparatus according to claim 10, further comprising heating means for heating the mixed solution in the water tank.   The processing apparatus according to claim 10 or 11, further comprising large-sized activated carbon having a particle size larger than that of the activated carbon in the water tank.   The processing apparatus according to claim 1, further comprising gas processing means for processing the third gas generated in the second processing unit.   The process according to claim 13, wherein the gas processing means comprises at least one selected from the group consisting of a thermal decomposition apparatus, a catalytic decomposition apparatus, a plasma decomposition apparatus, and a burner type combustion decomposition apparatus. apparatus. The first gas is a gas discharged from an apparatus that uses a hardly decomposable compound,
15. The apparatus according to claim 1, further comprising sequence control means for operating the nanobubble-containing water discharge means when the first gas is discharged from the apparatus using the hardly decomposable compound. The processing apparatus of any one of these.   The processing apparatus according to claim 1, wherein the first gas contains perfluorocarbon. The process according to claim 1, wherein the first gas includes at least one selected from the group consisting of CF ₄ , CHF ₃ , C ₃ F ₈ , SF ₆ , and NF _3. apparatus. The said nano bubble containing water discharge means is provided with following 1) -4), The processing apparatus in any one of Claims 1-17 characterized by the above-mentioned.
1) A first gas shearing unit that mixes and shears a supply liquid and a supply gas to produce microbubble-containing water. 2) A second gas shearing unit that further shears the microbubble-containing water to produce nanobubble-containing water. ) A third gas shearing section for further shearing the nanobubble-containing water to produce nanobubble-containing water containing a large amount of nanobubbles. 4) Further shearing the nanobubble-containing water discharged by the third gas shearing section to further increase the amount of nanobubbles. The 4th gas shearing part which produces nanobubble content water containing. The nanobubble-containing water discharge means is
A pump for mixing the supply liquid and the supply gas supplied to the first gas shearing section;
A third pipe for supplying the supply gas to the first gas shearing section;
The processing apparatus according to claim 18, further comprising second gas amount adjusting means for adjusting an amount of the supply gas supplied to the first gas shearing portion.   The processing apparatus according to claim 19, wherein the second gas amount adjusting means supplies the supply gas at a rate of 1.0 liter / min or less to the first gas shearing portion.   21. The processing apparatus according to claim 19, wherein the supply gas is taken into the first gas shearing section after the output of the pump reaches a maximum value.   21. The processing apparatus according to claim 19, wherein the supply gas is taken into the first gas shearing section after 60 seconds from the start of operation of the pump.   The said 3rd piping is connected to the said 1st gas shear part so that the angle of 18 degree | times may be made with respect to the inner surface of the said 1st gas shear part, The any one of Claims 19-22 characterized by the above-mentioned. The processing apparatus of Claim 1. The cross section inside the first gas shearing part is oval or perfect circle,
The processing apparatus according to any one of claims 18 to 23, wherein two or more grooves are provided on an inner surface of the first gas shearing portion. The depth of the groove is 0.3 mm to 0.6 mm,
The processing apparatus according to claim 24, wherein a width of the groove is 0.8 mm or less. In the first gas shearing section, the supply liquid is supplied through the first pipe, and the microbubble-containing water is discharged through the second pipe.
The processing apparatus according to any one of claims 18 to 25, wherein an area of a cross section of the lumen of the first pipe is larger than an area of a cross section of the lumen of the second pipe.   27. The processing apparatus according to claim 18, wherein a thickness of the partition wall of the first gas shearing part is 6 mm to 12 mm.   The processing apparatus according to any one of claims 18 to 27, wherein the supply gas contains ozone gas. A nanobubble-containing water discharging step of discharging nanobubble-containing water into the first processing unit;
A first treatment step having a micro-nano bubble generation step of generating micro-nano bubbles containing a first gas containing a hardly decomposable compound in the nano-bubble-containing water;
A second processing step of introducing and processing the second gas generated by processing the first gas into a second processing unit containing a calcium-containing material. The processing method for processing the gas containing a sex compound.   The method further comprises a third processing step of introducing a third gas generated by processing the second gas in the second processing step into a gas processing means for processing. The processing method according to 29.

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