JP5112231B2 - Processing apparatus and processing method - Google Patents

Description

  The present invention relates to a processing apparatus and a processing method for processing a liquid and a gas 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 an 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.

  Furthermore, the treatment by the combustion method and the supercritical method has a problem that the construction cost and the running cost are high. In addition to the above method, it is also possible to treat wastewater or irrigation water by an activated carbon adsorption method. However, activated carbon adsorbs all organic matter and breaks through if the treated material contains organic matter. The activated carbon needs to be replaced frequently. As a result, there is a problem that the running cost becomes high.

  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 when generated. 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 a surface-active action and a 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, in the liquid, 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; 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 ozone gas produced by an ozone generator and 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. Specifically, the conventional method using a bubble has a problem that a hardly decomposable compound cannot be decomposed.

  In addition, waste liquid discharged from an apparatus that uses a hardly decomposable compound, such as a semiconductor manufacturing apparatus, has been collected and decomposed in a waste liquid treatment apparatus installed at a location away from the apparatus. Therefore, the impurities in the waste liquid to be treated are increased, and the reaction efficiency between the bubbles and the hardly decomposable compound is lowered, so that the hardly decomposable compound cannot be sufficiently decomposed.

  Further, in recent years, for example, gases containing persistent compounds used in semiconductor factories or liquid crystal factories (for example, various PFC (perfluorocarbon) gases) have been regarded as one of the causes of global warming. It is also an important issue to reduce the hardly decomposable compounds.

  The present invention has been made in view of the above problems, and its purpose is a processing technique capable of easily and efficiently removing a hardly decomposable compound contained in a liquid and a gas discharged from a factory or the like. 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. In other words,
1) Dividing a liquid containing a hardly decomposable compound into a high concentration waste liquid containing a higher concentration of the hardly decomposable compound and a low concentration waste liquid (liquid) containing a lower concentration of the hardly decomposable compound, The waste liquid is treated by a conventional combustion method, etc., and gasified (second gas) by efficiently decomposing the hardly-decomposable compound in the low-concentration waste liquid using nanobubbles and containing the hardly-decomposable compound Processing with a gas (first gas) of
2) When low-concentration waste liquid is treated with nanobubbles in the presence of activated carbon, the decomposition of the hardly decomposable compound proceeds efficiently due to the oxidizing power of nanobubbles and the catalytic action of activated carbon.
3) By decomposing the hardly decomposable compound in the low-concentration waste liquid, it becomes a compound containing PFC (perfluorocarbon) having a lower carbon number,
4) When the activated carbon present in the treatment tank into which the liquid has been introduced is agitated with strong aeration, a part of the activated carbon is crushed into crushed fine activated carbon, and nanobubbles are discharged while maintaining the crushed fine activated carbon in the liquid at a high concentration. By doing so, the catalytic action of crushed fine activated carbon and the oxidation action of nanobubbles increase synergistically, and the decomposition efficiency of the hardly decomposable compound is improved,
5) When nanobubbles are discharged into the liquid, the nanobubble-containing water becomes partially mist-like, and this mist-like nanobubble-containing water is introduced into an apparatus for decomposing the first gas and the second gas. What can be done.

In order to solve the above problems, a processing apparatus according to the present invention is a processing apparatus for processing a liquid and a first gas, which is introduced from the outside of the apparatus and contains a hardly decomposable compound. Liquid treatment means for treating the liquid, second gas generated by treating the liquid, and gas treatment means for treating the first gas, wherein the liquid treatment means contains activated carbon inside. The nanobubble-containing water is mist-like by having a treatment tank into which the liquid is introduced, nanobubble-containing water discharge means for discharging nanobubble-containing water into the treatment tank, and pumping gas into the treatment tank a gas pumping mechanism to has a, the gas processing means, the first gas and the gas mixing means for mixing said second gas containing the mist of nano bubble-containing water generated in the treatment tank When Pyrolyzer, catalytic cracker, plasma decomposition unit, or burner system including a combustion decomposition apparatus, a mixed gas decomposing means for decomposing a mixed gas containing the mist of nano bubble-containing water that has been mixed by the gas mixing means It is characterized by having.

In order to solve the above-described problems, a processing method according to the present invention treats a liquid and a first gas, which are introduced from outside the own apparatus and contain a hardly decomposable compound , using the processing apparatus according to the present invention. a processing method for, by pumping the introducing step, the nanobubble-containing water discharge step of discharging nanobubbles containing water to the treatment tank, a gas into the processing bath for introducing the liquid into said processing bath The gas mixing step of mixing the second gas containing the mist-like nanobubble-containing water generated in the gas pumping step , and the first gas, by making the nanobubble-containing water mist-like decomposing the mixed gas containing the mist of nano bubble-containing water that has been mixed in the gas mixing step, the thermal decomposition apparatus, catalytic cracker, plasma decomposition unit, or by the burner type combustion cracker It is characterized in that it comprises a physical mixing gas decomposition treatment step.

According to the said structure, the processing apparatus which concerns on this invention is equipped with the liquid processing means which processes the liquid containing a hardly decomposable compound, and the gas processing means which processes the 1st gas containing a hardly decomposable compound. Yes. Thus, for example, waste liquid containing a hardly decomposable compound discharged from a semiconductor manufacturing apparatus or the like is processed, and at the same time, waste gas containing a hardly decomposable compound discharged from other than the apparatus is processed at a semiconductor manufacturing factory. Can do. Thus, in the processing apparatus according to the present invention, since the waste liquid and the waste gas are processed in one apparatus, the cost is low and the efficiency is high. And in the thermal decomposition apparatus, since the mixed gas of 1st gas and 2nd gas is processed with high temperature heat, decomposition | disassembly of mixed gas is accelerated | stimulated and it can decompose | disassemble efficiently. Further, since the mixed gas is processed by electric heating using a catalyst in the catalyst decomposition apparatus, the mixed gas can be reasonably decomposed even at a relatively low temperature. Moreover, since the mixed gas is processed with plasma in the plasma decomposition apparatus, the hardly decomposable compound in the mixed gas can be efficiently decomposed with plasma. Furthermore, in the burner type combustion decomposition apparatus, since the mixed gas is processed by the burner type combustion, the hardly decomposable compound in the mixed gas can be efficiently decomposed by the burner type combustion. And if gas is pumped in the processing tank in which nanobubble containing water exists with a gas pumping mechanism, nanobubble containing water will become mist-like. This mist-like nanobubble-containing water is transferred together with the second gas to the subsequent mixed gas decomposition treatment means. Usually, an apparatus for decomposing a gas containing a hardly decomposable compound such as PFC needs to supply water during the treatment. However, in the processing apparatus according to the present invention, since water containing mist-like nanobubbles is mixed with the second gas and transferred to the mixed gas decomposition processing means, it is not necessary to supply water. Therefore, the operation can be simplified.

  Moreover, the processing apparatus which concerns on this invention is equipped with the processing tank which has activated carbon inside, and the nano bubble containing water discharge means which discharges nano bubble containing water in this processing tank. Thereby, the hardly decomposable compound can be sufficiently decomposed and rendered harmless. That is, perfluorooctane sulfonic acid (PFOS), which is an example of a hardly decomposable compound, perfluorooctanoic acid (PFOA), or perfluorocarbon (PFC) which is a decomposition product thereof is a compound containing carbon and fluorine, The bond between these carbon and fluorine is very strong. In order to render such a hardly decomposable compound harmless, a strong bond between carbon and fluorine must be decomposed.

  Therefore, in the treatment apparatus according to the present invention, the catalytic action of the activated carbon and the nanobubbles are provided by including a treatment tank having activated carbon inside and a nanobubble-containing water discharge means for discharging the nanobubble-containing water into the treatment tank. A strong bond between carbon and fluorine can be decomposed by a synergistic effect with the oxidation action.

  Moreover, according to the processing method which concerns on this invention, there can exist an effect equivalent to the processing apparatus which concerns on this invention.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the said gas mixing means has a mushroom-like collision body structure.

  According to the said structure, the 1st gas containing a hardly decomposable compound and the 2nd gas generated by processing the liquid containing a hardly decomposable compound can fully be mixed. Thereby, the mixed gas decomposition processing means can reliably decompose the mixed gas of the first gas and the second gas.

  In the processing apparatus according to the present invention, the hardly decomposable compound contained in the liquid is preferably an organic fluorine compound.

  According to the said structure, the organic fluorine compound with a strong coupling | bonding between carbon and a fluorine can be decomposed | disassembled efficiently and detoxified.

  Such an organic fluorine compound is at least one selected from the group consisting of perfluorooctane sulfonic acid, perfluorooctanoic acid, perfluoroalkyl sulfonic acid, perfluorooctane sulfonic acid fluoride, and perfluorooctane sulfonic acid fluoride derivatives. One organic fluorine compound is preferred. If the organic fluorine compound is selected from the above group, it can be efficiently decomposed and rendered harmless.

