JP2010075834A - Treatment apparatus and treatment method - Google Patents

Abstract

Disclosed is a treatment technique capable of efficiently removing a hardly decomposable compound contained in a fluid.
A treatment tank 19 into which a PFC gas 31 containing a hardly decomposable compound is introduced, a nanobubble-containing water discharge section 54 for discharging nanobubble-containing water into the treatment tank 19, and a nanobubble-containing water in the treatment tank 19 Provided is a processing apparatus 20 for processing a fluid containing a hardly decomposable compound, which includes a micro / nano bubble generating unit 79 that generates micro / nano bubbles including PFC gas 31.
[Selection] Figure 1

Description

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

  Dioxins, PCB (polychlorinated biphenyl) 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.

  Therefore, in order to prevent environmental pollution, development of water treatment technology for appropriately treating waste water from factories using these hardly decomposable compounds as industrial materials is being promoted. In water treatment, a water treatment technique for removing these hardly decomposable compounds remaining in river water and the like is also required at the same time.

  For example, conventionally, as a water treatment technique for wastewater containing refractory compounds such as PFOS and PFOA, a combustion method in which a refractory compound is burned in an aqueous solution using fuel, or a high pressure is applied to the aqueous solution. A supercritical method is used in which a compound in an aqueous solution is decomposed by application.

  However, for example, the concentration of the organic fluorine compound in the organic fluorine compound-containing wastewater discharged from a semiconductor factory or the like is on the order of ppb, the concentration is low, and the amount of wastewater is several tens to several hundred tons per day. Many. In this case, in the present situation, the conventional method cannot completely treat the waste water.

  In addition, in the water treatment, the concentration of organic fluorine compounds in river water and lake water is much lower than in the case of drainage, and the amount of water is large, so that treatment is very difficult.

  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 water treatment technology using bubbles has a problem in that the hardly decomposable compound in the aqueous solution cannot be efficiently removed.

  In recent years, for example, gases containing persistent compounds that are 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. Since it is considered to have a greenhouse effect several thousand times that of carbon dioxide, it is an important issue to reduce such decomposable compounds in the gas.

  The present invention has been made in view of the above problems, and its purpose is to provide a processing technique capable of efficiently and easily removing a hardly decomposable compound contained in a fluid 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) A gas containing a decomposition product (such as PFC (perfluorocarbon)) generated by decomposing a liquid containing a hardly decomposable compound (for example, an organic fluorine compound) and a hardly decomposable compound discharged from a factory or the like Incorporating nanobubble-containing water mist into both the gas containing and being able to treat the hardly decomposable compound efficiently by mixing and treating them,
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) The gas containing the hardly decomposable compound can efficiently treat the hardly decomposable compound by containing a large amount of nanobubble-containing water mist.
4) A gas containing a large amount of nanobubble-containing water mist can be efficiently generated by introducing micro-nano bubbles containing the gas into the liquid.
5) The hardly decomposable compound can be physically decomposed by introducing micro-nano bubbles containing the gas into the liquid and further shearing the liquid in the nano-bubble-containing water discharge section.

  That is, the processing apparatus which concerns on this invention is a processing apparatus for processing the fluid containing a hardly decomposable compound, Comprising: The processing tank into which the 1st gas containing a hardly decomposable compound is introduce | transduced, In the said processing tank The nanobubble-containing water discharging means for discharging the nanobubble-containing water and the micro-nanobubble generating means for generating the micro-nanobubbles containing the first gas in the nanobubble-containing water in the treatment tank are provided.

  The treatment method according to the present invention is a treatment method for treating a fluid containing a hardly decomposable compound, and includes a nanobubble-containing water discharge step for discharging nanobubble-containing water into a treatment tank, and the nanobubbles in the treatment tank. And a micro / nano bubble generating step of generating micro / nano bubbles including a first gas containing a hardly decomposable compound in the contained water.

  With the above configuration, micro-nano bubbles containing the first gas containing the hardly decomposable compound are generated in the nanobubble-containing water discharged into the treatment tank. Thereby, in the treatment tank, the micro-nano bubbles containing the first gas can be retained in the nano-bubble-containing water for a long time, and the hardly decomposable compound contained in the first gas is efficiently decomposed by the nano bubbles. Can do.

  Moreover, in the processing apparatus which concerns on this invention, it is preferable that the said processing tank further introduces the liquid containing a hardly decomposable compound, and also contains activated carbon.

  By said structure, the liquid containing the hardly decomposable compound in a processing tank is efficiently processed with the nanobubble containing water discharged in the processing tank. In addition, the catalytic action of activated carbon has a synergistic effect with the oxidation action of nanobubble radicals, contributing to efficient decomposition.

  In the treatment apparatus according to the present invention, it is preferable that the nanobubble-containing water discharge means prepares nanobubble-containing water using the liquid and discharges it into the treatment tank.

  According to said structure, nanobubble containing water is discharged in a processing tank using the liquid containing a hardly decomposable compound. Thus, by producing nanobubble containing water using the liquid containing a hardly decomposable compound, the hardly decomposable compound in the said liquid can be decomposed | disassembled more efficiently.

  Further, the treatment apparatus according to the present invention is provided in the raw water tank into which the liquid is introduced, a first transfer means for transferring the liquid in the raw water tank to the nanobubble-containing water discharge means, and the treatment tank. Separation means for separating the activated carbon from the mixed solution of the nanobubble-containing water and the activated carbon, and the mixed solution from which the activated carbon has been separated by the separation means is transferred from the treatment tank to the raw water tank. 2 transfer means.

  According to said structure, activated carbon is isolate | separated from the mixed solution of nanobubble content water and activated carbon in a processing tank by a isolation | separation means, and the mixed solution from which activated carbon was isolate | separated is transferred to the raw | natural water tank. The liquid containing the hardly decomposable compound in the raw water tank is then transferred to the nanobubble-containing water discharge means. And a nanobubble content water discharge means produces nanobubble content water using the mixed solution transferred to the raw | natural water tank, and discharges it to a processing tank. Thus, the nanobubble containing water containing the micronano bubble containing the first gas is further sheared by circulating the nanobubble containing water containing the micronano bubble containing the first gas between the treatment tank and the raw water tank. Nano bubble-containing water is prepared and discharged into a treatment tank.

  Thereby, the hardly decomposable compound contained in the first gas can be decomposed more efficiently. In addition, it is possible to efficiently treat a liquid containing a hardly decomposable compound contained in nanobubble-containing water circulating between the treatment tank and the raw water tank, and it is possible to decompose the hardly decomposable compound more efficiently. . Furthermore, since the activated carbon in the treatment tank is separated by the separating means and stays in the treatment tank without being transferred to the raw water tank, it can exhibit a catalytic action for a long time in the treatment tank and contribute to the decomposition treatment. .

The processing apparatus according to the present invention, the activated carbon preferably contains ^{0.1 (cm 3 / cm 3)} ~0.3 (cm 3 / cm 3) with respect to the capacity of the treatment tank. According to said structure, the catalytic action of activated carbon can be improved more.

  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.

  Moreover, it is preferable that the processing apparatus which concerns on this invention is further equipped with the large sized activated carbon with a volume larger than the said activated carbon in the said raw | natural water tank. According to said structure, the hard-to-decompose compound contained in the liquid in a raw | natural water tank can be decomposed | disassembled efficiently by the catalytic action and adsorption | suction action of large sized activated carbon. Moreover, since the large activated carbon has a large volume, it is not taken into the nanobubble-containing water discharging means, and does not hinder the performance of the nanobubble-containing water discharging means.

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

  The processing apparatus according to the present invention preferably further includes a gas processing means for processing the first gas and the second gas generated by processing the liquid.

  According to said structure, the 2nd gas generated by processing the liquid containing the hardly decomposable compound in a processing tank, and the 1st gas which remains without being decomposed | disassembled in a processing tank are gas-processed. It can be further decomposed in the means.

  Here, in the treatment tank, the micro-nano bubbles containing the first gas and the nano-bubble-containing water containing the liquid containing the hardly decomposable compound are mixed, and a large amount of nano-bubble-containing water mist that is atomized nano-bubble-containing water is added. The mixed gas of the first gas and the second gas is generated in the gas phase in the treatment tank. And since the decomposition | disassembly is accelerated | stimulated by the nanobubble contained in the nanobubble containing water mist, the hardly decomposable compound in the said mixed gas and its decomposition product can be decomposed | disassembled more efficiently in the subsequent gas treatment means. Furthermore, the energy cost required for the decomposition of the first gas in the gas processing means can be suppressed by decomposing the first gas to some extent by the nanobubbles in the nanobubble-containing water in the treatment tank.

  In the processing apparatus according to the present invention, the gas processing means preferably includes at least one of a thermal decomposition apparatus, a catalytic decomposition apparatus, a plasma decomposition apparatus, and a burner type combustion decomposition apparatus.

  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.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the said gas processing means is equipped with the apparatus for processing a C4-C9 perfluorocarbon gas. According to said structure, when the hardly decomposable compound contained in the liquid in a processing tank contains an organic fluorine compound, for example, it is a C4-C9 perfluorocarbon contained in the 2nd gas generated by the decomposition | disassembly. The gas can be processed by a gas processing means.

  Moreover, in the processing apparatus according to the present invention, the liquid is a liquid discharged from an apparatus that uses the hardly decomposable compound, and when the liquid is discharged from an apparatus that uses the hardly decomposable compound, It is preferable to further comprise a sequence control means for operating the nanobubble-containing water discharging means and the micro / nanobubble generating means.

  According to said structure, when the said liquid is not discharged | emitted in order to operate the nano bubble containing water discharge means and micro nano bubble generation means in the processing apparatus which concerns on this invention when the said liquid is discharged | emitted by the sequence control means. The above-described means can be operated only when necessary without operating the above means, and energy consumption can be suppressed.

  Further, in the processing apparatus according to the present invention, the sequence control means includes a supply valve for supplying cleaning water for cleaning the hardly decomposable compound from an apparatus using the hardly decomposable compound, and the cleaning after the cleaning. It is preferable to operate the nanobubble-containing water discharge means and the micro-nanobubble generation means when a signal indicating that the discharge valve for discharging water is opened is received. According to said structure, the sequence control means can recognize correctly when the said liquid is discharged | emitted with the signal from the supply valve and discharge valve in the apparatus which uses a hardly decomposable compound.

  The processing apparatus according to the present invention further includes a high-concentration liquid processing means for processing the liquid preset as a high-concentration liquid containing the hardly decomposable compound at a high concentration by a combustion method or a supercritical method. The treatment tank preferably introduces the liquid set in advance as a low concentration liquid containing the hardly decomposable compound at a low concentration.

  According to the above configuration, the liquid containing the hardly decomposable compound is separated into a high-concentration liquid and a low-concentration liquid according to a preset concentration, and the high-concentration liquid is processed by a combustion method or a supercritical method. By treating the low concentration liquid in the treatment tank, it is possible to efficiently decompose the liquid containing the hardly decomposable compound according to the concentration, and to reduce the costly combustion method or supercritical method treatment. Can do.

  Further, in the processing apparatus according to the present invention, the micro / nano bubble generating means includes a spiral channel for converting the first gas into a spiral flow, and the first gas that has passed through the spiral channel. It is preferable to provide a mushroom-like impactor structure for generating micro-nano bubbles in the water containing nano bubbles.

  According to said structure, after converting the 1st gas which passes along a spiral flow path into a spiral flow, the collision and division | segmentation to the mushroom-like collision body of a mushroom-like collision body structure part are repeated, and 1st gas is changed. The contained micro / nano bubbles can be generated in the water containing nano bubbles. Thereby, the micro nano bubble which contains the 1st gas in nano bubble content water can be generated efficiently.

  Moreover, in the processing 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 water containing nano bubbles.

  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.

  Moreover, it is preferable that the processing apparatus according to the present invention further includes first gas amount adjusting means for adjusting the amount of the first gas introduced into the micro / nano bubble generating means.

  According to the above configuration, the amount of the first gas discharged from the micro / nano bubble generating means into the processing tank can be adjusted by adjusting the amount of the first gas introduced into the micro / nano bubble generating means. it can. Therefore, for example, by increasing the amount of the first gas introduced into the micro-nano bubble generating means, the inside of the treatment tank can be strongly aerated, so that the inside of the treatment tank can be efficiently stirred, and the 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 processing tank can be adjusted by adjusting the quantity of the 1st gas discharged in a processing tank from a micro nano bubble generating means.

  Furthermore, for example, when activated carbon is provided in the treatment tank, the activated carbon can be made to flow better by the aeration, so that the catalytic action of activated carbon can be effectively exhibited and the decomposition efficiency can be improved. In addition, for example, when granular activated carbon is provided, pulverized fine activated carbon can be produced from granular activated carbon by strongly aeration of the inside of the treatment tank, so that the catalytic action of activated carbon can be adjusted.

  In the processing apparatus according to the present invention, the hardly decomposable compound is preferably an organic fluorine compound. According to said structure, the strong coupling | bonding of the carbon and fluorine in an organic fluorine compound can be decomposed | disassembled by the oxidizing power by the radical which nanobubble has.

  In the processing apparatus according to the present invention, the organic fluorine compound comprises perfluorooctane sulfonic acid, perfluorooctanoic acid, perfluoroalkyl sulfonic acid, perfluorooctane sulfonic acid fluoride, and perfluorooctane sulfonic acid fluoride derivative. It is preferably at least one organic fluorine compound selected from the group. If the organic fluorine compound is selected from the above group, it can be efficiently decomposed and rendered harmless.

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, when the nanobubble-containing water discharge means, for example, when the liquid containing the hardly decomposable compound and the first gas are taken in, the hardly decomposable compound is sheared by shearing at least four shearing portions. The chemical compound 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.

  In the processing apparatus according to the present invention, the supply gas preferably contains 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.

  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.

  In the processing apparatus according to the present invention, the hardly decomposable compound is used in a photoresist process during semiconductor manufacturing, used in a photomask process during liquid crystal manufacturing, or used in a photo process during semiconductor manufacturing. It is preferable that any one of those contained in the antireflection film and those used in the desmear treatment process at the time of manufacturing the printed circuit board. According to said structure, even if a hardly decomposable compound is what was mentioned above, it can process successfully.

  Moreover, it is preferable that the processing method which concerns on this invention produces nanobubble containing water using the liquid containing a hardly decomposable compound in the said nanobubble containing water discharge process, and discharges it in the said processing tank.

  According to said structure, nanobubble containing water is produced using the liquid containing a hardly decomposable compound, and it discharges in a processing tank. Thereby, the liquid containing a hardly decomposable compound is processed by the nano bubbles together with the first gas contained in the micro / nano bubbles, and the hardly decomposable compound contained in the fluid can be efficiently decomposed.