  In the processing apparatus according to the present invention, it is preferable that the hardly decomposable compound contained in the first gas contains perfluorocarbon.

  According to the above configuration, the hardly decomposable perfluorocarbon, which is one of the environmental pollutants, can be rendered harmless and processed efficiently.

Moreover, the processing apparatus which concerns on this invention WHEREIN: The said processing tank is a tank which accommodates the said liquid, Comprising: The 1st processing tank which has the said activated carbon, The 2nd processing tank which accommodates the said 2nd gas it is preferable to provide.

According to the above configuration, the second gas generated from the hardly decomposable compound decomposed in the first treatment tank can be transferred to the second treatment tank .

Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the said gas pumping mechanism makes the activated carbon in a said 1st processing tank flow arbitrarily.

According to the above configuration, for example, when the concentration of the hardly decomposable compound in the liquid is relatively high, the flow rate of the activated carbon can be increased by increasing the number of revolutions of the electric motor equipped with the gas pumping mechanism. . Thus, the process according to the density | concentration of a hardly decomposable compound can be performed by adjusting the flow rate of activated carbon.

  In the processing apparatus according to the present invention, the activated carbon preferably includes granular activated carbon and crushed fine activated carbon.

  According to the said structure, a hardly decomposable compound can be decomposed | disassembled efficiently according to the catalytic action by the refined | pulverized fine activated carbon.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the said crushing fine activated carbon is contained 100g / L or more with respect to the volume of a said 1st processing tank.

  According to the said structure, a hardly decomposable compound can be decompose | disassembled still more efficiently by the effective catalytic action of the crushing fine activated carbon.

  Moreover, in the treatment apparatus according to the present invention, the first treatment tank further includes a separation means for separating the activated carbon from the mixed solution containing the nanobubble-containing water discharged by the nanobubble-containing water discharge means and the activated carbon. It is preferable to provide.

  According to the said structure, it can prevent that activated carbon is attracted | sucked by the nano bubble containing water discharge means. That is, the liquid containing nanobubbles discharged from the nanobubble-containing water discharging means is mixed with activated carbon introduced into the first treatment tank, and after the hardly decomposable compound is decomposed, the nanobubble-containing water discharging means is passed through. And return to the storage tank storing the liquid. At this time, by separating the activated carbon contained in the liquid by the separating means, the nanobubble-containing water discharging means can continue the smooth operation.

  Further, even when crushed fine activated carbon obtained by refining activated carbon is used, smooth operation of the nanobubble-containing water discharge means can be maintained by separation by the separation means.

  In the processing apparatus according to the present invention, the liquid processing means further includes a sending means for sending the second gas to the gas mixing means, and the gas processing means is decomposed by the mixed gas decomposition processing means. It is preferable that an impurity removing unit for removing impurities in the gas is further provided, and the liquid processing unit and the gas processing unit are controlled to operate in this order by the sequence control unit.

  According to the above configuration, at the same time when the processing is started, the sequence control means automatically controls the processing devices so as to sequentially operate. Therefore, the decomposition process can be performed easily and efficiently.

  In the processing apparatus according to the present invention, the sequence control means may operate the liquid processing means and the gas processing means in this order when the liquid is discharged from the apparatus using the hardly decomposable compound. preferable.

  According to the above configuration, when the liquid is discharged from the apparatus using the hardly decomposable compound, the sequence control means sequentially operates the processing apparatus, so that the operation is performed only when necessary, and energy can be saved.

  Further, in the processing apparatus according to the present invention, the sequence control unit is configured to open a cleaning water supply valve and a cleaning water discharge valve for cleaning the hardly decomposable compound in the apparatus using the hardly decomposable compound. When the signal indicating this is received, the liquid processing means and the gas processing means are preferably operated in this order.

  According to the above configuration, when the sequence control unit receives a signal indicating that the supply valve and the discharge valve are opened, the processing devices are sequentially operated. Therefore, the operation is performed only when necessary, and energy can be saved.

Further, in the processing apparatus according to the present invention, the liquid processing means, the raw water tank for storing the liquid, a transfer means for transferring the liquid to the treatment tank from the raw water tank, the liquid in the raw water tank It is preferable to further include a heater for heating.

  According to the said structure, the temperature of a liquid can be raised. Thereby, in a liquid processing means, decomposition | disassembly of the hardly decomposable compound in a liquid can be accelerated | stimulated.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable to provide the large sized activated carbon with a volume larger than the said activated carbon in the said raw | natural water tank.

  According to the said structure, the oxidation effect | action of a nano bubble can be heightened by the catalytic action of large sized activated carbon. Furthermore, the hard-to-decompose compound can be effectively decomposed by once adsorbing the hard-to-decompose compound in the liquid to the large-sized activated carbon.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the said nano bubble containing water discharge means is equipped with following 1) -3).

1) A first gas shearing section that mixes and shears the liquid and a third gas to produce microbubble-containing water. 2) A second gas shear that further shears the microbubble-containing water to produce nanobubble-containing water. Part 3) Third gas shear part for further shearing the nanobubble-containing water to produce nanobubble-containing water containing a large amount of nanobubbles According to the above configuration, a large amount of nanobubbles with strong oxidizing power are generated to generate a hardly decomposable compound Can be efficiently decomposed.

  Moreover, the processing apparatus which concerns on this invention WHEREIN: It is preferable that the said 3rd gas contains ozone gas.

  According to the said structure, since the nanobubble containing ozone gas is produced, a hardly decomposable compound can be oxidatively decomposed more strongly.

  The processing apparatus according to the present invention preferably further includes a gas amount adjusting means for supplying the third gas to the first gas shearing portion at a rate of 1.2 liters / minute or less. .

  According to the said structure, the ratio of the nanobubble in nanobubble containing water increases. Therefore, the hardly decomposable compound can be oxidatively decomposed more strongly.

Further, in the processing apparatus according to the present invention, the internal cross section of the first gas shearing part is an ellipse or a perfect circle,
It is preferable that two or more grooves are provided on the inner surface of the first gas shearing portion.

  According to the said structure, the 3rd gas supplied to a 1st gas shearing part can be sheared stably. Thereby, a large amount of microbubbles can be produced.

  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 the said structure, the 3rd gas supplied to a 1st gas shearing part can be sheared stably and a microbubble can be produced in large quantities.

  In the processing apparatus according to the present invention, in the first gas shearing section, the liquid is supplied through the first pipe, and the microbubble-containing water is discharged through the second pipe. It is preferable that the area in the cross section of the lumen of the pipe is larger than the area in the cross section of the lumen of the second pipe.

  According to the said structure, the 3rd gas supplied to a 1st gas shearing part can be sheared stably and a microbubble can be produced in large quantities.

In the processing apparatus according to the present invention, the first gas shearing section further includes a pump for mixing the third gas and the liquid and transferring the mixed gas to the processing tank, The gas 3 is preferably taken in after the time when the output of the pump reaches the maximum value.

  According to the above configuration, cavitation caused by the presence of air in the liquid can be prevented, and damage to the pump can be prevented.

Moreover, the processing apparatus which concerns on this invention WHEREIN: The said 1st gas shear part is further equipped with the pump for mixing the said 3rd gas and liquid, and transferring to the said processing tank, The 3rd into the said pump is carried out. The gas uptake is preferably performed after 60 seconds from the start of the operation of the pump.

  According to the above configuration, the third gas is taken in after 60 seconds set as a safety condition in which cavitation does not occur, so that damage to the pump can be reliably prevented.

  Further, in the processing apparatus according to the present invention, the third gas is supplied to the inside of the first gas shearing part via a third pipe, and the third pipe is connected to the inside of the first gas shearing part. It is preferable to be connected to the first gas shearing portion so as to form an angle of 18 degrees with respect to the side surface.

  According to the said structure, the 3rd gas supplied to a 1st gas shearing part can be sheared stably and a microbubble can be produced in large quantities.

  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.

  According to the said structure, the kinetic energy in a 1st gas shear part is not escaped outside. Therefore, the third gas supplied to the first gas shearing section can be sheared stably and efficiently, and a large amount of microbubbles can be produced.

  Moreover, the processing apparatus according to the present invention preferably includes a waste liquid processing means for further processing the waste liquid after the liquid is processed by the liquid processing means.

  According to the said structure, the waste liquid containing the ion generated by decomposing | disassembling the liquid containing a hardly decomposable compound can be further processed.

  In the processing method according to the present invention, 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 used in a photo process at the time of manufacturing a semiconductor. It is preferable that it is what is contained in a film | membrane or what is used in the desmear process process at the time of printed circuit board manufacture.

  According to the above configuration, the liquid and gas containing the hardly decomposable compound discharged from the semiconductor manufacturing factory, the liquid crystal manufacturing factory, or the printed circuit board manufacturing factory are decomposed, whereby the hardly decomposable compound that is an environmental pollutant is obtained. It can be detoxified.