  According to the treatment apparatus of the present invention, the nanobubble-containing water discharge means for discharging the nanobubble-containing water into the treatment tank into which the first gas containing the hardly decomposable compound is introduced, and the nanobubble-containing water in the treatment tank Since the micro-nano bubble generating means for generating the micro-nano bubbles containing one gas is provided, the hardly decomposable compound contained in the fluid can be efficiently and easily removed.

[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 connected to a semiconductor manufacturing apparatus 1. The processing apparatus 20 according to the present embodiment is for processing a fluid 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.

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 is contained. Examples of the organic fluorine compound include perfluorooctanesulfonic acid, perfluorooctanoic acid, perfluoroalkylsulfonic acid, perfluorooctanesulfonic acid fluoride, and perfluorooctanesulfonic acid fluoride derivatives. Further, the organic fluorine compound contains perfluorocarbon (PFC), for example, PFC having 4 to 9 carbon atoms existing as a gas, PFC such as CF ₄ , CHF ₃ , C ₃ F ₈ , SF ₆ , NF ₃ , etc. Can also be illustrated.

  In addition, the hardly decomposable compound processed in the processing apparatus 20 according to the present invention is used in a photoresist process during semiconductor manufacturing, used in a photomask process during liquid crystal manufacturing, or in a photo process during semiconductor manufacturing. What is used or what is used in the desmear process at the time of printed circuit board manufacture may be used. For example, PFOS is usually used in a photoresist in semiconductor manufacturing and a photomask in liquid crystal manufacturing. In addition, PFOS is usually included in an antireflection film used in a photo process in semiconductor manufacturing. Moreover, when performing the desmear process in printed circuit board manufacture, the etching liquid containing PFOS is normally used. The hardly decomposable compound to be treated in the present invention may contain such PFOS.

  If the hardly decomposable compound to be treated by the treatment apparatus 20 of the present invention is the above-described organic fluorine compound, a strong bond between 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 the present embodiment, the processing tank 19 includes an upper processing tank 21 and a lower processing tank 22, and a first gas containing an organic fluorine compound is introduced into the lower processing tank 22. The 1st gas containing an organic fluorine compound is a gas containing the organic fluorine compound mentioned above, for example, the gas discharged | emitted from the various apparatuses in a semiconductor factory, etc. are contained. In the present embodiment, as the first gas, a PFC gas 31 discharged from the semiconductor manufacturing apparatus 1 when performing fine pattern processing by dry etching in the semiconductor manufacturing process will be described as an example.

  Nanobubble-containing water is discharged from the nanobubble-containing water discharge unit 54 to the lower treatment tank 22. The micro / nano bubble generating unit 79 is provided in the lower processing tank 22 and generates micro / nano bubbles including the PFC gas 31 in the water containing nano bubbles in the lower processing tank 22. Thereby, in the lower treatment tank 22, the PFC gas 31 contained in the micro / nano bubbles 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, a liquid containing a hardly decomposable compound may be further introduced into the lower treatment tank 22 for treatment. That is, in this embodiment, the processing apparatus 20 processes the PFC gas 31 and the liquid containing a hardly decomposable compound.

  Examples of the liquid containing the hardly decomposable compound to be processed by the processing apparatus 20 according to the present invention include organic fluorine compound-containing water discharged from a factory, river water, lake water, and the like. Moreover, the liquid containing an organic chlorine compound, dioxin, an agricultural chemical, etc. can also be made into the process target of the processing apparatus 20 which concerns on this invention. In the present embodiment, a liquid containing an organic fluorine compound discharged from the semiconductor manufacturing apparatus 1 (hereinafter also referred to as “organic fluorine compound-containing liquid”) is taken as an example of the liquid introduced into the lower processing tank 22 and processed. However, the present invention is not particularly limited to this.

  In this embodiment, the processing apparatus 20 is connected to the semiconductor manufacturing apparatus 1, and the organic fluorine compound-containing liquid discharged from the semiconductor manufacturing apparatus 1 is introduced into the processing apparatus 20 from the semiconductor manufacturing apparatus 1 and processed. First, the stage until the organic fluorine compound containing liquid discharged | emitted from the semiconductor manufacturing apparatus 1 is introduce | transduced into the processing apparatus 20 is demonstrated. The processing apparatus 20 according to the present embodiment is installed in the vicinity of the semiconductor manufacturing apparatus 1. Thereby, for example, it becomes easy to operate the processing apparatus 20 based on a signal indicating the discharge condition or state of the waste liquid from the semiconductor manufacturing apparatus 1. That is, the semiconductor manufacturing apparatus 1 and the processing apparatus 20 can be easily linked by transmitting and receiving signals.

  The installation location of the processing apparatus 20 according to the present invention is not particularly limited. For example, the processing apparatus 20 can be installed in the vicinity of the semiconductor manufacturing apparatus 1 in a clean room to process a fluid containing an organic fluorine compound generated in the clean room. . Moreover, it is also possible to connect and use with the apparatus which discharge | emits the liquid or gas containing another hardly decomposable compound.

  A mode in which the processing apparatus 20 and the semiconductor manufacturing apparatus 1 according to the present embodiment are linked by transmission / reception of signals will be described below. In this aspect, the semiconductor manufacturing apparatus 1 supplies the organic fluorine compound-containing liquid pipe 3 for supplying the organic fluorine compound-containing liquid (resist liquid, antireflection film liquid, etc.) for processing the processing object 2 to the receiving container 43. An organic fluorine compound-containing liquid supply valve 56 that opens and closes and an organic fluorine compound-containing waste liquid discharge valve 58 that opens and closes the organic fluorine compound-containing liquid discharge pipe 60 are provided. Also, the semiconductor manufacturing apparatus 1 supplies cleaning ultrapure water for cleaning the processing object 2 and supplies a cleaning ultrapure water supply valve that opens and closes the cleaning ultrapure water pipe 4 (supply valve that supplies cleaning water). 57 and a cleaning ultrapure water discharge valve (a discharge valve for discharging cleaning water) 59 for opening and closing the cleaning ultrapure water discharge pipe 61.

  Here, the liquid discharged from the organic fluorine compound-containing liquid discharge pipe 60 contains a large amount of an organic fluorine compound that is a hardly decomposable compound. Therefore, the liquid is preset as a high-concentration liquid containing an organic fluorine compound at a high concentration, and is processed by a high-concentration liquid processing unit described later. In addition, the liquid discharged from the cleaning ultrapure water discharge pipe 61 contains a small amount of an organic fluorine compound remaining on the processing object 2. Therefore, the liquid is preset as a low-concentration liquid containing an organic fluorine compound at a low concentration, and is processed by the processing apparatus 20 described later.

  More specifically, the semiconductor manufacturing apparatus 1 is connected to the semiconductor manufacturing apparatus 1 and the processing apparatus 20 with a signal indicating that the cleaning ultrapure water supply valve 57 and the cleaning ultrapure water discharge valve 59 are opened. By transmitting by the sequencer 53 and receiving the signal by the sequencer 53, it is possible to identify that the liquid previously set as the low concentration liquid is introduced into the processing apparatus 20. In the present embodiment, the liquid set in advance as a low-concentration liquid is intended to be an organic fluorine compound-containing liquid to be processed by the processing apparatus 20.