The processing apparatus according to the present invention is a processing apparatus for processing a liquid and a first gas, which is introduced from the outside of the apparatus and contains a hardly decomposable compound, and processes the liquid. And a second gas generated by processing the liquid, and a gas processing means for processing the first gas, the liquid processing means having activated carbon inside, and the liquid is A treatment tank to be introduced; nanobubble-containing water discharge means for discharging nanobubble-containing water into the treatment tank; and a gas-feeding mechanism that makes the nanobubble-containing water mist by pumping gas into the treatment tank. comprises a, the gas processing means, a gas mixing means for mixing said second gas containing the mist of nano bubble-containing water generated in the first gas and the treatment tank, pyrolyzer, Catalyst Device, a plasma decomposition unit, or burner system including a combustion decomposition apparatus, since a mixed gas decomposing means for decomposing a mixed gas containing the mist of nano bubble-containing water that has been mixed by the gas mixing means, It is possible to provide a treatment technique capable of easily and efficiently removing a hardly decomposable compound contained in a liquid and a gas discharged from a factory or the like.

[Processing apparatus according to the present invention]
A processing apparatus according to the present invention is a processing apparatus for processing a liquid containing a hardly decomposable compound and a first gas containing a hardly decomposable compound, and includes a liquid processing means for processing the liquid, and a liquid. Gas treatment means for treating the second gas generated by the treatment and the first gas, the liquid treatment means having activated carbon inside, a treatment tank into which the liquid is introduced, and a treatment tank A nanobubble-containing water discharging means for discharging nanobubble-containing water therein, and the gas processing means includes a gas mixing means for mixing the first gas and the second gas, and a mixture mixed by the gas mixing means. What is necessary is just to provide the mixed gas decomposition processing means which decomposes | disassembles gas.

  The liquid containing the hardly decomposable compound processed by the processing apparatus according to the present invention is not particularly limited, and examples thereof 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 which concerns on this invention.

  Moreover, although the hard-to-decompose compound contained in the said liquid is not specifically limited, For example, an organic fluorine compound may be contained. Examples of the organic fluorine compound include perfluorooctanesulfonic acid, perfluorooctanoic acid, perfluoroalkylsulfonic acid, perfluorooctanesulfonic acid fluoride, and perfluorooctanesulfonic acid fluoride derivatives. If the hardly decomposable compound to be treated by the treatment apparatus of the present invention is the above-mentioned organic fluorine compound, a strong bond between carbon and fluorine can be efficiently decomposed.

  Such a liquid containing an organic fluorine compound is generally discharged as a waste liquid in a photoresist process during semiconductor manufacturing, a photomask process during liquid crystal manufacturing, or a desmear treatment process during printed circuit board manufacturing. Moreover, the liquid containing an organic fluorine compound may be discharged | emitted as waste liquid containing the antireflection film used in the photo process at the time of semiconductor manufacture, for example.

  Further, the hardly decomposable compound contained in the first gas and the second gas is not particularly limited, and may contain the hardly decomposable compound contained in the liquid described above. Fluorocarbons can be included.

  The first gas includes, for example, gas discharged from various apparatuses other than the apparatus that discharges the waste liquid to be processed by the processing apparatus of the present invention in the semiconductor factory. The second gas includes, for example, a gas generated by decomposing a hardly decomposable compound in the liquid processed in the processing apparatus of the present invention.

  Although the installation location of the processing apparatus according to the present invention is not particularly limited, for example, it is adjacent to a semiconductor manufacturing apparatus that discharges a waste liquid containing a hardly decomposable compound (for example, an organic fluorine compound) and connected to the semiconductor manufacturing apparatus. Good. Moreover, it is also possible to connect and use it with the apparatus which discharges | emits the waste liquid containing another hardly decomposable compound.

  Next, a specific configuration of the processing apparatus according to the present invention will be described in detail in the following embodiments.

[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 treatment apparatus according to the present invention connected to a semiconductor manufacturing apparatus 1. As shown in FIG. 1, the processing apparatus according to this embodiment mainly includes a liquid processing unit (liquid processing means) 20, a PFC gas mixing apparatus (gas mixing means) 32, and a PFC gas decomposition apparatus (mixed gas decomposition processing). Means) 33.

  First, steps until a liquid containing a hardly decomposable compound discharged from the semiconductor manufacturing apparatus 1 (hereinafter also referred to as “a hardly decomposable compound containing liquid”) is introduced into the liquid processing unit 20 will be described. . The processing apparatus according to this embodiment is installed on the semiconductor manufacturing apparatus 1 side. Thereby, for example, it becomes easy to operate the processing apparatus 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 can be a facility that is linked by transmitting and receiving signals.

  A mode in which the processing apparatus according to the present embodiment and the semiconductor manufacturing apparatus 1 are interlocked by transmitting and receiving signals will be described below. In this embodiment, the semiconductor manufacturing apparatus 1 supplies an organofluorine compound-containing liquid pipe 3 that supplies a receiving container 43 with a hardly decomposable compound-containing liquid (resist liquid, antireflection film liquid, etc.) for processing the processing object 2. And an organic fluorine compound-containing waste liquid discharge valve 58 for opening and closing the organic fluorine compound-containing liquid discharge pipe 60. The semiconductor manufacturing apparatus 1 also supplies a cleaning ultrapure water supply valve (cleaning water supply valve) 57 that opens and closes the cleaning ultrapure water pipe 4 for supplying cleaning ultrapure water for cleaning the processing object 2. And a cleaning ultrapure water discharge valve (cleaning water discharge valve) 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 set in advance as a low concentration liquid containing an organic fluorine compound at a low concentration, and is processed by the liquid processing unit 20 described later. More specifically, the semiconductor manufacturing apparatus 1 transmits a signal indicating that the cleaning ultrapure water discharge valve 59 is opened to the sequencer (sequence control means) 53, and the sequencer 53 receives the signal in advance. It can be identified that a liquid set as a low concentration liquid is introduced. In addition, the liquid containing the hardly decomposable compound to be processed by the processing apparatus according to the present embodiment refers to a liquid set as a low concentration liquid.

  Thus, according to the processing apparatus and processing method which concern on this embodiment, the low concentration liquid containing a low concentration hardly decomposable compound is processed using nanobubble and activated carbon, and a high concentration hardly decomposable compound is included. Since it is processed separately from the high-concentration liquid, it is possible to appropriately treat the liquid to be treated according to the concentration of the hardly-decomposable compound, and decompose the hardly-decomposable compound efficiently at a low cost. It is possible. In addition, by treating the liquid to be treated according to the concentration of the hardly decomposable compound, it is possible to directly treat the liquid containing the hardly decomposable compound discharged from the apparatus using the hardly decomposable compound. Yes, it is possible to treat the hardly decomposable compound in the vicinity of the apparatus. As a result, waste that is difficult to transfer, such as gas discharged from an apparatus that uses a hardly decomposable compound, can be treated successfully.

  As described above, in the present invention, whether to set a liquid containing a hardly decomposable compound such as an organic fluorine compound as a high concentration liquid or a low concentration liquid in advance, as in washing ultrapure water or the like, It may be set depending on whether or not a liquid-diluting liquid is further introduced, but is not limited to this. For example, the concentration of a liquid containing a hardly decomposable substance is manually measured, set to either a high-concentration liquid or a low-concentration liquid based on the measurement result, and the liquid set as the low-concentration liquid is introduced into the processing apparatus. 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 is transferred to the high-concentration waste liquid tank 45 through the organic fluorine compound-containing liquid discharge pipe 60. The cleaning ultrapure water discharge pipe 61 is connected to a low concentration waste liquid tank (raw water tank) 5 of the liquid processing unit 20, and the low concentration liquid is supplied to the low concentration waste liquid tank 5 through the cleaning ultrapure water discharge pipe 61. It is transferred to.

  An organic fluorine compound-containing liquid supply valve 56 and an organic fluorine compound-containing waste liquid discharge valve 58 of the semiconductor manufacturing apparatus 1 to which an inlet valve 73 provided in the organic fluorine compound-containing liquid discharge pipe 60 is transmitted via the signal line 44 are provided. When a signal indicating that it is open is received, the inlet valve 73 is opened, and the high-concentration liquid is introduced into the high-concentration waste liquid tank 45.

  On the other hand, when the cleaning ultrapure water supply valve 57 and the cleaning ultrapure water discharge valve 59 are opened, the low concentration liquid is introduced into the low concentration waste liquid tank 5 through the cleaning ultrapure water discharge pipe 61. A signal indicating that the cleaning ultrapure water supply valve 57 and the cleaning ultrapure water discharge valve 59 are open is transmitted to the sequencer 53 of the liquid processing unit 20 through the signal line 44, and the sequencer 53 that has received the signal You may control so that the nano bubble containing water discharge part (nano bubble containing water discharge means) 54, the blower (gas pumping mechanism) 23, and the exhaust fan (sending means) 41 operate | move sequentially. Alternatively, after the low-concentration liquid is introduced into the low-concentration waste liquid tank 5, or simultaneously with the introduction, the nanobubble-containing water discharge unit 54, the blower 23, and the exhaust fan 41 may be controlled to operate sequentially. Furthermore, at the same time as the low-concentration liquid is discharged from the semiconductor manufacturing apparatus 1, the nanobubble-containing water discharge unit 54, the blower 23, and the exhaust fan 41 may be controlled to operate sequentially by the sequencer 53.

  The opening / closing 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 were previously installed in the semiconductor manufacturing apparatus 1. It is set by the sequencer 53 and is controlled according to this condition. In other words, a pipe from which liquid is discharged is determined by a preset valve opening / closing condition, and is processed in the liquid processing unit 20 to which the pipe is connected.

(High-concentration liquid processing means)
The high-concentration liquid processing means includes a dedicated container A50 in which the introduction of the high-concentration liquid is controlled by opening and closing the inlet valve 73, the high-concentration waste liquid tank 45, the waste liquid pipe 46 for transferring the high-concentration liquid, the transfer pump 47, and 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 high-concentration liquid is treated by transporting the dedicated container to an incinerator or the like that disposes of the waste liquid, and incinerating at a combustion temperature of 1000 ° C. or higher, for example.

(Liquid processing unit 20)
The liquid processing unit 20 includes a liquid decomposition apparatus (processing tank) 19, a low-concentration waste liquid tank 5, a nanobubble-containing water discharge unit 54, and a sequencer 53. The liquid decomposition apparatus 19 includes a lower liquid treatment unit (first treatment tank) 22 that decomposes a hardly decomposable compound in a low-concentration liquid with nanobubbles and activated carbon, and a hardly decomposable compound decomposed in the lower liquid treatment unit 22. And an upper gas storage unit (second processing tank) 21 that stores the generated decomposition product gas 52 (second gas). Below, the lower liquid processing part 22 and the upper gas accommodating part 21 are each demonstrated.

(Lower liquid processing unit 22)
In this embodiment, the low-concentration liquid transferred from the semiconductor manufacturing apparatus 1 and stored in the low-concentration waste liquid tank 5 is introduced into the lower liquid processing unit 22 that is also the nanobubble generation tank 55 through the nanobubble-containing water discharge unit 54. . The nanobubble-containing water discharge unit 54 uses the low-concentration liquid transferred from the low-concentration waste liquid tank 5 to produce nanobubble-containing water and discharges the nanobubble-containing water to the lower liquid processing unit 22.

  Thus, the nanobubble-containing water discharge unit 54 discharges the low-concentration liquid containing nanobubbles as the nanobubble stream 30 to the lower liquid processing unit 22. Then, radicals are generated by the nanobubbles in the lower liquid processing unit 22, and the hardly decomposable compound in the low-concentration liquid is oxidatively decomposed by the radicals. For example, PFOS, PFOA, and the like are known to be stable substances, but these substances can be oxidatively decomposed by the treatment apparatus of this embodiment.

  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, the strong bond between carbon and fluorine is decomposed, and the decomposition product is gasified. 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 lower liquid processing part 22, activated carbon 26 is flowing. In the present embodiment, “Kuraray Coal (registered trademark)” (product of Kuraray Chemical Co., Ltd.), which is granular activated carbon, was used as the activated carbon 26. The low-concentration liquid containing nanobubbles mixes with the activated carbon 26 in the lower liquid processing unit 22. When the low concentration liquid is treated with nanobubbles in the presence of the activated carbon 26, the inventors improve the generation rate of the decomposition gas 52 as compared with the case where the low concentration liquid is treated only with the nanobubbles. I found.

  That is, it has been found that when a low-concentration liquid is treated with nanobubbles in the presence of activated carbon 26, the decomposition of the organic fluorine compound proceeds efficiently due to the oxidizing power of nanobubbles and the catalytic action of activated carbon 26. Therefore, in the lower liquid processing unit 22, the hardly decomposable compound in the low-concentration liquid is efficiently decomposed by the oxidation action of the nanobubbles and the catalytic action of the activated carbon 26. In particular, by increasing the concentration of the activated carbon 26 that flows into the lower liquid processing unit 22, the catalytic action by the activated carbon 26 is improved, so that the organic fluorine compound can be decomposed more efficiently.

  The present inventors have also found that aeration of a low-concentration liquid promotes decomposition of the hardly decomposable compound in the low-concentration liquid. That is, the lower liquid processing unit 22 is provided with an air diffusion pipe 28 that is discharged from the blower 23 and discharges air through the air pipe 24. The low concentration liquid in the lower liquid processing unit 22 is aerated by the air discharged from the air diffuser 28. The decomposition product gas 52 generated by the decomposition is removed together with the aerated air from the liquid phase of the low-concentration liquid and the vicinity of the liquid surface, thereby promoting the decomposition of the hardly decomposable compound.

Moreover, since the specific gravity of the activated carbon 26 in the lower liquid processing unit 22 is greater than 1, if the air flow in the lower liquid processing unit 22 is weak, the activated carbon 26 settles on the bottom of the lower liquid processing unit 22. For this reason, it is necessary to aerate so that the activated carbon 26 does not settle. The amount of air necessary for aeration to such an extent that the activated carbon 26 does not settle is, for example, 50 m ³ / hour / m ³ or more per volume of the lower liquid processing unit 22. By aeration with such an air amount, the activated carbon 26 flows without being settled, and at the same time, the decomposition product gas 52 of the organic fluorine compound in the low-concentration liquid can be reliably moved to the liquid surface and removed. .

  Furthermore, the lower liquid processing unit 22 is aerated by the air discharged from the diffuser tube 28, whereby the activated carbon 26 in the lower liquid processing unit 22 is agitated with strong aeration, and a portion of the activated carbon 26 is crushed fine activated carbon. 62 occurs. The present inventors further improve the catalytic action of the activated carbon 26 by the crushed fine activated carbon 62 generated in this way, and further improve the decomposition efficiency of the hardly decomposable compound by a synergistic effect with the oxidizing power of the nanobubbles. I also found out. The content of the crushed fine activated carbon 62 is preferably 100 g / L or more with respect to the volume of the nanobubble generation tank 55.

  In the lower liquid treatment part 22, treated water that has been treated with nanobubbles and activated carbon 26 and decomposed with a hardly decomposable compound is discharged through a primary treated water drain pipe 70. A part of the treated water treated in the lower liquid treatment unit 22 is returned to the low concentration waste liquid tank 5 through the distribution pipe 14. A filter 68 and a screen 69, which are separation means for separating activated carbon contained in the treated water, are disposed near the treated water discharge port (not shown) connected to the primary treated water drain pipe 70 in the lower liquid treatment unit 22. Is provided. Further, a filter portion 16 including a filter 17 and a screen 18 is provided in the vicinity of a treated water drain (not shown) connected to the distribution pipe 14.

  The filters 17 and 68 are respectively disposed closer to the treated water discharge port, and the screens 18 and 69 are disposed so as to overlap the filter 17 or 68, respectively. The screens 18 and 69 separate the activated carbon 26 having a relatively large size, and the filters 17 and 68 separate the finer crushed fine activated carbon 62. Thereby, the activated carbon 26 and the crushed fine activated carbon 62 are sufficiently separated from the treated water, and the activated carbon 26 and the crushed fine activated carbon 62 are prevented from flowing out from the lower liquid treatment unit 22. The activated carbon 26 and the crushed fine activated carbon 62 deposited on the filters 17 and 68 and the screens 18 and 69 are air-washed by the bubbles 27 discharged from the air diffuser 28 and flow in the lower liquid processing unit 22.

  In this 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. In addition, outlets 63 and 67 for exchanging and maintaining the filters 17 and 68 and the screens 18 and 69 are provided at both ends of the upper part of the lower liquid processing unit 22.

  The distribution pipe 14 that connects the lower liquid processing unit 22 and the low concentration waste liquid tank 5 is provided with flanges 13 and 15 that increase the degree of freedom in designing the distribution pipe 14. Water is transferred to the low concentration waste liquid tank 5. At this time, the treated water transferred from the lower liquid treatment unit 22 to the low-concentration waste liquid tank 5 contains nanobubbles. Since the activated carbon 26 and the crushed fine activated carbon 62 are removed from the treated water, a clogging phenomenon does not occur when the treated water is discharged again from the nanobubble-containing water discharge section 54 to the lower liquid processing section 22. Thus, the treated water treated in the lower liquid treatment unit 22 circulates between the lower liquid treatment unit 22 and the low-concentration waste liquid tank 5 and is supplied with nanobubble-containing water. Further, the activated carbon 26 and the crushed fine activated carbon 62 stay in the lower liquid processing unit 22 without being discharged, so that the resolution of the organic fluorine compound by these catalytic actions can be maintained.

  Here, as the blower 23, it is preferable to use a blower capable of controlling the rotation speed of the electric motor so that the inverter can be operated. By controlling the rotational speed of the electric motor, it is possible to change the flow state of the activated carbon 26 and the crushed fine activated carbon 62 in the lower liquid processing unit 22. Deposition can be prevented.