  Thus, according to the processing apparatus 20 which concerns on this embodiment, the organic fluorine compound containing liquid containing a low concentration organic fluorine compound is processed using nanobubble and activated carbon, and the high concentration containing a high concentration organic fluorine compound is contained. Since it can be processed separately from the liquid, it is possible to appropriately treat the liquid to be treated according to the concentration of the organic fluorine compound, and to decompose the organic fluorine compound efficiently at low cost Is possible. Further, by treating the liquid to be treated according to the concentration of the organic fluorine compound, it is possible to directly treat the liquid containing the organic fluorine compound discharged from the apparatus using the organic fluorine compound. The organofluorine compound can be treated in proximity to the apparatus. As a result, waste that is difficult to transfer, such as gas exhausted from an apparatus that uses an organic fluorine compound, can be successfully treated.

  As described above, in the present invention, the liquid containing the organic fluorine compound is previously set as a high-concentration liquid or a low-concentration liquid. Further, it may be set depending on whether or not it is introduced, but is not limited to this. For example, the concentration of the liquid containing the organic fluorine compound is manually measured, set to one of the high concentration liquid and the low concentration liquid based on the measurement result, and the liquid set as the low concentration liquid is introduced into the treatment tank 19. May be.

  The organic fluorine compound-containing liquid discharge pipe 60 is connected to the high-concentration waste liquid tank 45, and the high-concentration liquid containing the organic fluorine compound at a high concentration passes through the organic fluorine compound-containing liquid discharge pipe 60 to the high-concentration waste liquid tank 45. Be transported. The cleaning ultrapure water discharge pipe 61 is connected to a low-concentration waste liquid tank (raw water tank) 5 provided in the processing apparatus 20, and the organic fluorine compound-containing liquid is processed through the cleaning ultrapure water discharge pipe 61. 20 is transferred to the low concentration waste liquid tank 5.

  The sequencer 53 includes an organic fluorine compound-containing liquid supply valve 56, an organic fluorine compound-containing waste liquid discharge valve 58, an electric valve 78 provided in the organic fluorine compound-containing liquid discharge pipe 60, a cleaning ultrapure water supply valve 57, and a cleaning ultrapure. A water discharge valve 59 is connected via a signal line 44. Therefore, a signal indicating the open / closed state of each valve is transmitted to the sequencer 53 via the signal line 44. The sequencer 53 can also control the opening and closing of each valve. That is, the open / close conditions of the organic fluorine compound-containing liquid supply valve 56, the cleaning ultrapure water supply valve 57, the organic fluorine compound-containing waste liquid discharge valve 58, and the cleaning ultrapure water discharge valve 59 are set in advance by the sequencer 53. It may be controlled according to this condition.

  In the present embodiment, when the sequencer 53 receives a signal indicating that the organic fluorine compound-containing liquid supply valve 56 and the organic fluorine compound-containing waste liquid discharge valve 58 of the semiconductor manufacturing apparatus 1 are open via the signal line 44. Then, the electric valve 78 is opened to introduce the high concentration liquid into the high concentration waste liquid tank 45.

  On the other hand, when the sequencer 53 receives a signal indicating that the cleaning ultrapure water supply valve 57 and the cleaning ultrapure water discharge valve 59 are opened via the signal line 44, the sequencer 53 generates a cleaning ultrapure water discharge pipe 61 in accordance with the signal. It is recognized that the organic fluorine compound-containing liquid is introduced into the low-concentration waste liquid tank 5 through. As described above, the sequencer 53 introduces the organic fluorine compound-containing liquid into the low concentration waste liquid tank 5 by a signal indicating that the cleaning ultrapure water supply valve 57 and the cleaning ultrapure water discharge valve 59 are opened. You may recognize that, but it is not particularly limited to this. For example, it may be directly detected that the organic fluorine compound-containing liquid has been introduced into the low concentration waste liquid tank 5.

  In the present embodiment, the sequencer 53 is further provided with each apparatus described later provided in the processing apparatus, that is, a gas-liquid mixing circulation pump (pump) 7 in the nanobubble-containing water discharge section 54, an inverter control blower (first gas amount adjusting means). ) 23, the exhaust fan 41, the PFC gas decomposition apparatus (gas processing means) 33, and the scrubber 34 are also connected via a signal line 44. When the sequencer 53 receives a signal indicating that the organic fluorine compound-containing liquid is introduced into the low-concentration waste liquid tank 5, the sequencer 53 operates each of the devices. With the above-described configuration, each device can be operated when the organic fluorine compound-containing liquid is introduced into the processing device 20, so that it can be operated only when necessary and energy consumption can be suppressed. In addition, the timing which operates each said apparatus is not limited to what was mentioned above, After an organic fluorine compound containing liquid is introduce | transduced into the low concentration waste liquid tank 5, it may be simultaneous with introduction, or an organic fluorine compound It may be simultaneous with the contained liquid being discharged from the semiconductor manufacturing apparatus 1.

(High-concentration liquid processing means)
The high-concentration liquid processing means according to the present embodiment includes a device for processing a liquid by a combustion method, and includes an electric valve 78, a high-concentration waste liquid tank 45, a waste liquid pipe 46 for transferring the high-concentration liquid, and a transfer pump 47. And a dedicated container A50 in which the introduction of the high-concentration liquid is controlled by opening and closing the valve 48, and a dedicated container B51 in which the introduction of the high-concentration liquid is controlled by opening and closing the valve 49. The high-concentration liquid containing the high-concentration organic fluorine compound discharged from the semiconductor manufacturing apparatus 1 flows into the high-concentration waste liquid tank 45 through the organic fluorine compound-containing liquid discharge pipe 60 and is stored. When the liquid level in the high-concentration waste liquid tank 45 rises, it is transferred to the dedicated container A50 or the dedicated container B51 by the transfer pump 47. Thereafter, the dedicated container A and the dedicated container B are transported to an incinerator or the like that disposes of the waste liquid, and incinerated at a combustion temperature of 1000 ° C. or higher, for example, to process the high-concentration liquid.

  The high-concentration liquid processing means according to the present invention may be composed of an apparatus that performs processing by the combustion method described above, but is not particularly limited thereto, and may be composed of, for example, an apparatus that performs processing by a supercritical method.

(Lower treatment tank 22)
In the present embodiment, the organic fluorine compound-containing liquid introduced from the semiconductor manufacturing apparatus 1 to the processing apparatus 20 is first transported to the low-concentration waste liquid tank 5 and further transported from the low-concentration waste liquid tank 5 to the nanobubble-containing water discharge unit 54. . And the nano bubble containing water discharge part 54 produces nano bubble containing water using the organic fluorine compound containing liquid conveyed from the low concentration waste liquid tank 5, and the said nano bubble containing water is put into the lower processing tank 22 of the processing tank 19 in it. Discharge.

  In the lower treatment tank 22, nanobubble-containing water produced using the organic fluorine compound-containing liquid introduced from the semiconductor manufacturing apparatus 1 is discharged as a nanobubble flow 30 from the nanobubble-containing water discharge portion 54. Further, the micro / nano bubble generating unit 79 generates micro / nano bubbles containing the PFC gas 31 generated in the semiconductor manufacturing factory in the nano bubble-containing water in the lower treatment tank 22. Thereby, in the lower treatment tank 22, the organic fluorine compound contained in the nanobubble-containing water and the PFC gas 31 contained in the micro-nanobubble can be decomposed by the oxidizing power of the nanobubble.

  Thus, radicals are generated by the nanobubbles 27 in the lower treatment tank 22, and the organic fluorine compound in the PFC gas 31 and the organic fluorine compound-containing liquid is oxidatively decomposed by the radicals. For example, PFOS, PFOA and the like are known to be stable materials, but these materials can also be oxidatively decomposed by the processing apparatus 20 according to the present invention.

  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 carbon and fluorine in the organic fluorine compound is decomposed. The oxidizing power of nanobubbles produced in the nanobubble-containing water discharge section 54 is much stronger than the oxidizing power of microbubbles and micro / nanobubbles.

  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 organic fluorine compound-containing liquid containing nanobubbles mixes with the granular activated carbon 26 in the lower treatment tank 22. Compared to the case where the organic fluorine compound-containing liquid is treated only with nanobubbles, the present inventors, when the organic fluorine compound-containing liquid is treated with nanobubbles in the presence of activated carbon, the decomposition product of the organic fluorine compound is a gas. It has been found that the generation rate of the decomposed gas 52 generated by the conversion is improved.

That is, it has been found that when an organic fluorine compound-containing liquid is treated with nanobubbles in the presence of activated carbon, decomposition of the organic fluorine compound proceeds efficiently due to the oxidizing power of the nanobubbles and the adsorption and catalytic action of the activated carbon. Therefore, in the lower treatment tank 22, the organic fluorine compound in the organic fluorine compound-containing liquid 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. Thus, the processing apparatus 20 according to the present invention, activated ^{carbon, 0.1 (cm 3 / cm 3} ) with respect to the volume of the processing tank ^{19 ~0.3 (cm 3 / cm 3} ) containing it is preferable that at.

  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 decomposition efficiency of the hardly decomposable compound is further enhanced by the synergistic effect with the oxidizing power of the nanobubbles. improves. The present inventors have found that the catalytic action of activated carbon further promotes the decomposition of hydrogen peroxide, and therefore in the treatment apparatus 20 according to the present invention, activated carbon acts catalytically and the oxidation possessed by the nanobubbles. The resolving power can be increased.

  In the treatment apparatus 20 according to the present invention, the activated carbon contained in the treatment tank 19 may be granular activated carbon, crushed fine activated carbon, or both, as long as it can enhance the oxidizing power of nanobubbles by catalytic action. The activated carbon may have other shapes.

  In the lower treatment tank 22, the nanobubble-containing water is stirred and mixed by aeration by the micro / nano bubble generating unit 79 together with the micro / nano bubbles including the PFC gas 31 remaining without being decomposed by the nano bubbles, 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 treatment tank 22 is returned to the low concentration waste liquid tank 5 through the distribution pipe (second transfer means) 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 returned to the low concentration waste liquid tank 5 from the lower treatment tank 22 through the distribution pipe 14 by the filter unit 16.

  In the lower treatment tank 22, a part of the mixed solution treated with nanobubble-containing water, granular activated carbon 26 and crushed fine activated carbon 62 and decomposed with the organic fluorine compound is discharged through the primary treated water drain pipe 70. The 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 as in the filter unit 16. And the filter 68 and the screen 69 which isolate | separate the crushing fine activated carbon 62 are provided.

  The filters 17 and 68 are disposed near the mixed solution outlet, respectively, and the screens 18 and 69 are disposed on the liquid phase side of the filter 17 or 68 so as to cover the filter 17 or 68, respectively. A relatively large granular activated carbon 26 is separated by the screens 18 and 69, and a finer crushed fine activated carbon 62 is separated by the filters 17 and 68. Thereby, the granular activated carbon 26 and the crushed fine activated carbon 62 are sufficiently separated from the mixed solution, and the granular activated carbon 26 and the crushed fine activated carbon 62 are prevented from flowing out from the lower treatment tank 22.

  In the present embodiment, a synthetic resin sponge is used as the filters 17 and 68, and a resin mesh sheet is used as the screens 18 and 69. However, the present invention is not limited to this. Further, outlets 63 and 67 are provided in the lower processing tank 22 for replacement and maintenance of the filters 17 and 68 and the screens 18 and 69.

  The distribution pipe 14 connecting the lower treatment tank 22 and the low-concentration waste liquid tank 5 is provided with flanges 13 and 15 that increase the degree of freedom of design of the distribution pipe 14. Transfer to the low concentration waste liquid tank 5. At this time, the mixed solution transferred from the lower treatment tank 22 to the low-concentration waste liquid tank 5 contains nanobubbles and micro / nanobubbles including the PFC gas 31 remaining without being decomposed by the nanobubbles. Since the granular activated carbon 26 and the crushed fine activated carbon 62 are removed from the mixed solution, a clogging phenomenon does not occur when the mixed solution is discharged from the nanobubble-containing water discharge unit 54 to the lower treatment tank 22 again.

  Thus, since the mixed solution in the lower treatment tank 22 circulates between the lower treatment tank 22 and the low concentration waste liquid tank 5 and the nanobubble-containing water is repeatedly supplied, the oxidation action by the nanobubbles is stronger. Become. Further, the granular activated carbon 26 and the crushed fine activated carbon 62 are retained in the lower treatment tank 22 without being discharged, so that the resolution of the organic fluorine compound by these catalytic actions can be maintained.

  Moreover, since the mixed solution processed in the lower processing tank 22 contains micro-nano bubbles including the PFC gas 31 remaining in the lower processing tank 22 without being decomposed by the nanobubbles, the PFC gas 31 is also processed in the lower processing tank. It circulates between the tank 22 and the low concentration waste liquid tank 5 and is taken into the nanobubble-containing water discharge part 54. The PFC gas 31 is repeatedly sheared by the nanobubble-containing water discharge unit 54, and the strong bond between carbon and fluorine in the PFC gas 31 is physically decomposed. Moreover, the nanobubble containing water discharge part 54 produces nanobubble containing water repeatedly using the mixed solution containing the PFC gas 31 which circulates, and discharges it to the lower process tank 22, thereby nanobubbles the PFC gas 31 in the nanobubble containing water. It can also be efficiently decomposed by the oxidizing power of. Part of the PFC gas 31 is decomposed into hydrogen fluoride (HF) or the like by the oxidizing power of the nanobubbles 27 and the physical decomposition in the nanobubble-containing water discharge section 54 and dissolved as fluorine ions in the liquid.

  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 they are 30 degrees-60 degrees, it is more preferable that they are 40 degrees-60 degrees, 45 degrees- Most preferably, it is 55 degrees. 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 generation unit 79 includes a spiral channel 32 and a current cutter (mushroom-like collision body structure) 37. The micro / nano bubble generating unit 79 includes a spiral flow path 32 that converts the PFC gas 31 into a spiral flow, and a current cutter 37 that has a large number of protrusions (mushroom-like collision bodies) that finely crush the PFC gas 31 that has become a spiral flow. And. By converting the PFC gas 31 sent to the micro / nano bubble generating unit 79 into a spiral flow by passing through the spiral flow path 32, the PFC gas 31 is collided with the mushroom-like collision body of the current cutter 37, and repeatedly collides and shears. Then, micro-nano bubbles containing the PFC gas 31 are generated in the water containing nano bubbles in the lower treatment tank 22. By generating the micro / nano bubbles containing the PFC gas 31 in the nano bubble-containing water in the lower treatment tank 22, the PFC gas 31 can be retained in the nano bubble-containing water for a longer period of time. Can be decomposed well.