  The specific configuration of the nanobubble generation tank 55 is not particularly limited, and a known water tank can be used as appropriate. In addition, it is preferable that the nano bubble generation tank 55 is provided with the inclined part 25 which comprises the taper shape which tapers toward a bottom part. According to the said structure, the low concentration liquid in the lower liquid process part 22 can be stirred more effectively only by the discharge pressure of nanobubble content water. As a result, the oxidative decomposition reaction of the hardly decomposable compound contained in the low-concentration liquid can be further promoted. The angle formed between the bottom surface of the lower liquid processing unit 22 and the inclined portion 25 is not particularly limited, but is preferably, for example, 30 degrees to 60 degrees, more preferably 40 degrees to 50 degrees, and 45 degrees. Most preferably.

(Nanobubble-containing water discharge part 54)
Next, the nanobubble-containing water discharge unit 54 will be described.

  The nanobubble-containing water discharge section 54 includes a waste liquid pipe (first pipe, transfer means) 6, a first gas shearing section 8 having a gas-liquid mixing circulation pump (pump) 7, a waste liquid pipe (second pipe) 9, and a second gas. A shearing part 10, an electric needle valve (gas amount adjusting means) 11, an air pipe (third pipe) 12, and a third gas shearing part 29 are provided.

  A waste liquid pipe 6 and a waste liquid pipe 9 are connected to the first gas shearing portion 8. The waste liquid pipe 6 is connected to the low-concentration waste liquid tank 5, and the liquid is supplied to the first gas shearing part 8 via the waste liquid pipe 6 and to the first gas shearing part 8 via the air pipe 12. Gas (third gas) is supplied. 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 processed in the low concentration liquid discharged from the semiconductor manufacturing apparatus 1 or stored in the low concentration waste liquid tank 5 or the low concentration liquid and the lower liquid processing unit 22. Further, it may be a mixed liquid with a processing liquid circulating between the lower liquid processing unit 22 and the low concentration waste liquid tank 5. Thereby, the liquid processing part 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 air 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 supply of the low-concentration liquid into the first gas shearing unit 8 is performed 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, the operation of the gas-liquid mixing circulation pump 7 is started to introduce the low-concentration liquid into the first gas shearing portion 8 and stir the low-concentration liquid. 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 1.2 liters / minute 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 an air pipe 12. When the air pipe 12 is connected to the first gas shearing part 8, the connection position of the air pipe 12 on the first gas shearing part 8, the connection angle of the air pipe 12 with respect to the first gas shearing part 8, etc. are not particularly limited.

  For example, the air 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 at an angle. In other words, when considering the locality at the connection location of the air pipe 12, the air pipe 12 forms an angle of 18 degrees with respect to the moving direction of the mixture of the gas and the low-concentration 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 low-concentration liquid is rotated at an extremely high speed to form a negative pressure portion, and gas is introduced into the negative pressure portion. The gas is efficiently sheared by the difference in rotational speed between the gas and the low-concentration 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 low-concentration liquid.

  In the first gas shearing process, the pressure of the mixture of the gas and the low-concentration liquid is controlled hydrodynamically in the first gas shearing section 8 using the gas-liquid mixing circulation pump 7, and the negative pressure section Gas is inhaled. In addition, the “negative pressure part” intends a region where the pressure in the mixture of the gas and the low-concentration liquid is smaller than the surroundings. 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 low-concentration 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 multiphase swirl | vortex flow which consists of the low concentration 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 low-concentration 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 multiphase swirl is rotated while further cutting and crushing the microbubbles. In addition, the said cutting | disconnection and grinding | pulverization arises by the difference in the rotational speed of the gas-liquid two-phase fluid in the inside and outside of the exit of the 1st gas shearing part 8. FIG. 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. That is, the microbubble-containing water can be produced by pumping the low-concentration liquid and the gas by using the gas-liquid mixing / circulation pump 7 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 low concentration liquid at high speed, a 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, the generation of the swirling turbulence of the mixture of the low-concentration liquid and the gas in the first gas shearing portion 8 can be controlled, so that many fine microbubbles can be generated, Eventually, many nanobubbles can be generated.

  Further, a low concentration liquid is supplied to the first gas shearing portion 8 via the waste liquid pipe 6, and microbubble-containing water is discharged via the waste liquid pipe 9. At this time, the area of the cross section of the lumen of the waste liquid pipe 6 for supplying the low-concentration liquid is preferably larger than the area of the cross section of the lumen of the waste liquid 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 29 can further be provided as needed. If the 3rd gas shearing part 29 is provided, while the magnitude | size of the nanobubble produced by the 2nd gas shearing part 10 can be made further smaller, the quantity of nanobubble can be increased.

  Microbubble-containing water is pumped from the first gas shearing portion 8 to the second gas shearing portion 10 and further to the third gas shearing portion 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 and further to the third gas shearing portion 29 via a pipe, the direction in which the microbubble-containing water is pumped It is preferable that the diameter of the pipe decreases gradually or stepwise. 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 and the 3rd 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 and the third gas shearing portion 29 is preferably an elliptical shape, and most preferably a perfect circle. According to the above configuration, since the resistance (friction) of the inner surfaces of the second gas shearing portion 10 and the third gas shearing portion 29 is small, the microbubble-containing water can be swirled at a high speed and the microbubble-containing water can be efficiently used. It can shear well 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 and the third 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 part 10 and the third gas shearing part 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 section 10 and the third gas shearing section 29. As a result, nanobubbles can be stably generated by the second gas shearing portion 10 and the third gas shearing portion 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, and the 3rd gas shearing part 29 mentioned above, For example, using a commercially available thing is used. Is possible. For example, it is possible to use a Bavidas HYK type manufactured by Kyowa Kikai Co., Ltd., but is not limited to this.

  The nanobubble-containing water thus produced becomes a nanobubble flow 30 and is discharged into the lower liquid processing unit 22. And in the lower liquid processing part 22, the oxidative decomposition reaction of a hardly decomposable compound advances. The decomposition product containing perfluorocarbon (PFC) generated by the reaction is gasified and diffused into the upper gas storage unit 21.

(Upper gas accommodating part 21)
Next, in the upper gas storage unit 21, the decomposed gas 52 diffused inside and the nanobubble-containing water mist (mist-like nanobubble-containing water) 76 are mixed. Here, the decomposition product gas 52 and the nanobubble-containing water mist 76 are mixed for the following reason.

  In order to decompose PFC, which is a hardly decomposable compound contained in the decomposition product gas 52, water is required for the decomposition reaction as shown in the following reaction formula.

CF ₄ + 2H ₂ O → 4HF + CO ₂
C ₂ F ₆ + 3H ₂ O → 6HF + CO ₂ + CO
Therefore, in order to decompose PFC in the PFC gas decomposition apparatus 33 described later, usually water must be supplied. However, in the present invention, when air is discharged from the air diffuser 28 into the nanobubble generating tank 55, it is possible to generate the nanobubble-containing water mist 76 by adjusting the amount of aerated air with the blower 23. Therefore, by mixing the nanobubble-containing water mist 76 with the decomposition product gas 52 and transferring it through the PFC gas mixing device 32, it can be used as water necessary for the decomposition reaction in the PFC gas decomposition device 33.

  The decomposition product gas 52 thus mixed with the nanobubble-containing water mist 76 in the upper gas storage unit 21 is exhausted to the PFC gas mixing device 32 through the exhaust fan 41. Below, the gas processing using the gas processing means which concerns on this Embodiment is demonstrated.

(Gas treatment means)
In the PFC gas mixing device 32 according to the present embodiment, the gas containing the hardly decomposable compound (first gas) and the decomposition product gas 52 generated by the processing in the liquid processing unit 20 are mixed. In the present embodiment, the gas containing the hardly decomposable compound is an in-plant PFC gas 31 generated from an etching apparatus (not shown) in the semiconductor factory. The in-plant PFC gas 31 generated from the etching apparatus is introduced into the PFC gas mixing apparatus 32 through the PFC gas pipe 36.

  Although it does not specifically limit as the PFC gas mixing apparatus 32, For example, the line mixer by an OHR fluid engineering laboratory can be used. The structure of the PFC gas mixing device 32 is not particularly limited, but preferably has a mushroom-like collision body structure. The mushroom-like impactor structure means an impactor structure composed of a part that causes a swirl flow in the gas and a part that has many protrusions (called mushroom-like cutters) that finely crush the gas. If the PFC gas mixing device 32 has a mushroom-like collision body structure, the in-plant PFC gas 31 and the decomposition product gas 52 introduced into the PFC gas mixing device 32 can be sufficiently mixed. This is advantageous in that the hardly decomposable compound in the gas can be sufficiently decomposed in the decomposition reaction performed by the PFC gas decomposition apparatus 33 described later. Next, a gas mixing process using the PFC gas mixing device 32 will be described.

  In the PFC gas mixing device 32, first, a swirling flow of the PFC gas is generated, and then the PFC gas is introduced into a portion having a large number of protrusions that are finely crushed and further refined and mixed.