  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 generation unit 79 preferably includes a gas refining mechanism that generates fine micro / nano bubbles including the PFC gas 31 in the water containing nano bubbles. In particular, it is more preferable to generate 0.5 to 3 μm micro-nano bubbles containing the PFC gas 31 in the nanobubble-containing water in the lower treatment tank 22. With the above configuration, micronanobubbles containing finer PFC gas 31 can be generated in the water containing nanobubbles. As a result, PFC gas 31 contained in the micronanobubbles and the water containing nanobubbles are sufficiently mixed. 31 is efficiently decomposed by nanobubbles. 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 an introduction amount of the PFC gas 31 introduced into the micro / nano bubble generation 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 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 31 from the micro / nano bubble generating unit 79 to the lower processing tank 22 is adjusted by the inverter control blower 23. As a result, the amount of micro / nano bubbles 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 31 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 amount of micro / nano bubbles generated by controlling the rotational 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 obtained by sufficiently stirring the decomposition product gas 52 of the organic fluorine compound and the PFC gas 31 in the liquid phase of the lower processing tank 22. It is preferable that the amount of aeration is such that the gas can be raised to the liquid level in the lower processing tank 22 and released to 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. Further, by controlling the amount of aeration by inverter, it is possible to adjust the amount of aeration so that the granular activated carbon 26 and the crushed fine activated carbon 62 are not deposited on the screens 18 and 69 and the filters 17 and 68 described later.

(Nanobubble-containing water discharge part 54)
Next, the nanobubble-containing water discharge unit 54 will be described. The nanobubble-containing water discharge unit 54 includes a first pipe (first transfer means) 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, and an electric needle valve. (Second gas amount adjusting means) 11, third pipe 12, third gas shearing portion 80, and fourth gas shearing portion 29 are provided. In this embodiment, the nanobubble containing water discharge part 54 is provided between the low concentration waste liquid tank 5 and the processing tank 19, and the fourth gas shearing part 29 of the nanobubble containing water discharge part 54 is a lower treatment of the processing tank 19. Provided in the tank 22, 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 low-concentration waste liquid tank 5, and the liquid (supply liquid) is supplied to the first gas shearing part 8 through the first pipe 6, and through the third pipe 12. A gas (supply gas) is supplied to the first gas 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 an organic fluorine compound-containing liquid discharged from the semiconductor manufacturing apparatus 1 and stored in the low-concentration waste liquid tank 5 or the organic fluorine compound-containing liquid and the lower treatment tank 22. The mixed solution with the mixed solution transferred to the low concentration waste liquid tank 5. 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, it is preferable that they are air, ozone, or oxygen. The gas is more 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 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.

  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 lower treatment tank 22, the organic bubbles in the organic fluorine compound-containing water and the PFC gas 31 contained in the micro-nano bubbles are decomposed by the nanobubbles 27, the granular activated carbon 26 and the crushed fine activated carbon 62. Here, the organic fluorine compound is decomposed to generate a decomposed gas (second gas) 52 containing PFC, and the PFC gas 31 that remains in the lower processing tank 22 without being decomposed rises in the lower processing tank 22. To the upper processing tank 21. At this time, the mixed gas of the decomposed gas 52 and the PFC gas 31 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 31 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 PFC gas 31 and the decomposition product gas 52 including the nanobubble-containing water mist 76 diffused in the upper processing tank 21 are introduced into the PFC gas decomposition apparatus 33 and further decomposed.

(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 PFC gas 31 and the decomposed gas 52 containing the nanobubble-containing water mist 76 diffused into the upper processing tank 21 rise to the exhaust duct 40 provided in the upper part of the upper processing tank 21, and the exhaust gas provided in the exhaust duct 40. It is introduced into the PFC gas decomposition apparatus 33 via the PFC gas pipe 36 via the fan 41 and decomposed.

Meanwhile, in order to decompose the PFC gas 31, 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 / 2H ₂ O → 3HF + 1 / 2NO + 1 / 2NO 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 in the PFC gas decomposition apparatus 33, usually water (H ₂ O) must be supplied. However, since the nanobubble containing water mist 76 containing water with the gas to be decomposed is introduced into the PFC gas decomposition apparatus 33 according to the present embodiment, it is not necessary to supply further water.

  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 is promoted, and the decomposition of the PFC gas 31 is easily promoted. As such temperature, it is preferable that it is 850 to 1400 degreeC, for example.

  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 that is decomposed in the PFC gas decomposition apparatus 33 is decomposed into, for example, hydrogen fluoride (HF), carbon monoxide, carbon dioxide, and nitrogen oxides. 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 processing device 20 may further include a wastewater treatment device 35 for treating the waste liquid discharged from the scrubber 34 and the lower treatment tank 22. The waste water treatment device 35 is connected to the scrubber 34 by a drain pipe 42, and waste liquid containing hydrogen fluoride 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 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. Fluorine in the waste liquid transferred from the scrubber 34 and the lower treatment tank 22 to the waste water treatment device 35 reacts with calcium in slaked lime to form calcium fluoride and precipitate. Moreover, the waste liquid discharged | emitted from the lower process tank 22 contains the sulfate ion produced when an organic fluorine compound (for example, PEOS) is decomposed | disassembled, This sulfate ion reacts with calcium in slaked lime, and forms calcium sulfate. And detoxified. The waste liquid rendered harmless in this way is discharged as treated water from the secondary treated water drain pipe 71. 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 formed calcium fluoride floc (aggregate), for example.

  As described above, according to the processing apparatus 20 according to the present invention, a liquid and a gas containing a hardly decomposable compound such as an organic fluorine compound are processed, and the organic fluorine compound is oxidized by the oxidation action of nanobubbles and the catalytic action of activated carbon. The strong bond between carbon and fluorine is broken and decomposed. In addition, the decomposition gas generated by processing the liquid containing the organic fluorine compound and the PFC gas 31 are further decomposed in the PFC gas decomposition apparatus 33. Thereby, the organic fluorine compound in the liquid discharged | emitted from the semiconductor manufacturing apparatus 1 etc. and gas can be decomposed | disassembled efficiently.

  Further, according to the processing apparatus 20 according to the present invention, since a part of the PFC gas 31 is processed in the nanobubble-containing water, the PFC gas 31 remaining without being processed is gas-processed in the PFC gas decomposition apparatus 33. Energy consumption in gas processing can be suppressed.

[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 view showing a second embodiment of the processing apparatus 20 according to the present invention connected to the semiconductor manufacturing apparatus 1. The second embodiment is different from the first embodiment in that a PFC gas thermal decomposition apparatus 72 is used as a decomposition apparatus for the PFC gas 31, and the other structure is the same as that of the first embodiment. ing. 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 material of the inner peripheral surface of the housing and the outer peripheral surface of the heater is ceramics, and PFC gas is introduced into the heating reaction portion and subjected to thermal decomposition treatment.

  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 connected to the semiconductor manufacturing apparatus 1. The third embodiment is different from the first embodiment in that a PFC gas catalytic cracking device 74 is used as a cracking device for the PFC gas 31, and the rest is configured in the same manner as in the first embodiment. ing. 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 decomposition apparatus 74, the PFC gas in the exhaust gas is electrically heated in an electric furnace and further brought into contact with the catalyst, whereby the PFC gas can be decomposed at about 750 ° C. 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 view showing a fourth embodiment of the processing apparatus 20 according to the present invention connected to the semiconductor manufacturing apparatus 1. The fourth embodiment is different from the first embodiment in that a PFC gas plasma decomposition apparatus 75 is used as a decomposition apparatus for the PFC gas 31, and the other structure is the same as that of the first embodiment. Yes. 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 device 75 is a device that decomposes PFC gas in exhaust gas with plasma and adds water or oxygen thereto to prevent recombination of the decomposed PFC gas and convert it into a processable gas. . 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 connected to the semiconductor manufacturing apparatus 1. The fifth embodiment is different from the first embodiment in that a PFC gas combustion decomposition apparatus 77 is used as a decomposition apparatus for the PFC gas 31, and the other structure is the same as that of the first embodiment. ing. 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, PFC gas is introduced into a fuel furnace, fuel and oxygen gas are blown into a burner and burned, and the PFC gas is decomposed into hydrogen fluoride. Thereafter, washing is performed with washing water, and hydrogen fluoride is transferred to washing water.