  The PFC gas mixing device 32 includes a gas refining mechanism (not shown) for refining the hardly decomposable compounds in the factory PFC gas 31 and the decomposition product gas 52 to 0.5 μm or more and 3 μm or less. It is more preferable. Thereby, it becomes easy to make a difficult-to-decompose compound refine | miniaturize and fully mix, and to advance the decomposition reaction in the PFC gas decomposition apparatus 33 smoothly.

  Next, the mixed gas of the in-factory PFC gas 31 and the decomposition product gas 52 mixed in the PFC gas mixing device 32 is introduced into the PFC gas decomposition device 33 through the PFC gas mixing pipe 37.

  The PFC gas decomposition apparatus 33 is not particularly limited, and for example, a PFC gas thermal decomposition apparatus, a PFC gas catalyst decomposition apparatus, a PFC gas plasma decomposition apparatus, and a PFC gas combustion decomposition apparatus may be provided. Here, the mixed gas decomposition process using the PFC gas decomposition apparatus 33 will be described below.

In the PFC gas decomposition apparatus 33, first, various PFC gases (CF ₄ , C ₂ F ₆ , NF ₃ , SF ₆ ) contained in the mixed gas introduced from the PFC gas mixing apparatus 32 are decomposed in the presence of H ₂ O. To do. The reaction formula is shown below.

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
Further, as described above, it is preferable that the decomposition product gas 52 contains nanobubble-containing water mist 76 (H ₂ O). According to the above configuration, water (H ₂ O) usually needs to be supplied for the decomposition reaction of the mixed gas in the PFC gas decomposition apparatus 33, but the nanobubble-containing water mist 76 (H ₂ O) is added to the decomposition product gas 52. The mist can be used as water (H ₂ O) necessary for the decomposition reaction.

Here, the nanobubble-containing water mist 76 in the PFC gas decomposing apparatus 33 works particularly effectively, for example, when 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 (H ₂ O) is present is at a high temperature, the PFC decomposition reaction is promoted and the decomposition proceeds easily. As such a temperature, it is preferable that it is 850 to 1,400 degreeC, for example.

  In this Embodiment, although the PFC gas mixing apparatus 32 and the PFC gas decomposition | disassembly apparatus showed the aspect integrated with the processing apparatus, it is not limited to this.

  The hardly decomposable compound in the mixed gas to be decomposed in the PFC gas decomposition apparatus 33 becomes a decomposition product such as hydrogen fluoride (HF), carbon monoxide, carbon dioxide, and nitrogen oxide after decomposition. Among these, since hydrogen fluoride has toxicity, it is necessary to detoxify before discharging the gas containing hydrogen fluoride into the atmosphere. Therefore, the processing apparatus according to the present embodiment 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 pipe. The scrubber 34 is not particularly limited, and for example, a water scrubber using water as cleaning water and an alkali scrubber using an alkaline aqueous solution as cleaning water can be used. As a method for removing impurities using such a scrubber 34, for example, a method using a wet packed tower scrubber TRS type manufactured by Seiko Koki Co., Ltd. may be mentioned.

  In the present embodiment, the cleaning water used in the impurity removal method is not particularly limited, and for example, water or alkaline water can be used. For example, hydrogen fluoride in the gas comes into gas-liquid contact with the cleaning water as a liquid and dissolves as fluoride ions in the cleaning water as a liquid, thereby being removed from the gas and detoxified. Then, the hydrogen fluoride in the hydrogen fluoride-containing gas is removed by the scrubber 34 and discharged as a waste liquid together with the cleaning water, and the gas from which the hydrogen fluoride has been removed is discharged out of the processing apparatus as a processing exhaust gas 39.

  In the processing apparatus according to the present embodiment, the signal line 44 is also provided in the PFC gas decomposition processing apparatus 33 and the scrubber 34. Therefore, the PFC gas decomposition processing device 33 and the scrubber 34 are also operated under the control of the sequencer 53.

  The processing apparatus according to the present embodiment further includes a slaked lime coagulation sedimentation wastewater treatment apparatus (waste liquid treatment means) 35 for treating the waste liquid discharged from the scrubber 34 and the lower liquid treatment unit 22. The slaked lime coagulation sedimentation wastewater treatment device 35 is connected to a scrubber 34 by a drainage pipe 42, and a waste liquid containing fluorine discharged from the scrubber 34 is introduced. Further, the slaked lime coagulation sedimentation wastewater treatment device 35 is also connected to the nanobubble generation tank 55 by the primary treated water drainage pipe 70, and the waste liquid discharged from the nanobubble generation tank 55 is introduced.

  The slaked lime coagulation sedimentation wastewater treatment device 35 includes, for example, a coagulation tank to which slaked lime and a polymer coagulant are added, and drainage configured from a precipitation tank for precipitating the formed calcium fluoride flocs (aggregates). A processing apparatus can be used, slaked lime (calcium hydroxide) is added as an inorganic flocculant, and a polymer flocculant is added as an organic flocculant. In the present embodiment, as the polymer flocculant that can be added to the slaked lime flocculent sedimentation wastewater treatment device 35, for example, a polyacrylamide organic flocculant (Cliff Rock of Kurita Kogyo Co., Ltd.) is employed.

  In the slaked lime coagulation sedimentation wastewater treatment device 35, first, the above-described inorganic coagulant and organic coagulant are added to the waste liquid introduced from the scrubber 34 and the lower liquid treatment unit 22. As a result, the fluorine contained in the waste liquid discharged from the scrubber 34 reacts with calcium to form calcium fluoride and precipitate. In addition, the waste liquid discharged from the lower liquid processing unit 22 includes sulfate ions generated when a hardly decomposable compound (for example, PEOS) is decomposed, and the ions are added by adding an inorganic flocculant and an organic flocculant. It reacts with calcium in slaked lime to form calcium sulfate and is rendered harmless. The waste liquid thus rendered harmless is discharged from the secondary treated water drain pipe 71.

  As described above, according to the processing apparatus according to the present embodiment, the liquid processing unit 20 processes the liquid containing the hardly decomposable compound, and the nanobubble oxidizing action and the activated carbon catalytic action in the hardly decomposable compound. Breaks down the strong bond between carbon and fluorine. Further, the gas generated by the treatment of the liquid and the gas containing the hardly decomposable compound introduced from the outside of the apparatus are mixed to decompose the hardly decomposable compound in the gas. Thereby, it is possible to efficiently decompose the hardly decomposable compound in the liquid and gas discharged from the semiconductor device or the like.

[Second Embodiment]
A second embodiment of the processing apparatus 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 treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The second embodiment is different from the first embodiment except that a PFC gas thermal decomposition apparatus 72 is used as the PFC gas decomposition apparatus. Therefore, in the present embodiment, only differences from the first embodiment will be described, and the same member numbers are used for members having the same configuration.

  In the present embodiment, a PFC gas thermal decomposition apparatus 72 (manufactured by Kanken Techno Co., Ltd.) used as a PFC gas decomposition apparatus includes a ceramic heater (not shown). In general, when the temperature during the reaction is increased, the decomposition of the hardly decomposable compound is promoted. Therefore, by increasing the temperature in the PFC gas thermal decomposition apparatus 72 with a ceramic heater, the decomposition efficiency of the hardly decomposable compound is improved. In addition to the ceramic heater, an electric heater can be used as a heating means in the PFC gas pyrolysis device 72.

  In the PFC gas thermal decomposition apparatus 72, first, the gas introduced from the PFC gas mixing apparatus 32 is introduced into a heating reaction section (not shown) and subjected to thermal decomposition treatment. The heating reaction section is composed of a cylindrical casing, a cleaning gas introduction pipe, and a heater. In addition, ceramics are mainly used for the material of the inner peripheral surface of the housing and the outer peripheral surface of the heater.

  The temperature raised by the ceramic heater varies depending on various conditions such as the type of perfluorocarbon contained in the hardly decomposable compound or the amount of gas introduced, but it is particularly preferably raised to 1,300 ° C. Thereby, the hardly decomposable compound in gas can be decomposed | disassembled efficiently.

[Third Embodiment]
A third embodiment of the processing apparatus according to the present invention will be described below with reference to FIG. FIG. 3 is a schematic diagram showing a third embodiment of the treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The third embodiment is different from the first embodiment except that a PFC gas catalyst decomposition device 74 is used as the PFC gas decomposition device.

  In the present embodiment, a PFC gas catalyst decomposition device 74 (manufactured by Hitachi, Ltd.) is used as the PFC gas decomposition device. In the PFC gas catalyst decomposing apparatus 74, a gas containing the hardly decomposable compound introduced into the apparatus is treated by electric heating using a catalyst.

  As the catalyst, for example, a Ni · Al catalyst or a Pd / Ni / Al catalyst can be used. As the electric heating means, for example, an electric furnace may be used.