  The temperature 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 it 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 view showing a sixth embodiment of the processing apparatus 20 according to the present invention connected to the semiconductor manufacturing apparatus 1. The sixth embodiment is different from the first embodiment only in that a heater 64 is provided in the low-concentration waste liquid 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 low concentration waste liquid tank 5, the temperature of the liquid containing the hardly decomposable compound in the low concentration waste liquid 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. Therefore, 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 connected to the semiconductor manufacturing apparatus 1. 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 low-concentration waste liquid tank 5, and the others are the first embodiment. It is comprised similarly to a form. 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 low concentration waste liquid tank 5 is provided with a large activated carbon storage 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. Similarly, the large activated carbon 65 has pores and is large, so that the amount and surface area of the activated carbon contained in the low concentration waste liquid tank 5 is increased. Has strong catalytic action. The low-concentration waste liquid tank 5 contains the nanobubbles 27 transferred from the lower treatment tank 22, and thus the catalytic action of the large-sized activated carbon 65 can further enhance the oxidation action by the nanobubbles in the low-concentration waste liquid tank 5. Therefore, the hardly decomposable compound contained in the liquid can be efficiently decomposed. Moreover, since the large activated carbon 65 also has an adsorption action, it can be decomposed by the oxidizing power of nanobubbles after adsorbing a hardly decomposable substance.

[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 connected to the semiconductor manufacturing apparatus 1. 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, the hardly decomposable compound in the liquid can be more strongly oxidized and decomposed.

  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 organic fluorine compound (PFOS) containing water was produced.

In the processing apparatus 20 used in this example, the capacity of the low concentration waste liquid tank 5 is 0.5 m ³ , the capacity of the upper processing tank 21 of the processing tank 19 is about 0.3 m ³ , and the capacity of the lower processing tank 22 is about 1 m. ^3. The capacity of the PFC gas pyrolyzer 72 was about 1 m ³ and the capacity of the scrubber 34 was about 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.

The PFC gas 31 was introduced into the micro / nano bubble generation unit 79. Moreover, the discharge amount of the PFC gas 31 discharged from the micro / nano bubble generating unit 79 to the lower processing tank 22 adjusted by the inverter control blower 23 was 80 m ³ / hour / m ³ per volume of the lower processing tank 22.

  A liquid containing a low-concentration organic fluorine compound was introduced into the low-concentration waste liquid tank 5 of the processing apparatus 20 configured as described above, and all the series of equipment related to the processing equipment were operated. Twelve days after the start of operation, the PFOS concentration, total fluorine amount, and sulfate ion concentration in the low concentration waste liquid tank 5 and in the liquid obtained from the primary treated water drain pipe 70 were measured. The PFOS concentration was measured by LC / MS / MS method (liquid chromatograph-tandem mass spectrometer method), the total fluorine content was measured by combustion ion chromatography, and the sulfate ion concentration was measured by ion chromatography. The results are shown in Table 1.

  Further, 12 days after the start of operation, the PFOS concentration in the processing gas 39 discharged from the scrubber 34 was measured, and a decomposition product qualitative test was performed. The measurement was performed 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) to d) became clear.
a) Compared with the PFOS concentration in the liquid in the low concentration waste liquid tank 5, the PFOS concentration in the liquid obtained from the primary treated water drain pipe 70 was remarkably low, so the PFOS was decomposed in the lower treatment tank 22. It became clear.
b) Compared with the total fluorine amount in the liquid in the low concentration waste liquid 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 31 is It was revealed that it was decomposed in the lower treatment tank 22 to become hydrogen fluoride (HF) or the like and dissolved in the liquid as fluorine ions.
c) Compared with the sulfate ion concentration in the liquid in the low-concentration waste liquid tank 5, the PFOS concentration in the liquid obtained from the primary treated water drain pipe 70 was remarkably high, so that PFOS was decomposed in the lower treatment tank 22. It became clear that it became sulfate ion.
d) Since the concentration of PFOS in the processing gas 39 discharged from the scrubber 34 is remarkably low, and no decomposition products such as perfluorocarbon were detected, it became clear that the decomposition products as gases were reliably decomposed. It was.

[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 the present embodiment, 20 liters of a liquid containing an organic fluorine compound discharged from a semiconductor factory is introduced into the lower treatment tank 22, and the following conditions 1) to 4)
1) The inside of the lower processing tank 22 is aerated by the micro / nano bubble generating unit 2) The inside of the lower processing tank 22 is aerated by the micro / nano bubble generating unit and the nanobubble-containing water is discharged 3) The inside of the lower processing tank 22 is micro / nano bubble generating unit The processing apparatus 20 was operated by discharging the nanobubble-containing water and adding crushed fine activated carbon.

  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.

  INDUSTRIAL APPLICABILITY The present invention can be used in the field of manufacturing industrial water, agricultural water, domestic water, and other wastewater treatment devices such as industrial wastewater, agricultural wastewater, and domestic wastewater.

1 is a schematic diagram showing a first embodiment of a processing apparatus according to the present invention connected to a semiconductor manufacturing apparatus 1. It is a schematic diagram which shows 2nd Embodiment of the processing apparatus which concerns on this invention connected with the semiconductor manufacturing apparatus. It is a schematic diagram which shows 3rd Embodiment of the processing apparatus which concerns on this invention connected with the semiconductor manufacturing apparatus. It is a schematic diagram which shows 4th Embodiment of the processing apparatus which concerns on this invention connected with the semiconductor manufacturing apparatus. It is a schematic diagram which shows 5th Embodiment of the processing apparatus which concerns on this invention connected with the semiconductor manufacturing apparatus. It is a schematic diagram which shows 6th Embodiment of the processing apparatus which concerns on this invention connected with the semiconductor manufacturing apparatus. It is a schematic diagram which shows 7th Embodiment of the processing apparatus which concerns on this invention connected with the semiconductor manufacturing apparatus. It is a schematic diagram which shows 8th Embodiment of the processing apparatus based on this invention connected with the semiconductor manufacturing apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor manufacturing apparatus 2 Process target object 3 Organo fluorine compound containing liquid piping 4 Washing | cleaning ultrapure water piping 5 Low concentration waste liquid tank (raw water tank)
6 First piping (first transfer means)
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 (2nd transfer means)
15 Flange 16 Filter (separation means)
17 Filter 18 Screen 19 Processing tank 20 Processing device 21 Upper processing tank 22 Lower processing tank 23 Inverter control blower (first gas amount adjusting means)
24 Gas piping 25 Inclined part 26 Granular activated carbon 27 Nano bubble 29 4th gas shear part 30 Nano bubble flow 31 PFC gas (1st gas)
32 Spiral channel 33 PFC gas decomposition equipment (gas processing means)
34 Scrubber 35 Wastewater treatment equipment 36 PFC gas piping 37 Current cutter (mushroom-like impactor structure)
38 Pipe after PFC gas decomposition 39 Process gas 40 Exhaust duct 41 Exhaust fan 42 Drainage pipe 43 Receiving container 44 Signal line 45 High concentration waste liquid tank 46 Waste liquid piping 47 Transfer pump 48, 49 Valve 50 Dedicated container A
51 Dedicated container B
52 Decomposed gas (second gas)
53 Sequencer (sequence control means)
54 Nano bubble-containing water discharge part (nano bubble-containing water discharge means)
55 Inclined part 56 Organic fluorine compound-containing liquid supply valve 57 Cleaning ultrapure water supply valve (supply valve for supplying cleaning water)
58 Organic fluorine compound-containing waste liquid discharge valve 59 Cleaning ultrapure water discharge valve (discharge valve for discharging cleaning water)
60 Organic fluorine compound-containing liquid discharge pipe 61 Cleaning ultrapure water discharge pipe 62 Crushed fine activated carbon 63 Outlet 64 Heater 65 Large activated carbon 66 Large activated carbon container 67 Outlet 68 Filter 69 Screen 70 Primary treated water drain pipe 71 Secondary treatment Water drain pipe 72 PFC gas thermal cracking device 74 PFC gas catalytic cracking device 75 PFC gas plasma cracking device 76 Nano bubble-containing water mist 77 PFC gas combustion cracking device 78 Electric valve 79 Micro nano bubble generating part 80 Third gas shearing part