  In the PFC gas catalyst decomposition apparatus 74, first, PFC gas contained in the gas introduced from the PFC gas mixing apparatus 32 is brought into contact with the catalyst in an electric furnace under electric heating. As a result, the PFC gas can be decomposed even at a relatively low temperature, for example, about 750 ° C. during the reaction. Note that the PFC gas catalyst decomposition apparatus 74 includes a high-performance catalyst containing a component that immediately absorbs hydrogen fluoride generated during decomposition.

[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 treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The fourth embodiment is different from the first embodiment except that a PFC gas plasma decomposition apparatus 75 is used as the PFC gas decomposition apparatus, and the other configuration is the same as that of the first embodiment.

  In the present embodiment, a PFC gas plasma decomposition apparatus 75 (manufactured by Taiyo Nippon Sanso Corporation) used as a PFC gas decomposition apparatus is a cavity resonator type apparatus using microwaves, although not shown, a pre-processing unit , A plasma generation unit, a reaction unit, and a gas cooler.

In the PFC gas plasma decomposition apparatus 75, first, PFC gas contained in the gas introduced from the PFC gas mixing apparatus 32 is decomposed by plasma, and H ₂ O or O ₂ is added thereto. These additions serve to prevent the once decomposed PFC gas from being combined again and convert it into a processable gas. As a result, the hardly decomposable compound in the gas can be efficiently decomposed.

[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 treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The fifth embodiment differs from the first embodiment only in that a PFC gas combustion decomposition apparatus 77 is used as the PFC gas decomposition apparatus, and the other configuration is the same as in the first embodiment.

  In the present embodiment, a PFC gas combustion decomposition apparatus 77 (manufactured by Taiyo Nippon Sanso Co., Ltd.) used as a PFC gas decomposition apparatus includes a burner as a 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, it is difficult to increase the temperature in the PFC gas combustion decomposition apparatus 77 by injecting fuel from the burner and increasing the temperature. The decomposition efficiency of the decomposable compound is improved.

  In the PFC gas combustion decomposition apparatus 77, first, the PFC gas introduced from the PFC gas mixing apparatus 32 is introduced into a combustion furnace (not shown), fuel and oxygen gas are blown and burned, and the PFC gas is converted into hydrogen fluoride. Disassemble until Then, the hydrogen fluoride is washed with washing water, and the hydrogen fluoride is transferred to the liquid phase.

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

[Sixth Embodiment]
A sixth embodiment of the processing apparatus 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 treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The sixth embodiment is the same as the first embodiment except that the heater 64 is provided in the low concentration waste liquid tank 5.

  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, when the temperature of the liquid rises, the decomposition of the compound is promoted. Therefore, the decomposition efficiency of the hardly decomposable compound is improved by treating the liquid with the raised temperature with nanobubbles and activated carbon in the lower liquid treatment unit 22. However, the temperature setting of the liquid varies depending on the type of the liquid substrate, the specifications of the nanobubble-containing water discharge unit 54, the amount of activated carbon 26 in the lower liquid processing unit 22, the amount of air discharged from the diffuser tube 28, and the like. Based on experimental data obtained in advance, it may be determined from a comprehensive viewpoint (energy saving, cost, decomposition performance, etc.).

[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 treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The seventh embodiment is the same as the first embodiment except that a large activated carbon storage container 66 filled with a large activated carbon 65 is provided in the low concentration waste liquid tank 5. ing.

  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 activated carbon 26 added to the nanobubble generating tank 55, so that the oxidizing action of nanobubbles is strengthened. be able to.

  That is, the activated carbon that acts as a catalyst has pores, and the large activated carbon 65 has pores as well. Since the large activated carbon 65 is large, the amount of the activated carbon to be filled greatly increases. As a result, the amount of activated carbon and the surface area of the activated carbon are greatly increased, and the catalytic action, that is, the oxidizing action can be enhanced. Therefore, the hardly decomposable compound can be efficiently decomposed.

  Further, by installing the large activated carbon 65 in the low concentration waste liquid tank 5, the hardly decomposable compound in the liquid may be once adsorbed on the large activated carbon 65.

[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 treatment apparatus according to the present invention connected to the semiconductor manufacturing apparatus 1. The eighth embodiment is configured in the same manner as the first embodiment except that the gas introduced to produce nanobubbles in the nanobubble-containing water discharge unit 54 is specified as ozone gas. ing.

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

  Based on FIG. 2, the processing apparatus which processes an organic fluorine compound (PFOS) containing water was produced.

In the processing apparatus used in this example, the capacity of the low concentration waste liquid tank 5 is 0.5 m ³ , the capacity of the upper gas storage unit 21 of the liquid decomposition apparatus 19 is about 1 m ³ , and the capacity of the lower liquid processing unit 22 is about 1 m. ^3. The capacity of the PFC gas mixing device 32 was 0.5 m ³ , the capacity of the PFC gas decomposition device 33 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, what has the 3.7kw gas-liquid mixing circulation pump 7 (HYK type by Kyowa Kikai Co., Ltd.) was used. Further, “lower activated carbon Kuraray Coal GW (for liquid phase) (registered trademark)” (manufactured by Kuraray Chemical Co., Ltd.) was introduced into the lower liquid processing unit 22.

  A low-concentration liquid containing a low-concentration hardly decomposable compound was introduced into the low-concentration waste liquid tank 5 of the treatment apparatus thus configured, and a series of facilities related to the treatment of the low-concentration liquid were all operated. The test operation was started, and the concentration of each compound in the liquid obtained from the low-concentration waste liquid tank 5 and the secondary treated water distribution pipe 71 after 12 days was compared. The results are shown in Table 1. In the measurement items in Table 1, the PFOS concentration was determined by LC / MS / MS method (liquid chromatograph-tandem mass spectrometer method), the total fluorine amount was determined by combustion ion chromatography, and the sulfate ion was determined by ion chromatography. It was measured.

  Next, the compound concentration in the processing gas 39 at the outlet of the scrubber 34 was measured. The results are shown in Table 2. In the measurement items in Table 2, the PFOS concentration and degradation product qualitative tests were measured by a gas chromatograph-mass spectrometer method.

  From the results shown in Tables 1 and 2, the following a) to c) 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 secondary treated water distribution pipe 71 was remarkably low, and the PFOS was reliably decomposed.

  b) Compared with the total fluorine amount and sulfate ion concentration in the liquid in the low concentration waste liquid tank 5, the total fluorine amount and sulfate ion concentration in the liquid obtained from the secondary treated water distribution pipe 71 are remarkably low. Was reliably disassembled.

  c) The concentration of PFOS in the processing gas 39 at the outlet of the scrubber 34 was remarkably low, and no decomposition products such as perfluorocarbon were detected, and the decomposition products in the processing gas 39 were reliably decomposed.

  As described above, according to the processing apparatus and the processing method according to the present embodiment, a low-concentration liquid containing a low-concentration hardly-decomposable compound is treated using nanobubbles and activated carbon, and a high-concentration hardly-decomposable compound is treated. Since it is processed separately from the high-concentration liquid it contains, it is possible to appropriately treat the liquid to be treated according to the concentration of the hardly-decomposable compound, and efficiently decompose the hardly-decomposable compound at low cost. Is possible.

  In addition, by treating the liquid to be treated according to the concentration of the hardly decomposable compound, it is possible to directly treat the liquid containing the hardly decomposable compound discharged from the apparatus using the hardly decomposable compound. Yes, it is possible to treat the hardly decomposable compound in the vicinity of the apparatus. As a result, the installation space for the processing apparatus can be reduced, and space saving can be realized.

  Furthermore, according to the processing apparatus and the processing method according to the present embodiment, there is an effect that a large amount of radicals are generated by nanobubbles, and the hardly decomposable compound can be strongly oxidatively decomposed by the radicals.

  In addition, the decomposition product generated by oxidative decomposition is gasified, but since the gasified decomposition product can be effectively removed, it is possible to prevent the progress of the oxidative decomposition reaction from being suppressed. Play.

  In addition, although the removed decomposition product contains hardly decomposable PFC gas, it can be decomposed by mixing with other PFC gas generated in the semiconductor factory, for example, so that the PFC gas can be efficiently decomposed at low cost. There exists an effect that it can process.

  It should be noted that the present invention is not limited to the configurations described above, and various modifications are possible within the scope shown in the claims, and technical means disclosed in different embodiments and examples are appropriately combined. The obtained embodiments and examples are also included in the technical scope of the present invention.

  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 device. It is a schematic diagram which shows 2nd Embodiment of the processing apparatus based on this invention connected with the semiconductor device. It is a schematic diagram which shows 3rd Embodiment of the processing apparatus based on this invention connected with the semiconductor device. It is a schematic diagram which shows 4th Embodiment of the processing apparatus based on this invention connected with the semiconductor device. It is a schematic diagram which shows 5th Embodiment of the processing apparatus based on this invention connected with the semiconductor device. It is a schematic diagram which shows 6th Embodiment of the processing apparatus based on this invention connected with the semiconductor device. It is a schematic diagram which shows 7th Embodiment of the processing apparatus based on this invention connected with the semiconductor device. It is a schematic diagram which shows 8th Embodiment of the processing apparatus based on this invention connected with the semiconductor device.

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 Waste liquid piping (first piping, transfer means)
7 Gas-liquid mixing circulation pump (pump)
8 First gas shearing part 9 Waste liquid piping (second piping)
10 Second gas shearing part 11 Electric needle valve (gas amount adjusting means)
12 Air piping (third piping)
13 Flange 14 Distribution piping 15 Flange 16 Filter part 17 Filter (separation means)
18 screen (separation means)
19 Liquid decomposition equipment (treatment tank)
20 Liquid processing part (liquid processing means)
21 Upper gas container (second treatment tank)
22 Lower liquid processing section (first processing tank)
23 Blower (gas pumping mechanism)
24 Air piping 25 Inclined portion 26 Activated carbon 27 Bubbles 28 Air diffuser tube 29 Third gas shearing portion 30 Nano bubble flow 32 PFC gas mixing device (gas mixing means)
31 Factory PFC gas (first gas)
33 PFC gas decomposition equipment (mixed gas decomposition treatment means)
34 Scrubber (impurity removal means)
35 Slaked lime coagulation sedimentation wastewater treatment equipment (waste liquid treatment means)
36 PFC gas piping 37 PFC gas mixing piping 38 PFC gas decomposition piping 39 Treatment exhaust gas 40 Exhaust duct 41 Exhaust fan (outlet means)
43 Receiving container 44 Signal line 45 High-concentration waste liquid tank 46 Waste liquid piping 47 Transfer pump 48 Valve 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 Nano-bubble generation tank 56 Electric fluorine compound-containing liquid electric valve 57 Cleaning ultrapure water electric valve (cleaning water supply valve)
58 Electric fluorine compound-containing waste liquid electric valve 59 Cleaning ultrapure water waste liquid electric valve (wash water discharge valve)
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 pyrolysis unit 73 Inlet valve 74 PFC gas catalytic decomposition unit 75 PFC gas plasma decomposition unit 76 Nano bubble-containing water mist 77 PFC gas combustion decomposition unit

Claims (28)

A processing apparatus for processing a liquid and a first gas, which is introduced from outside the apparatus and contains a hardly decomposable compound,
Liquid processing means for processing the liquid;
A second gas generated by processing the liquid, and a gas processing means for processing the first gas,
The liquid processing means includes
A treatment tank having activated carbon therein and into which the liquid is introduced;
Nanobubble-containing water discharging means for discharging nanobubble-containing water into the treatment tank;
A gas-feeding mechanism that mists the nanobubble-containing water by pumping gas into the treatment tank, and
The gas processing means includes
Gas mixing means for mixing the first gas and the second gas containing the mist-like nanobubble-containing water generated in the treatment tank ;
A mixed gas decomposition treatment means comprising a thermal decomposition apparatus, a catalytic decomposition apparatus, a plasma decomposition apparatus, or a burner type combustion decomposition apparatus, which decomposes the mixed gas containing the mist-like nanobubble-containing water mixed by the gas mixing means; A processing apparatus comprising:   The processing apparatus according to claim 1, wherein the gas mixing means has a mushroom-like collision body structure. Persistent compounds the liquid is contained, the processing apparatus according to any one of claims 1 or 2, characterized in that the 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 3 , wherein the processing apparatus is a compound. The hardly decomposable compound first gas contains, the processing apparatus according to any one of claims 1 to 4, characterized in that it contains perfluorocarbons. It said processing tank claims, characterized in that it comprises a first treatment tank having the active carbon a tank for accommodating the liquid, and a second processing tank for accommodating the second gas The processing apparatus of any one of 1-5 . The processing apparatus according to claim 6 , wherein the gas pressure feeding mechanism allows the activated carbon in the first processing tank to flow arbitrarily. The processing apparatus according to claim 6 or 7 , wherein the activated carbon includes granular activated carbon and crushed fine activated carbon. The processing apparatus according to claim 8 , wherein the crushed fine activated carbon is contained in an amount of 100 g / L or more with respect to the volume of the first processing tank. The said 1st processing tank is further provided with the isolation | separation means which isolate | separates the said activated carbon from the mixed solution containing the nano bubble containing water and the said activated carbon which the said nano bubble containing water discharge means discharged. processing apparatus according to any one of 6-9. The liquid processing means further includes delivery means for delivering the second gas to the gas mixing means,
The gas treatment means further includes an impurity removal means for removing impurities in the gas decomposed by the mixed gas decomposition treatment means,
The liquid processing means and said gas processing means, the sequence control means, processing device according to any one of claims 1 to 10, characterized in that it is controlled to operate in this order. 12. The process according to claim 11 , wherein the sequence control unit operates the liquid processing unit and the gas processing unit in this order when the liquid is discharged from the apparatus using the hardly decomposable compound. apparatus. When the sequence control means receives a signal indicating that a supply valve for cleaning water for cleaning the nondegradable compound and a discharge valve for the cleaning water are opened in the apparatus using the nondegradable compound, The processing apparatus according to claim 11 or 12 , wherein the liquid processing means and the gas processing means are operated in this order. The liquid processing means includes
A raw water tank for storing the liquid;
And transfer means for transferring the liquid to the treatment tank from the raw water tank,
Processing apparatus according to any one of claims 1 to 12, characterized by further comprising a heater for heating the liquid in the raw water tank. The processing apparatus according to claim 14 , wherein the raw water tank includes large-sized activated carbon having a volume larger than that of the activated carbon. The said nano bubble containing water discharge means is provided with following 1) -3), The processing apparatus of any one of Claims 1-15 characterized by the above-mentioned.
1) A first gas shearing section that mixes and shears the liquid and a third gas to produce microbubble-containing water. 2) A second gas shear that further shears the microbubble-containing water to produce nanobubble-containing water. Part 3) A third gas shear part for further shearing the nanobubble-containing water to produce nanobubble-containing water containing a large amount of nanobubbles The processing apparatus according to claim 16 , wherein the third gas contains ozone gas. According to claim 16 or 17, characterized in that it further comprises a gas quantity adjusting means for supplying the third gas at 1.2 l / min or less with respect to the first gas shearing section Processing equipment. The cross section inside the first gas shearing part is elliptical or true circular,
The processing apparatus according to any one of claims 16 to 18 , wherein two or more grooves are provided on an inner surface of the first gas shearing portion. The depth of the groove is 0.3 mm to 0.6 mm,
The processing apparatus according to claim 19 , wherein the groove has a width of 0.8 mm or less. In the first gas shearing section, the liquid is supplied through the first pipe, and the microbubble-containing water is discharged through the second pipe.
The area of cross section of the lumen of the first pipe, the processing apparatus according to any one of claims 16 to 20, characterized in that larger than the area of the cross section of the lumen of the second pipe. The first gas shearing unit further includes a pump for mixing the third gas and the liquid and transferring them to the treatment tank,
The processing apparatus according to any one of claims 16 to 21 , wherein the third gas is taken into the pump after the time when the output of the pump reaches a maximum value. The first gas shearing unit further includes a pump for mixing the third gas and the liquid and transferring them to the treatment tank,
23. The processing apparatus according to claim 22 , wherein the third gas is taken into the pump after 60 seconds from the start of operation of the pump. The third gas is supplied into the first gas shearing section through a third pipe,
The third pipe is at an angle of 18 degrees with respect to the inner surface of the first gas shearing section, any of claims 16-23, characterized in that it is connected to the first gas shearing section The processing apparatus of Claim 1. The thickness of the first gas shearing section of the partition wall, the processing apparatus according to any one of claims 16 to 24, characterized in that it is 6 mm to 12 mm. The processing apparatus according to any one of claims 1 to 25 , further comprising a waste liquid processing means for further processing a waste liquid after the liquid is processed by the liquid processing means. 27. A treatment method for treating a liquid and a first gas, which is introduced from outside the own device and contains a hardly decomposable compound , using the treatment device according to any one of claims 1 to 26. ,
An introduction step of introducing the liquid to the treatment tank,
A nanobubble-containing water discharging step for discharging nanobubble-containing water into the treatment tank;
A gas pumping step for making the nanobubble-containing water mist by pumping gas into the treatment tank;
A gas mixing step of mixing the second gas containing the atomized nanobubble-containing water generated in the gas pumping step , and the first gas;
A mixed gas decomposition treatment step of decomposing the mixed gas containing the atomized nanobubble-containing water mixed in the gas mixing step with a thermal decomposition device, a catalytic decomposition device, a plasma decomposition device, or a burner type combustion decomposition device ; A processing method characterized by including. The above-mentioned hardly decomposable compound is used in a photoresist process at the time of semiconductor manufacture, used in a photomask process at the time of liquid crystal manufacture, contained in an antireflection film used in a photo process at the time of semiconductor manufacture, 28. The processing method according to claim 27 , wherein the processing method is used in a desmear processing step when manufacturing a printed circuit board.

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