Claims (33)

A treatment tank into which a first gas containing a hardly decomposable compound is introduced;
Nanobubble-containing water discharging means for discharging nanobubble-containing water into the treatment tank;
A processing apparatus for processing a fluid containing a hardly decomposable compound, comprising: micro / nano bubble generating means for generating micro / nano bubbles including a first gas in the nano bubble-containing water in the processing tank.   The processing apparatus according to claim 1, wherein the treatment tank is further introduced with a liquid containing a hardly decomposable compound and further contains activated carbon.   The processing apparatus according to claim 2, wherein the nanobubble-containing water discharging unit is configured to produce nanobubble-containing water using the liquid and discharge the water into the processing tank. A raw water tank into which the liquid is introduced;
First transfer means for transferring the liquid in the raw water tank to the nanobubble-containing water discharge means;
Separation means provided in the treatment tank and separating the activated carbon from a mixed solution of the nanobubble-containing water and the activated carbon;
The processing apparatus according to claim 3, further comprising: a second transfer unit that transfers the mixed solution from which the activated carbon has been separated by the separation unit to the raw water tank from the inside of the treatment tank. The activated carbon is contained in an amount of 0.1 (cm ³ / cm ³ ) to 0.3 (cm ³ / cm ³ ) with respect to the capacity of the treatment tank. The processing apparatus according to item.   The processing apparatus according to claim 2, wherein the activated carbon is granular activated carbon or crushed fine activated carbon.   The processing apparatus according to any one of claims 4 to 6, further comprising large-sized activated carbon having a volume larger than that of the activated carbon in the raw water tank.   The processing apparatus according to claim 4, further comprising heating means for heating the liquid in the raw water tank.   The gas processing means for processing the first gas and the second gas generated by processing the liquid is further provided. The processing apparatus as described.   The processing apparatus according to claim 9, wherein the gas processing means includes at least one of a thermal decomposition apparatus, a catalytic decomposition apparatus, a plasma decomposition apparatus, and a burner type combustion decomposition apparatus.   The said gas processing means is equipped with the apparatus for processing a C4-C9 perfluorocarbon gas, The processing apparatus of Claim 9 or 10 characterized by the above-mentioned. The liquid is a liquid discharged from a device using the hardly decomposable compound,
The apparatus further comprises sequence control means for operating the nanobubble-containing water discharge means and the micro / nanobubble generation means when the liquid is discharged from the apparatus using the hardly decomposable compound. The processing apparatus of any one of 2-11.   In the sequence control means, a supply valve for supplying washing water for washing the hardly decomposable compound from a device using the hardly decomposable compound and a discharge valve for discharging the washing water after washing are opened. The processing apparatus according to claim 12, wherein the nanobubble-containing water discharge means and the micro / nanobubble generation means are activated when a signal indicating that the signal is received. A high-concentration liquid treatment means for treating the liquid preset as a high-concentration liquid containing the hardly decomposable compound at a high concentration by a combustion method or a supercritical method;
The treatment according to any one of claims 2 to 13, wherein the treatment tank introduces the liquid set in advance as a low concentration liquid containing the hardly decomposable compound at a low concentration. apparatus. The micro-nano bubble generating means is
A helical flow path for converting the first gas into a helical flow;
15. A mushroom-like impactor structure that generates micro-nano bubbles in nanobubble-containing water using the first gas that has passed through the spiral flow path. The processing apparatus according to item 1.   The processing apparatus according to claim 1, wherein the micro-nano bubble generating means generates micro-nano bubbles having a diameter of 0.5 μm to 3 μm in nanobubble-containing water.   The process according to any one of claims 1 to 16, 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 processing apparatus according to claim 1, wherein the hardly decomposable compound is an organic fluorine compound.   The organic fluorine compound is at least one organic fluorine selected from the group consisting of perfluorooctanesulfonic acid, perfluorooctanoic acid, perfluoroalkylsulfonic acid, perfluorooctanesulfonic acid fluoride, and perfluorooctanesulfonic acid fluoride derivatives. The processing apparatus according to claim 18, wherein the processing apparatus is a compound. The said nano bubble containing water discharge means is equipped with following 1) -4), The processing apparatus in any one of Claims 1-19 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. 4th gas shear part which produces nano bubble 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;
21. The processing apparatus according to claim 20, 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 21, 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.   23. The processing apparatus according to claim 21, wherein the supply gas is taken into the first gas shearing section after the output of the pump reaches a maximum value.   23. The processing apparatus according to claim 21, 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 21-24 characterized by the above-mentioned. The processing apparatus of Claim 1.   The processing apparatus according to any one of claims 20 to 25, wherein the supply gas contains ozone gas. The cross section inside the first gas shearing part is oval or perfect circle,
27. The processing apparatus according to claim 20, wherein two or more grooves are provided on the inner surface of the first gas shearing portion. The depth of the groove is 0.3 mm to 0.6 mm,
28. The processing apparatus according to claim 27, 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 20 to 28, 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.   30. The processing apparatus according to claim 20, wherein a thickness of the partition wall of the first gas shearing part is 6 mm to 12 mm.   The above-mentioned hardly decomposable compound is used in a photoresist process at the time of manufacturing a semiconductor, used in a photomask process at the time of manufacturing a liquid crystal, or contained in an antireflection film used in a photo process at the time of manufacturing a semiconductor, The processing apparatus according to any one of claims 1 to 30, wherein the processing apparatus is any one of those used in a desmear processing step when manufacturing a printed circuit board. A nanobubble-containing water discharge step for discharging nanobubble-containing water into the treatment tank;
A fluid containing a hardly decomposable compound, comprising: a micro / nano bubble generating step for generating micro / nano bubbles containing a first gas containing a hardly decomposable compound in the nanobubble-containing water in the treatment tank. Processing method for processing.   33. The processing method according to claim 32, wherein in the nanobubble-containing water discharging step, nanobubble-containing water is produced using a liquid containing a hardly decomposable compound and discharged into the processing tank.

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